CN101489941A

CN101489941A - Catalytically treating water contaminated with halogenated organic compounds

Info

Publication number: CN101489941A
Application number: CNA2006800507490A
Authority: CN
Inventors: B·伯科威茨; I·德罗尔
Original assignee: Yeda Research and Development Co Ltd
Current assignee: Yeda Research and Development Co Ltd
Priority date: 2005-11-10
Filing date: 2006-11-09
Publication date: 2009-07-22
Also published as: CN101466262B; CN101466262A

Abstract

The invention provides a catalytically treating groundwater (10), surface water, or above surface water, contaminated (12) with halogenated organic compounds being members of chlorotriazine, chloroacetanilide, or halogenated aliphatic, herbicide groups, and, halogen containing analogs and derivatives thereof. Method: exposing contaminated water to catalytic amount of electron transfer mediator (18) under reducing conditions, to decrease concentrations of halogenated organic compounds. System: at least one electron transfer mediator (18) contained in at least one (in-situ or/and ex-situ) unit (20), for exposing to contaminated water under reducing conditions. Exemplary electron transfer mediators are porphyrinogenic organometallic complexes, being metalloporphyrins, metallocorrins, or metallochlorins. Exemplary metalloporphyrins are a [TMPyP], [TP(OH)P], [TPP], or [TBSP], free base porphyrin complexed to a transition metal (cobalt, nickel, iron, zinc, or copper). Implemented according to homogeneous or/and heterogeneous catalysis, via batch or flow mode. Reducing conditions naturally exist, or/and are anthropogenically produced, in the contaminated water. The invention is applicable to in-situ groundwater permeable reactive barriers (PRBs) (22).

Description

The water of catalytic treatment contaminated with halogenated organic compounds

Invention field and background of invention

The present invention relates to pay close attention to environmental science and the technical field of handling or remedying the water of (remediate) contaminated with halogenated organic compounds, wherein said contaminated water is the form of underground water, the surface water, ground water or its combination.More particularly, the present invention relates to a kind of method and system thereof of water of catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.The weedicide of these halogenated organic compounds types is non-volatile particulate matter (almost whole) or liquid (part) down in room temperature and normal atmosphere, and it is removable and soluble in water in water under common Pollutant levels (for example ppb-ppm scope).The present invention is applicable to that (original position is or/and off normal (offing normal)) homogeneous phase is or/and heterogeneous catalyst is handled this contaminated water, described contaminated water is multiple different form, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its combination on the ground.

The problem of the water of the contaminated with halogenated organic compounds that is faced with:

In various dissimilar water pollutants, can prove halogenation in various forms of water (particularly chlorination) organic compound for the most common, generally (scope is wide), (for example the transformation period is a couple of days to 10 lastingly, 000 year), be proved dangerous or have the undesirable pollutent of danger (poisonous), described water is underground water (underground water zone for example for example, water reservoir or aqueous stratum), the surface water (river for example, the lake, the pond, pond or surface water water reservoir), water (water water reservoir on the ground for example on the ground, the source, ground or the supply of dwelling house or commercial potable water) or its combination.Many in the water of this form are the drinking water source or produce the drinking water source.Until later 1960s, many halogenations (particularly chlorination) organic compound also utilizes its high-performance to be used for various agricultural and commercial run except utilizing its advantages of higher stability and chemically-resistant and biology degradation property.Have recognized that now industrial these essential character have damaging influence to environment, that is to say to cause undesirable short-term and long-term health problem.

Because (human origin or synthetic) the halogenated organic compounds pollutent that artificially produces in environment confirmation maybe may confirm or the character and the feature of potentially dangerous (poisonous), therefore causes the concern that people are very big.Earthward with underground environment in the discharging these compounds cause the large-area surface water and groundwater pollution.Mainly taking up an area of ball based on underground water can be with about 95% the fact at fresh water source, groundwater pollution is a critical problem, and continue to drop into the improved and new technology that a large amount of effort comes development process or remedies the water of contaminated with halogenated organic compounds, wherein said contaminated water is underground water, the surface water, ground water or its array configuration.

Halogenation organic herbicide and concrete grouping thereof:

Weedicide typically refers to the material that is used to destroy plant (particularly weeds).Therefore, think that this material that destroys plant has weeding activity.As expected, there are various many dissimilar weedicides.For convenience's sake, and when discussing or describe weedicide or comprising or when relating to the various theme of weedicide, in order to set up certain type order, scientific community is with numerous weedicide classification and be grouped into various independent weedicide group, and wherein each weedicide group is determined by each weedicide member common universal performance or distinguishing characteristics at least a this weedicide group or character (for example chemical structure).

In many known weedicide groups, three kinds of well-known especially halogenation organic herbicide groups are: chlorotriazine weedicide group, chloro-acetanilide herbicide group and halogenation aliphatic series weedicide group, wherein universal performance or distinguishing characteristics or the character of each halogenation organic herbicide group by each halogenation organic herbicide member common chemical structure in this halogenation organic herbicide group is determined.Fig. 1,2 and 3 usefulness tabulars go out " common name ", chemical formula and the chemical abstracts service department (CAS) number of compound, and have represented the chemical structure of the known halogenation organic herbicide member of each in these the three kinds corresponding halogenation organic herbicide groups.Among these known halogenation organic herbicide members each also has other not too common chemical titles (for example by CAS and IUPAC name), though unlisted herein, these not too common chemical titles appear in disclosed chemical literature and relevant prior art.In the explanation hereinafter, in three kinds of halogenation organic herbicide groups of following exemplary description, provide other details of the chemical structure of relevant halogenation organic herbicide member, its halogen-containing analogue and halogen-containing derivative thereof.

As the chlorotriazine weedicide group of Fig. 1 definition and explanation be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein R ₁-R ₄Independently be selected from hydrogen atom [H] and organic substituent separately:

As the chloro-acetanilide herbicide group of Fig. 2 definition and explanation be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein R ₁-R ₄Independently be selected from hydrogen atom [H] and organic substituent separately:

As the halogenation aliphatic series weedicide group of Fig. 3 definition and explanation be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein n is 1-4, and A, B, R ' and R ＂ independently are selected from hydrogen atom [H] and organic substituent separately, wherein at least one is halogen atom (being fluorine [F], chlorine [Cl], bromine [Br] or iodine [I]) among A, B, R ' and the R ＂

A-(C-R′-R＂)n-B。

Application range of the present invention is specifically related to three kinds of halogenation organic herbicide groups of above-mentioned exemplary description and wherein halogenation organic herbicide member, its halogen-containing analogue, its halogen-containing derivative and combination thereof, these materials are the particular type or the kind of the halogenated organic compounds of wideer and more general kind, are focussed in particular on the environmental science and the technical field that are used to handle or remedy contaminated water.

Halogenation organic herbicide as problematic water pollutant:

Usually the halogenation organic herbicide for example comprises all halogenation organic herbicide members in three kinds of halogenation organic herbicide groups of above exemplary description (chlorating organic nitrogen-containing weedicide (CONH) particularly, for example be included in all the halogenation organic herbicide members in chlorotriazine weedicide group (particularly triazine, for example atrazine and cyanazine) and the chloro-acetanilide herbicide group (for example alachlor and metolachlor)) be the most widely used agricultural chemicals.That uses triazine halogenation organic herbicide is popular based on its weeding ratio, commercial burden with lack comparable surrogate.Common halogenation organic herbicide (particularly CONH) is usually used in before the emerging in the process of growth of various crops (for example corn, soybean and sugarcane) and the back weeds control of emerging, and becomes the whole integral part of modern agriculture circle.Environmental Defense (EPA) estimates that annual American National has 36000000 and 16000000 kilograms of atrazines and cyanazine to be scattered in [1] in the farmland respectively; The application and the atrazine of alachlor similar [2-4].

Usually halogenation organic herbicide (particularly CONH) and many degraded products thereof are non-volatile particulate matter (almost whole) or liquid (part), and be removable and soluble in water in water under common Pollutant levels (for example ppb-ppm scope).Many halogenation organic herbicides are atrazine for example, cyanazine and simazine (being included in the CONH (Fig. 1) in the chlorotriazine weedicide group) and alachlor and metolachlor (being included in the CONH (Fig. 2) in the chloro-acetanilide herbicide group) and degraded product (derivative that particularly comprises higher water movability halogen (particularly chlorine)) thereof are for general in various forms of water, lastingly, confirm or the undesirable pollutent of potentially dangerous (poisonous) that described water is underground water (underground water zone for example for example, water reservoir or aqueous stratum), the surface water (river for example, the lake, the pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its combination on the ground.Many in the water of this form are the drinking water source or produce the drinking water source.

Under the concentration of the greatest contamination thing content (MCL) that surpasses its EPA announcement, measure the halogenation organic herbicide [2,4,5] in the drinking water source.Owing to use the halogenation organic herbicide and subsequently halogenation organic herbicide and degraded product thereof run off from the farmland, large-area water contamination of heavy and the water-quality deterioration that therefore causes make needs the relevant halogenated organic compounds of research distribution (spreading all over), transmission (moving), consequence (for example relating to persistence, conversion or/and degrade), ecological risk and healthy effect of (in particular for the drinking water source or produce the water form of drinking water source) in water.

Wide coverage persistence in the underground water or the surface water of common halogenation organic herbicide (particularly CONH) and many degraded products thereof [for example 1,6-11].The research of United States Geological Survey (USGS) [6,7,12-14] shows that some parent CONH (particularly atrazine) last for several years in soil and river, and a plurality of CONH degraded product continues equally with removable.The transformation period of atrazine is about 125 days, and since atrazine can not easily be absorbed by soil particle or adsorb, easier to be mobile in sandy soil, make the further polluted water of atrazine.For example in the U.S., USGS has found atrazine in the phreatic research of 36 all river basins, and USGS estimates that the persistence of atrazine in dark lake can be above 10 years.For diethyl atrazine, atrazine degradation by-products similar discovery is arranged also, and have report [1] to claim the concentration of finding parent compound atrazine, alachlor and cyanazine in river, the Minnesota State once in a while to surpass its MCL.Well water exploration [for example 8] shows that many aqueous stratums are polluted by high-load CONH.

Owing to have CONH and a degraded product thereof in the underground water or the surface water, clearly indicating may be to health affected in many researchs [for example 8,9,11-14].Many CONH have acute under lower concentration and chronic toxicity [15-17], and usually known or suspect that these CONH are carcinogenic, mutagenesis is or/and teratogenesis [1,15-19].Some researchs [20-25] hint or explanation are used as the concrete CONH (for example atrazine) or/and the degraded product of internal secretion agent interfering and teratogen in Amphibians.In addition, find that the atrazine be exposed to low levels induces frog sexual abnormality [26-28].CONH studies show that to other of ecological influence the mixture of each CONH and multiple CONH and degraded product thereof as the internal secretion agent interfering of fish, for example cause influencing unfriendly the breeding of game fish (for example perch (Micropterus salmoides)).

In the U.S., the strict restriction atrazine since 1993, and limiting its content in tap water during the 1993-1995.Some countries of EU (European Union) particularly France, Denmark, Germany, Norway and Sweden have banned use of atrazine [26].Although these restrictions, regulations and ban are arranged, atrazine (only for being included in a kind of among numerous CONH in the halogenation organic herbicide more extensive and more generally kind) is still main dangerous water pollutant.In addition because conventional water treatment practice can not be removed solubility halogenation organic herbicide from pending thick water source usually, therefore the concentration of this weedicide in tap water can with the concentration identical [7,29-31] in thick water source.

In the lasting water pollutant of number of different types, although many halogenation organic herbicides are verified and may have environment and Health hazard, still have international applications widely at present, thereby present problem continues to exist.Main concern is a large amount of common halogenation organic herbicides (particularly CONH) and degraded product is present in or near various forms of water, described water is that the mankind are or/and the water source that animal directly or indirectly exposes or the source at this water source.

Handle or remedy phreatic problem:

After the halogenation organic herbicide is used in the farmland, finally, because rainwater is or/and the irrigated farmland, removable and solubility halogenation organic herbicide and possible initial degraded product dissolving thereof and transfer to and by ground and underground, and be distributed in various subterranean layers or the zone by diffusion, absorption and separating process usually heterogeneously.When arriving underground water (for example underground water zone, water reservoir or aqueous stratum), dissolving and transmission bigger pollutent region or the zone that can produce extension of these pollutents in underground water is called pollutent plumage (contaminant plume).Handle or remedy phreatic subject matter and be that these pollutent regions or zone (plumage) can be very difficult to the location, detect, characterize and handle; In groundwater environment, there is ununiformity usually; And long-term groundwater flow continuously needs pollutent and possible degraded product fully to remove from contaminated underground water.With river be flip-flop transition two weeks different be that the underground water residence time is 10-1000.

Handle or remedy the current techniques of the water of contaminated with halogenated organic compounds:

Exist various dissimilar prior art (method, material, composition, device and system) well-known and that use to handle or remedy the water of contaminated with halogenated organic compounds, described halogenated organic compounds for example is generally halogenation organic herbicide (particularly CONH) and degraded product thereof, and wherein said contaminated water is underground water, the surface water, ground water or its array configuration.Each concrete technology is a kind of based in principle, phenomenon, mechanism and the method for following primary categories mainly: (a) physics/physical chemistry, (b) biology, or (c) chemistry.The common ultimate aim of each water treatment or remedial technique is an original position or/and the concentration of the halogenated organic compounds pollutent of eliminating or be reduced at least danger in the contaminated water or potentially dangerous (poisonous) of offing normal.Below be the brief description of the above-mentioned sorting technique of the water that is used to handle or remedy contaminated with halogenated organic compounds and the selectivity example of prior art instruction.

(a) be used to handle or remedy the physics/physical chemistry technology of the water of contaminated with halogenated organic compounds:

Physics/physical chemistry the technology of water that is used to handle or remedy contaminated with halogenated organic compounds is based on phenomenon, mechanism and the method for utilizing physics or physical chemistry type, for example absorbs, adsorbs by filtering and remove halogenated organic compounds; Chemical depletion, the chemical bond of use temperature halogenated organic compounds or/and the extreme condition of pressure ruptures; Or/and photodissociation, wherein use the rupture chemical bond of halogenated organic compounds of UV (ultraviolet) line.Halogenated organic compounds is removed or is transferred to from contaminated water in another medium (for example strainer) by " physically " or " passing through physico-chemical process " or is converted, transforms or be degraded to not dangerous in contaminated water or/and the compound of not too dangerous (poisonous).

Use the example that filters the water of handling or remedy contaminated with halogenated organic compounds based on activated carbon filtration.Typical activated charcoal filter produces the highly porous and active material with the very high surface area that is used for absorb polluted matter by making derived from small bunch of the carbon atom of the particulate body form of the particle in any amount of various sources or powder size.Contaminated water is exposed to activated charcoal filter, during halogenated organic compounds Pollutants Diffusion and by charcoal absorption, on gac, concentrate, thereby from contaminated water, remove.After significantly accumulating on the gac, the pollutent that comprises the passivation carbon filter is removed from contaminated water at pollutent, and handles or wash or handle (regeneration) to remove pollutent and reactivate carbon to utilize again.Activated carbon filtration technology significant limitations is that the halogenated organic compounds pollutent only is transferred to carbon filter from contaminated water basically, and can not transform or disinfection for not dangerous or/and acceptable compound on the dangerous environment not too.In addition, the realization of this technology needs various resources (manpower and equipment) to remove and handle or regenerate and comprises the pollutent of passivation carbon filter.

Use chemical depletion to handle or remedy the example of water of contaminated with halogenated organic compounds based under the situation that does not have chemical reagent, use extreme or destructive temperature or/and pressure condition comes break chemical bonds, thus will be in the halogenated organic compounds in contaminated water conversion, transform or be degraded to not dangerous or/and the compound of dangerous (poisonous) not too.Have been proposed in this technology [32] of degraded atrazine under high temperature (150-200 ℃) and the high pressure (3.0-6.0MPa) (for being included in the exemplary CONH (figure I) in the chlorotriazine weedicide group).

The example that uses photodissociation to handle or remedy the water of contaminated with halogenated organic compounds is separated (and photochemical catalysis of particular type) method based on ultraviolet (UV) linear light.More particularly, shown as the metal oxide particle that will wherein comprise suspension (titanium dioxide [TiO for example ₂] or zinc oxide [ZnO]) the aqueous solution by the atrazine Contaminated soil when being exposed to ultraviolet ray, by the oxidisability photochemical catalysis with atrazine by the physico-chemical process modification, form various atrazine and transform and degraded product [33].Research photochemical catalysis water purifies the large-sized solar equipment [34] of (comprising the degraded atrazine).Several selected more recent research that relates to ultraviolet photodissociation (photochemical catalysis) halogenated organic compounds concentrates on: relatively atrazine is at Fe (ClO ₄) ₃The aqueous solution and TiO ₂The photodegradative kinetics of oxidisability [35] in the suspension; Porphyrin-phthalocyanine photochemical reaction the catalyzer [36] that is used for the photocatalytic degradation atrazine; Kinetics and mechanism [37,38] with ultraviolet photolysis atrazine on soil surface.

(b) be used to handle or remedy the biotechnology of the water of contaminated with halogenated organic compounds:

The biotechnology of water that is used to handle or remedy contaminated with halogenated organic compounds is based on phenomenon, mechanism and the method for utilizing biology (microbiology) type, relate to use biology organism (for example microorganism (microbes), microorganism (microorganisms), bacterium) by " biological method " will be in the conversion of the halogenated organic compounds in the contaminated water, transform or be degraded to not dangerous or/and the compound of danger (poisonous) not too.

Several dissimilar microorganisms can effectively be handled the water of contaminated with halogenated organic compounds.For example known anaerobic type microorganism is used to the CONH that degrades.Use the important advantage of microorganism to be that dehalogenation (particularly dechlorination) technology original position carries out, and compound is degraded fully usually, need to use the another kind of method intermediate degraded product of halogenated organic compounds of degrading thereby get rid of.But, using microbial technique to handle contaminated water significant limitations is, usually by change in water treatment procedure, particularly envrionment conditions (for example pH, temperature and nutrition supply) influences this technology strongly in long-term water treatment procedure, and possibility inactivation.

Change the limitation of envrionment conditions when using microorganism system to handle the water that is polluted by atrazine, for example " biological degradation and the bioremediation to atrazine in the waste water carried out many researchs by the atrazine Contaminated soil up to now in [39] statement such as Pranab.Pure culture microorganism has been used in these researchs of great majority, except indivedual mixt bacteria cultures that used.Pure culture bacterium is used the unique source of atrazine as carbon and/or nitrogen, but only issues first portion degraded and mineralising in seldom situation.Atrazine biodegradation rate and palliating degradation degree depend on pure culture bacterium type, whether have various exterior carbon and nitrogen source and concentration separately, carbon/nitrogen ratio, pH and moisture content.The pure culture bacterium of operation is the work of a trouble in the condition of the field of reality, and atrazine original position mineralising condition exists hardly.Mandelbaum etc. [40] find, at 200 independently in the bacterial classification, the mineralising of atrazine only could take place after will be many pure culture bacterial classifications mixing.”

The another kind of significant limitations of using microorganism system to handle the water of contaminated with halogenated organic compounds is that the high pollution substrate concentration can be poisonous to the contaminant degradation bacterium.For example show [41] in the dechlorination process of trieline (TCE) and vinylchlorid (VC), the no life intermediate materials of acetylene for forming, it suppresses biotransformation, conversion or the degraded of initial halogenated organic compounds pollutent.

(c) be used to handle or remedy the chemical technology of the water of contaminated with halogenated organic compounds:

The chemical technology of water that is used to handle or remedy contaminated with halogenated organic compounds is based on phenomenon, mechanism and the method for utilizing on-catalytic chemical reaction or (homogeneous phase or heterogeneous) catalyzed chemical reaction type, relate to use (inorganic) chemical reagent or/and organic " pass through chemical process " will be in the conversion of the halogenated organic compounds in the contaminated water, transform or be degraded to not dangerous or/and the compound of dangerous (poisonous) not too.

In the chemical technology of on-catalytic chemical reaction type, at least a chemical reagent in on-catalytic chemical reaction (being generally redox (redox) chemical reaction) with the principal reaction thing of halogenated organic compounds pollutent direct reaction (not using catalyzer), will be in the conversion of the halogenated organic compounds in the contaminated water, transform or be degraded to not dangerous or/and Wei Xian compound not too.In the chemical technology of homogeneous phase or heterogeneous catalyst chemical reaction type, at least a chemical reagent is participant, promotor or accelerator, be used as homogeneous phase or heterogeneous catalyst in the homogeneous phase that relates to the halogenated organic compounds pollutent or heterogeneous catalyst chemical reaction (being generally homogeneous phase or heterogeneous oxidation reduction (redox) catalyzed chemical reaction), halogenated organic compounds in contaminated water is used for changing, transform or degrades.

Herein for clear unambiguous purpose, prior art instruction of below introducing and theme of the present invention be the homogeneous catalysis chemical reaction be wherein said catalyzer (particularly for example electron transfer mediator) begin for not by another kind of material load, matrixization (matrixed), insert or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in the whole contaminated water.The heterogeneous catalyst chemical reaction be wherein said catalyzer (particularly for example electron transfer mediator) begin for by load, matrixization, insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material, be scattered in subsequently in (promptly being insoluble to) whole contaminated water.Usually begin the fixed catalyzer and become equally and be scattered in (promptly being insoluble to) whole contaminated water, still, parameter and condition according to the reality of given heterogeneous catalyst chemical reaction system can be partially soluble in the contaminated water at least.

Reductive dehalogenation:

The most of chemical technologies of water that are used to handle or remedy contaminated with halogenated organic compounds at present are based on on-catalytic or (homogeneous phase or heterogeneous) catalytic oxidation-reduction chemical reaction, phenomenon, mechanism and the method for reductive dehalogenation (being generally dechlorination) type, relate to use (organic or/and inorganic) chemical reagent and " pass through chemical process " and make halogenated organic compounds dehalogenation (dechlorination) in contaminated water.Usually, reductive dehalogenation relate to catalyzer (for example electron transfer mediator type catalyzer) do not exist or in the presence of, with many electronics (ne ^-) be transferred to electron acceptor(EA) from body electron donor(ED) or reductive agent, described electron donor(ED) or reductive agent be multiple organic or/and inorganic chemical and many possible organic or/and combinations of inorganic chemical (for example natural existence, originate from or by synthetic method derived from mineral substance, plant or biological agents), described electron acceptor(EA) is halogenation (being generally a chlorination) orgnic compound pollution thing ([R-X]; The X=halogen is generally chlorine [Cl]).The reductive dehalogenation chemical reaction is (on-catalytic or catalysis) hydrogenolysis form, its common flow process (not containing or contain catalyzer) chemical equation (1) expression, wherein Y ⁺Be proton [H ⁺] or any other positive charge atom or part:

R-X+ne ^-+Y ⁺→R-Y ⁺X ^- (1)

Be used for handling or remedying the photoreduction dehalogenation of the water of (light is remedied) contaminated with halogenated organic compounds:

Be used to handle or remedy the exemplary reductive dehalogenation of the first kind of water of contaminated with halogenated organic compounds based on vegetable chemistry.Fully studied and related to the chemical that uses aquatic or land plant or plant derivation and " pass through photochemical method " and make various different types of halogenated organic compounds dehalogenation (dechlorination) or " photodegradation " [for example 42-46] in the contaminated water as reductive dehalogenation (the being generally dechlorination) on-catalytic of the photochemistry type of body electron donor(ED) or reductive agent or catalytic oxidation-reduction chemical reaction.But, these researchs are not clearly or the relevant catalytic treatment of hint property ground instruction or remedy the water that (light is remedied) polluted by the halogenation organic herbicide, described halogenation organic herbicide is generally for example halogenation organic herbicide member, particularly chlorating organic nitrogen-containing weedicide (CONH) in three kinds of halogenation organic herbicide groups (Fig. 1,2 and 3) of above-mentioned exemplary description.

Be used to handle or remedy zero-valent metal (ZVM) reductive dehalogenation of the water of contaminated with halogenated organic compounds:

Be used to handle or remedy the exemplary reductive dehalogenation of second class of water of contaminated with halogenated organic compounds based on using metal element or zero-valent metal (ZVM).Zero-valent metal (ZVM) reductive dehalogenation (being generally dechlorination) technology usually based on do not exist at electron transfer mediator type catalyzer or in the presence of; the water of contaminated with halogenated organic compounds is exposed to (preferred nanometer size) particle that a large amount of metals are zero-valent state or/and the metal element particle of powdered, during with the pollutent conversion, transform or be degraded to not dangerous or/and not too Wei Xian compound or/and for example by adsorbing or/and depositing technology is fixed on the surface of metal particles.Usually for example adopting, the mode under reduction (anaerobism or anoxic) condition is exposed to the zero-valent metal particle with contaminated water; make that in contaminated water only pollutent is reduced by the zero-valent metal particle, and at contaminated water or/and near the uncontamination thing the intermediate at contaminated water (for example oxygen) do not reduced by the zero-valent metal particle.

Do not throw a flood of light on zero-valent metal (ZVM) reductive dehalogenation cutter reason really, but according to there not being or existing catalyzer, usually seem directly on the metallic surface or/and by some intermediates (catalyzer) bielectron takes place and shift, particularly be transferred to halogenated organic compounds pollutent ([R-X] as electron acceptor(EA) from body electron donor(ED) or reductive agent (oxidized) bielectron; The X=halogen is generally chlorine [Cl]), thus the halogenated organic compounds pollutent is reduced to the form of for example reducing [R-H], and this point is usually with chemical equation (2) expression, wherein Y ⁺Be proton [H ⁺] or any other positive charge atom or part:

R-X+M ⁰+Y ⁺→M ²⁺+R-Y+X ^- (2)

Though different elements or zero-valent metal (iron [Fe for example ⁰], cobalt [Co ⁰], nickel [Ni ⁰], copper [Cu ⁰] and zinc [Zn ⁰]) applicable, but Zero-valent Iron [Fe ⁰] (ZVI) be most commonly used to realize the ZVM technology.The known existing several years of zero-valent metal reductive dehalogenation method, still, generally speaking, only the use of ZVM (particularly ZVI) can be accepted as one of efficient manner that underground water remedies in the past ten years.The ZVI particle is cheap and be used for original position rationally and effectively or various types of groundwater pollutants of the catalytic reduction different concns of offing normal, and described groundwater pollutant for example is organic compound (for example halogenated organic compounds and degraded product thereof) and mineral compound (for example oxo-anions, metal and metal ion and radionuclide).

The prior art instruction [for example 47-54] of relevant ZVM technology is widely reported, is usually directed to use in the uncatalyzed reaction system Zero-valent Iron (ZVI) to make the dechlorination of chlorating organic solvent non-catalytic reduction, for example tetracol phenixin (CT) [C (Cl) ₄], Ethylene Dichloride (DCE) [C ₂H ₂Cl ₂], trieline (TCE) [C ₂HCl ₃], tetrachloroethylene (PCE) (zellon) [C ₂Cl ₄] etc., these are evident as, and environment pays close attention to.

Also there is the prior art instruction of relevant ZVM technology, relate to and in the uncatalyzed reaction system, use Zero-valent Iron (ZVI) to make in the aqueous solution (tertiary butyl azine (TBA), to take off sec.-propyl atrazine (DIA) and (CONH) member's non-catalytic reduction dechlorination of chlorination dimethoxy-triazine (CDMT) [57] as the exemplary chlorination organic nitrogen-containing weedicide atrazine [55,56] of chlorotriazine weedicide group (Fig. 1) and other triazine herbicides.

But, undeclared or relevant (homogeneous phase or the heterogeneous) catalytic treatment of hint of these prior aries or remedy the instruction of the water that is polluted by the halogenation organic herbicide, described halogenation organic herbicide is generally for example halogenation organic herbicide member, particularly chlorination organic nitrogen-containing weedicide (CONH) in three kinds of halogenation organic herbicide groups (Fig. 1,2 and 3) of above-mentioned exemplary description.

Electron transfer mediator as the reductive dehalogenation catalysts:

The environmental science of paying close attention to the water of handling or remedy contaminated with halogenated organic compounds relates to the field of enlivening of technical field that use electron transfer mediator (homogeneous phase or heterogeneous) makes halogenated organic compounds catalytic reduction dehalogenation (being generally dechlorination) under reduction (being generally anaerobism or anoxic) condition.

Electron transfer mediator is a chemical substance, be used as the catalyzer or the cocatalyst of catalytic activity, and by participate in, mediation and quickening or/and by the intermediate forms of stablize the oxidation reducing agents electronics is transferred to electron acceptor(EA) from body electron donor(ED) or reductive agent, the chemical reaction (for example reductive dehalogenation) of acceleration (catalysis) redox (redox) type.Owing to carry electronics and reciprocal electronics, therefore specifically be used for by participating in, mediate and quickening that the electron transfer mediator that electronics is transferred to electron acceptor(EA) from body electron donor(ED) or reductive agent also is called electron carrier or electronics is reciprocal by these chemical substances.

Based on the above-mentioned general mechanism of reductive dehalogenation and with reference to chemical equation (1), the general mechanism of the reductive dehalogenation system of the electronics re alphapro type that comprises electron transfer mediator type catalyzer is described below.Under reductive condition, in the presence of electron transfer mediator type catalyzer, body electron donor(ED) or reductive agent are with electronics (ne ^-) be transferred to the electron transfer mediator molecule that is reduced, during body electron donor(ED) or reductive agent oxidized.The electron transfer mediator molecule that has been reduced subsequently carry (back and forth) and with transfer transport to halogenated organic compounds pollutent [R-X] electron acceptor(EA), be reduced to [R-Y], during the electron transfer mediator molecule oxidized.Therefore already oxidised subsequently electron transfer mediator molecule can repeat the catalytic reduction dehalogenation circulation of electron transport mediation once more by body electron donor(ED) or reductive agent reduction.

Many laboratory studyes [for example 58-66] show, can quicken (being catalysis) some the easily reductibility of oxidized organic compound (for example halogenated organic compounds) conversion, change or degraded by use electron transfer mediator type catalyzer in the reciprocal system of electronics (electronshuttle system).Usually the reciprocal system of electronics relates to the naturally occurring organic macrocycle of use and transition metal complex as electron transfer mediator, electronics also makes electronics reciprocal between body electron donor(ED) or reductive agent and electron acceptor(EA), thus reductibility conversion, conversion or degraded electron acceptor(EA) (halogenated organic compounds).With respect to the system of using direct biological reducing reaction, these better simply laboratories abiotic (but intending biological) system has speed of reaction faster usually.A plurality of naturally occurring biochemicals for example mineral substance, naturally occurring organic substance (NOM), bacterium transition metal coenzyme and come from the organometallic complex (porphyrinogenicorganometallic complex) (as metalloporphyrin and metalloid porphyrin complex) of porphyrin and other intend biological big ring as electron transfer mediator type catalyzer [for example 58 have been proposed and have studied, 64,67-73].

Prior art comprises the various instructions of the catalytic reduction dehalogenation reaction system of these electron transport mediation, and wherein electron transfer mediator type catalyzer is humic substance [for example 74-76], quinone [for example 77] or protein [for example 78].But, these researchs of great majority up to now relate to uses the organometallic complex (for example metalloporphyrin or metalloid porphyrin complex) that comes from porphyrin to come catalytic reduction dehalogenation (being generally dechlorination) halogenated organic compounds, particularly halogenation organic solvent as electron transfer mediator type catalyzer in (homogeneous phase or heterogeneous) catalystic converter system.

Come from the organometallic complex (electron transfer mediator catalysis) of porphyrin:

Term " come from the organometallic complex of porphyrin " and be meant neutral metal atom or metal ion and come from porphyrin or class come from the organometallic complex that forms between the member ring systems of porphyrin, and further definition and for example in the explanation of the present invention hereinafter.

Metal porphyrin complex (being commonly referred to metalloporphyrin) is the organometallic complex that comes from porphyrin of metal ion and porphyrin part, the big ring of organic tetrapyrrole of serving as reasons and connecing and forming with four pyrroles's type rings of central metallic ions complexing by methane (methylene radical) bridging.Formation comprises the hither plane structure of the big ring of aromatics that is up to 22 conjugated pi electron, and according to [4n+2] aromaticity rule of Huckel, wherein 18 conjugated pi electron are attached to the delocalization path.The peripheral two keys of one or two of the porphyrin part of metalloporphyrin can carry out addition reaction to form metal porphyrin derivative, for example organometallic complex that comes from porphyrin of metal corrin or metal dihydride porphin phenols type.

About there are detailed instruction [for example 79] in the origin of the organometallic complex that comes from porphyrin and a lot of physics, chemistry and biology character, feature and behavior, thousands of kinds have been carried out identifying and research [for example 80,81].Exemplary well-known metal porphyrin complex is chlorophyll (for magnesium (II) complex compound) and protoheme (for iron (II) complex compound).Vitamins B ₁₂The serve as reasons organometallic complex that comes from porphyrin of the metal corrin type formed with the corrin part (the some of them methylene bridge is substituted or/and non-existent porphyrin analogue) of cobalt (III) ion complexation of (cyanocobalamin) (metalloid porphyrin complex of a kind of natural existence or synthetic dependency structure and function).

The organometallic complex (for example metalloporphyrin, metalloid porphyrin complex and derivative thereof) that comes from porphyrin is present in many biological chemical environments, for example active somatic cell, soil, settling, pitch, coal, resinous shale, oil and be rich in the naturally occurring settling [82-84] of the other types of organic substance.The organometallic complex that comes from porphyrin as everyone knows is as electron transfer mediator, and various biochemical pathway for example oxygen transmission and storing in (respectively at oxyphorase and myohaemoglobin) and in the transfer transport in redox (redox) reaction (cytopigment) play an important role.

The organometallic complex that comes from porphyrin has some special character, feature and behavior, it is particularly suitable under reduction (anaerobism or anoxic) condition, in catalytic reduction dehalogenation (the being generally dechlorination) reaction system of homogeneous phase or heterogeneous electron transport mediation, is used as electron transfer mediator type catalyzer and makes halogenated organic compounds pollutent catalytic reduction dehalogenation in the water.The organometallic complex that comes from porphyrin is: (1) is used for the effective redox catalyst of many reactions, and has large-scale redox active; (2) with the electrochemical activity of any central metal almost; (3) with the condition of various multi-form contaminated water (for example underground water, the surface water, water or its combination on the ground) environmental correclation under the aqueous solution in active catalyst; (4) advantages of higher stability take place thereby can make to be reflected under the exacting terms, and the reaction of other types may not take place with this understanding.

The organometallic complex (for example metalloporphyrin and metalloid porphyrin complex) that comes from porphyrin as everyone knows is used as electron transfer mediator type catalyzer in the homogeneous catalysis reduction method.There is many prior aries instructions [58-66 for example in homogeneous catalysis reductive dehalogenation (the being generally dechlorination) reaction system of relevant electron transport mediation, 85-97], relate to and use the various organometallic complex that comes from porphyrin (promptly to begin to not by another kind of material load as homogeneous phase electron transfer mediator type catalyzer, matrixization, insert or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in whole contaminated water) make halogenated organic compounds homogeneous catalysis reductive dehalogenation, described halogenated organic compounds for example is halogenation organic solvent or other non-weeding formulation halogenated organic compounds, particularly those known problematic pollutents in water.In the above-mentioned prior art of quoting, studying extensive and the most frequent halogenation (chlorination) organic compound has: chloromethane, Narcotile, ethylene chloride, chlorinated phenols (chlorinated phenol) and polybiphenyl (PCB).

Also exist and use hematin (the reduction form of porphyrinemia red pigment) or metalloporphyrin oxyphorase to instruct [46], at hyposulfite [S as body electron donor(ED) (bulk electron donor) or reductive agent as the prior art of electron transfer mediator type catalyzer ₂O ₄ ^-2] there are down the homogeneous catalysis reductive dehalogenation (dechlorination) and (bridging phenylbenzene) the halogenated organic compounds DDT that degrades in the aqueous solution (p, (the dichloro-diphenyl-trichloro-ethane) [C of p '-DDT) ₁₄H ₉Cl ₅] various enantiomerism forms and analogue, these materials are as everyone knows as sterilant with as miticide (fatal to flat lice and tick) material and turn out to be the water pollutant of murther.

But, these prior aries do not describe or hint relevant (homogeneous phase or heterogeneous) catalytic treatment in detail or remedy the instruction of the water that is polluted by the halogenation organic herbicide, described halogenation organic herbicide is generally for example halogenation organic herbicide member, particularly chlorination organic nitrogen-containing weedicide (CONH) in three kinds of halogenation organic herbicide groups (Fig. 1,2 and 3) of above-mentioned exemplary description.

The electron transfer mediator that is used for reductive dehalogenation as the heterogeneous composite material catalyzer:

Studies show that the organometallic complex (for example metalloporphyrin) that comes from porphyrin can be attached to (by insert) and be fixed on multilayer mineral or the amorphous silica gel surface or/and among, form the heterogeneous composite material that can be used for the reaction that the heterogeneous catalyst electron transport mediates.For example by being attached on silica gel and the double-deck clay or/and among cobalt metalloporphyrin, the heterogeneous composite material that tetramethyl pyridine porphyrin [5,10,15,20-four (1-methyl-4-pyridine)-porphines-cobalt] [TMPyP-Co] is formed be used for water tetracol phenixin [CCl ₄] heterogeneous catalyst reductibility dechlorination [98].Prior art [for example 99] also instructed about on the solid carrier of agarose, sephadex or polystyrene type or the body material or/and among mix and the fixing metal porphyrin, form the heterogeneous composite material of the reductibility dechlorination reaction that can be used for heterogeneous catalyst electron transport mediation.

Instruct [for example 46 based on the prior art of the relevant ZVM technology instruction [for example 47-57] (relate to and in the uncatalyzed reaction system, use zero-valent metal to make the dechlorination of chlorinated organic cpd non-catalytic reduction) and the prior art of relevant electron transfer mediator, 58-66,85-97] (organometallic complex that for example comes from porphyrin is used as effective catalyzer in the homogeneous catalytic reaction system makes the dechlorination of chlorinated organic cpd homogeneous catalysis reductibility) and prior art instruction [for example 98,99] (electron transfer mediator that relevant fixed comes from the organometallic complex type of porphyrin makes the dechlorination of chlorinated organic cpd heterogeneous catalyst reductibility as the effective catalyst that is included in the various dissimilar heterogeneous composite materials) and further extend, cause this transferee/applicant's proposition and simplification to put into practice scope of the present invention, to be incorporated in as the particle of the electron transfer mediator of the organometallic complex type that comes from porphyrin of catalyzer and zero-valent metal (ZVM) nanometer size on pulverous diatomite support or the matrix (the optional vermiculite that comprises) or/and among, the heterogeneous catalyst that is used to form diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type comes heterogeneous catalyst reductive dehalogenation (particularly dechlorination) reaction, this method is applicable to catalytic treatment or remedy contaminated water, described contaminated water for example comprises halogenated organic compounds, particularly halogenation organic solvent, for example chlorinated organic solvent.

Recently, be among the disclosed pct international patent application publication number WO2006/072944 on July 13rd, 2006, the system that this transferee/applicant has described diatomite of the present invention/ZVM/ electron transfer mediator matrix material, its manufacture method and using method thereof and comprised described material comes (original position or off normal) heterogeneous catalyst to handle polluted water, and wherein said contaminated water is underground water, the surface water, water, steam is or/and gas form on the ground.In matrix material, exemplary zero-valent metal (as body electron donor(ED) or reductive agent) is a Zero-valence transition metal, and for example Zero-valent Iron, cobalt, nickel, copper are or/and zinc.Preferred electron is transmitted medium (as the main catalytic active component of heterogeneous composite material) for coming from the organometallic complex of porphyrin, for example metalloporphyrin (as chlorophyll (magnesium (II) complex compound) or protoheme (iron (II) complex compound)) or/and the metalloid porphyrin complex (as organometallic complex, the vitamins B of metal corrin type ₁₂(cyanocobalamin is with the corrin part (porphyrin analogue) of cobalt (III) ion complexation).In order to realize that under reduction (being generally anaerobism or anoxic) condition, heterogeneous composite material is dispersed in the whole contaminated water.

Diatomite/ZVM/ electron transfer mediator matrix material heterogeneous catalytic system can be described as the heterogeneous catalytic oxidation reduction reaction mechanism of cyclical patterns usually.With reference to above chemical equation (2), under reduction (being generally anaerobism or anoxic) condition, at electron transfer mediator (as the main catalytic active component of matrix material heterogeneous catalyst), as the zero-valent metal atom [M of body electron donor(ED) or reductive agent ⁰] exist down, electronics (for example two electronics) is transferred to the electron transfer mediator molecule that is reduced, during the zero-valent metal atom be oxidized to metal ion, metal (II) ion [M for example ²⁺].The electron transfer mediator molecule that is reduced subsequently carry (back and forth) and with transfer transport to halogenated organic compounds pollutent [R-X] electron acceptor(EA), it is reduced to [R-Y], during the electron transfer mediator molecule oxidized.Already oxidised subsequently electron transfer mediator molecule is once more by another kind of zero-valent metal atom [M ⁰] body electron donor(ED) or reductive agent reduction, catalysis zero-valent metal (ZVM) the reductive dehalogenation circulation of electron transport mediation is repeated.

But, the a large amount of existing instruction of above-mentioned (homogeneous phase or heterogeneous) catalytic reduction dehalogenation (being generally dechlorination) reaction system about non-catalytic reduction dehalogenation (being generally dechlorination) reaction system and relevant electron transport mediation relates to the reductive dehalogenation that uses the various organometallic complex that comes from porphyrin to come homogeneous phase or heterogeneous catalyst halogenated organic compounds (for example halogenation organic solvent or other non-weeding formulation halogenated organic compounds) as electron transfer mediator type catalyzer, do not describe in detail or relevant (homogeneous phase or the heterogeneous) catalytic treatment of hint or remedy the instruction of the water that is polluted by the halogenation organic herbicide, three kinds of halogenation organic herbicide group (Fig. 1 that described halogenation organic herbicide for example is generally in above-mentioned exemplary description, 2 and 3) the halogenation organic herbicide member in, particularly chlorination organic nitrogen-containing weedicide (CONH).

Say that more generally (homogeneous phase or heterogeneous) catalytic reduction dehalogenation (the being generally dechlorination) reaction system of present known non-catalytic reduction dehalogenation (being generally dechlorination) reaction system or electron transport mediation is being handled or remedied aspect the water that is polluted by the halogenation organic herbicide usually technically or/and infeasible economically.

Therefore, for satisfy strict water quality standard and reduce be present in or be in close proximity to the people or/and the water source that animal directly or indirectly exposes or produce halogenation organic herbicide (particularly CONH) in the various forms of water at this water source and degraded product bring to environment and healthy risk, need development of new technically with viable economically and effectively processing and remedial technique.

Therefore, need and highly beneficial method and the system thereof with water of a kind of catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.Need the present invention to be applicable to that (original position is or/and off normal) homogeneous phase or heterogeneous catalyst handle contaminated water, described contaminated water is various form, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its combination on the ground.In addition, need the present invention technically with viable economically and be used to handle contaminated water effectively, its degree can be used described halogenation organic herbicide continuously in the farmland and can influence environment sharply.

Summary of the invention

The present invention relates to a kind of method and system thereof of water of catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.The halogenated organic compounds of these weedicide types is non-volatile particulate matter (almost whole) or liquid (some) down in room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, removable and soluble in water in water under common Pollutant levels (for example ppb-ppm scope), and in the environmental science of handling or remedy contaminated water and technical field particularly important.The present invention is applicable to (original position is or/and off normal) homogeneous phase or/and heterogeneous catalyst is handled this contaminated water, described contaminated water is various form, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its combination on the ground.

The method of the water of described catalytic treatment contaminated with halogenated organic compounds is included in the described at least a electron transfer mediator that under the reductive condition contaminated water is exposed to catalytically effective amount, thereby be reduced in the main process of the concentration of at least a halogenated organic compounds in the contaminated water, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

The system of the water of described catalytic treatment contaminated with halogenated organic compounds comprises following main component and function thereof: (a) at least a electron transfer mediator; (b) be used to comprise at least a (original position is or/and off normal) device of the described at least a electron transfer mediator of catalytically effective amount, be used under reductive condition described contaminated water being exposed to described at least a electron transfer mediator, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

Method of the present invention and system are utilized the chemical technology of phenomenon, mechanism and the contaminated water of method catalytic treatment of catalyzed chemical reaction type based on use, relate under reduction (being generally anaerobism or anoxic) condition, use at least a electron transfer mediator as the active oxidation reducing catalyst, will be in the halogenated organic compounds original position in the contaminated water or/and off normal homogeneous phase or/and heterogeneous catalyst degraded, conversion or transform (particularly by reductive dehalogenation (being generally dechlorination)) for not dangerous or/and the chemical substance of danger (poisonous) not too.Realization of the present invention causes the concentration of at least a halogenated organic compounds in the contaminated water to reduce.

Usually under reduction (anaerobism or anoxic) condition, any basically electron transfer mediator that is used as the active oxidation reducing catalyst can be used for realizing method of the present invention and system.Preferred described at least a electron transfer mediator is selected from organometallic complex, its analogue, its derivative and any combination thereof that comes from porphyrin.The preferred at least a organometallic complex that comes from porphyrin is selected from metal porphyrin complex, metal corrin complex compound, metal dihydride porphin phenol complex compound and any combination thereof.

Preferred metal porphyrin complex comprises and the transition metal that is selected from following porphyrin complexing:

Tetramethyl pyridine porphyrin [5,10,15,20-four (1-methyl-4-pyridine)-porphines] [TMPyP];

Tetrahydroxy phenyl tetrazaporphin [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines] [TP (OH) P];

Tetraphenylporphyrin [5,10,15,20-tetraphenyl-21H, 23H-porphines] [TPP]; With

4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acid) [TBSP].

Described transition metal is for being used to form any basically transition metal of corresponding metal porphyrin complex with above-mentioned porphyrin complexing.Preferred described transition metal is selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].

Therefore, in order to realize the present invention, preferred metal porphyrin complex is:

Tetramethyl pyridine porphyrin-transition metal [5,10,15,20-four (1-methyl-4-pyridine)-porphines-transition metal] [TMPyP-transition metal];

Tetrahydroxy phenyl tetrazaporphin-transition metal [5,10,15,20-four (4-hydroxybenzene

Base)-and 21H, 23H-porphines-transition metal] [TP (OH) P-transition metal];

Tetraphenylporphyrin-transition metal [5,10,15,20-tetraphenyl-21H, 23H-porphines-transition metal] [TPP-transition metal]; With

4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acid)-transition metal [TBSP-transition metal],

Wherein, in various metal porphyrin complexes, described transition metal is cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] or copper [Cu].

Be suitable for realizing that other exemplary metal porphyrin complexes of the present invention are selected from chlorophyll [magnesium (II) complex compound] and protoheme [iron (II) complex compound].Be suitable for realizing that exemplary metal corrin complex compound of the present invention is a vitamins B ₁₂[with the corrin part (porphyrin analogue) of cobalt (III) ion complexation].

The contaminated water of catalytic treatment relates to the halogenated organic compounds catalyzed degradation in contaminated water, transforms or change into not dangerous or/and Wei Xian chemical substance not too, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water, this realizes under reduction (anaerobism or anoxic) condition according to homogeneous catalysis or/and according to heterogeneous catalyst.According to homogeneous catalysis, the beginning of the described at least a electron transfer mediator (catalyzer) of described catalytically effective amount for by another kind of material load, matrixization, insertion or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in the whole contaminated water.According to heterogeneous catalyst; the described at least a electron transfer mediator (catalyzer) of described catalytically effective amount begin for by load, matrixization (matrixed), insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material, be scattered in subsequently in (promptly being insoluble to) whole contaminated water.Usually the described at least a electron transfer mediator (catalyzer) that begins the fixed catalytically effective amount is scattered in (promptly being insoluble to) whole contaminated water similarly.But in implementation procedure of the present invention, according to the actual parameter and the condition of given heterogeneous catalyst chemical reaction system, electron transfer mediator any or various fixed can be partially soluble in the contaminated water at least.

In order to realize the present invention according to heterogeneous catalyst, the heterogeneous catalyst of any kind (preferably but not limited to particle) solid carrier or body material can be used for load, matrixization and fixing described at least a electron transfer mediator (catalyzer) basically usually.Suitable (particle is or/and the non-particulate) solid carrier or the exemplary type of body material are diatomite, soft silica, crystalline silica, silica gel, aluminum oxide, mineral, pottery, carbohydrate (for example agarose, sephadex), clay, plastics (for example polystyrene), matrix material and combination thereof.

As this transferee/applicant on July 13rd, 2006 disclosed being entitled as: disclosed among the pct international patent application publication number WO 2006/072944 of " Zero ValentMetal Composite Catalyst; Manufacturing; System And Method UsingThereof; For Catalytically Treating Contaminated Water (the zero-valent metal composite catalyst that is used for the contaminated water of catalytic treatment; its manufacturing; system and using method) ", the specific examples of this electron transfer mediator solid supported or matrix structure (electron transfer mediator solidsupported or matrixed configuration) has the heterogeneous catalyst of diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type of being made up of pulverous diatomite support or matrix (the optional vermiculite that comprises), on or/and among mix as at least a (preferably coming from the organometallic complex type of the porphyrin) electron transfer mediator of catalyzer with as for example size of body electron donor(ED) or reductive agent and be about 5nm particle of zero-valent metal (ZVM) the nanometer size of about 600nm extremely.

(promptly relative under reduction (anaerobism or anoxic) condition with oxidizing condition, reductive condition is got the upper hand in contaminated water), for example carry out according to homogeneous catalysis or according to heterogeneous catalyst (separately by intermittent mode or pass through separately flow pattern), contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount, forms corresponding homogeneous phase of each pattern or heterogeneous catalytic reaction system.By intermittently or flow pattern, according to homogeneous catalysis, partly or entirely the described at least a electron transfer mediator of catalytically effective amount is with particle form, promptly uses with the independent particulate matter of common drying or the form of mixtures " former state " of several particulate matters.Select or in addition as another kind, before being exposed to contaminated water, under appropriate condition (temperature, pH, mixing), partly or entirely the described at least a electron transfer mediator of catalytically effective amount is dissolved in one or more suitable (water-based is or/and organic) solvents, subsequently with the solution form, promptly with the solution form of the independent particulate matter of dissolved or the solution form of the mixture of several particulate matters of dissolved use.By intermittence or flow pattern, according to heterogeneous catalyst, usually all the described at least a electron transfer mediator of catalytically effective amounts is with particle form, promptly uses with the independent particulate matter of the common drying of one or more electron transfer mediator solid supported or matrix structure or the form of mixtures " former state " of several particulate matters.

The natural existence of reductive condition in contaminated water is or/and produce by mankind's activity (artificially).When in contaminated water, not having reductive condition or think that phenomenon, mechanism and the method for (homogeneous phase or heterogeneous) catalytic reduction dehalogenation reaction of being not enough to effectively utilize the electron transport mediation makes halogenated organic compounds pollutent catalytic reduction dehalogenation in the contaminated water, then need in contaminated water, produce reductive condition artificially.

The described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, by contaminated water being exposed at least a body electron donor(ED) or the reductive agent artificial reductive condition that produces in contaminated water.Perhaps comprised at least a body electron donor(ED) or reductive agent heterogeneous catalyst artificial reductive condition that produces in contaminated water as the electron transfer mediator solid supported or the matrix structure type of the part of heterogeneous catalyst structure or composition by using.

Usually can under reduction (anaerobism or anoxic) condition, can be used for realizing the present invention by any basically body electron donor(ED) or the reductive agent of reduction electron transfer mediator.Preferred described at least a body electron donor(ED) or reductive agent comprise metal element (zero-valent metal).Preferred described body electron donor(ED) or reductive agent metal element (zero-valent metal) chosen from Fe [Fe], lithium [Li], sodium [Na], potassium [K], beryllium [Be], magnesium [Mg], titanium [Ti] and any mixture thereof.Perhaps, described body electron donor(ED) or reductive agent are selected from citric acid titanium [Ti (OC (CH ₂COOH) ₂COOH], POTASSIUM BOROHYDRIDE [KBH ₄], sodium borohydride [NaBH ₄], lithium hydride [LiH], potassium hydride KH [KaH], sodium hydride [NaH], boron trihydride [BH ₃], three aluminum hydride [AlH ₃], hydrazine [H ₂NNH ₂], triphenylphosphate [PPh ₃], V-Brite B [Na ₂S ₂O ₄] and any combination.

Usually in order to realize the present invention, under reductive condition, contaminated water being exposed to the time degree of described at least a electron transfer mediator of catalytically effective amount or time length (for example hour, day, week etc.) depends on the various parameters and the condition of given intermittence or flow pattern homogeneous phase or heterogeneous catalytic reaction system.

In order to realize the present invention, be used to comprise as the exemplary original position device that is suitable for of the described at least a electron transfer mediator of the catalytically effective amount of heterogeneous catalyst descend active restraining mass (PRB) form of water permeate at least in part or be the form of the part of underground water pumping and system for handling for the ditch of filling continuously or wall construction or independent filling well construction.Be used to comprise as homogeneous catalyst or/and the device of offing normal that is suitable for as the described at least a electron transfer mediator of the catalytically effective amount of heterogeneous catalyst exemplary is the form of the part of water processing reactor system on the ground.

After heterogeneous catalyst was handled contaminated water, the heterogeneous catalyst of electron transfer mediator solid supported or matrix structure type can be from being used to handle the given original position of contaminated water or the device of offing normal is removed, and recirculation is used to handle contaminated water.This recirculation can for example comprise that the heterogeneous catalyst with electron transfer mediator solid supported or matrix structure type carries out cleaning process, relate to from solid carrier or matrix selectivity and remove the pollutent that is adsorbed, nondestructive ground is handled and processing solid carrier or matrix simultaneously.

The present invention is specially adapted to the water of catalytic treatment contaminated with halogenated organic compounds, and wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.But, method of the present invention and system are applicable to the water that catalytic treatment is polluted by the halogenated organic compounds of other types or kind usually, and the halogenated organic compounds of described other types or kind is not limited to halogenation organic herbicide, its halogen-containing analogue or its halogen-containing derivative.

Therefore, the invention provides a kind of method of water of catalytic treatment contaminated with halogenated organic compounds, described method is included in the described at least a electron transfer mediator that under the reductive condition contaminated water is exposed to catalytically effective amount, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogenated analogs, its halide derivative and combination thereof.

Another aspect of the present invention provides a kind of system of water of catalytic treatment contaminated with halogenated organic compounds, and system of the present invention comprises following major portion and function thereof: (a) at least a electron transfer mediator; (b) be used to comprise at least a (original position is or/and off normal) device of the described at least a electron transfer mediator of catalytically effective amount, be used under reductive condition described contaminated water being exposed at least a electron transfer mediator, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogenated analogs, its halide derivative and combination thereof.

Summary of drawings

This paper only is described with reference to the drawings the present invention by embodiment.Now specifically with reference to the accompanying drawings, should emphasize be only by by way of example and for the schematic description preferred embodiment of the invention purpose represent described details, the details that provides is considered to the description to the principle of the invention and the most useful and easy understanding in notion aspect.In this, the details of describing of the present invention is only necessary by basic comprehension the present invention, do not illustrate in greater detail CONSTRUCTED SPECIFICATION of the present invention,, make several forms that the present invention can comprise in the practice apparent to those skilled in the art with reference to the description that accompanying drawing carries out.In the accompanying drawings:

Fig. 1 is listed in compound common name, chemical formula and CAS number and the description architecture of the known member in the interior chlorotriazine weedicide group of the present patent application scope with table;

Fig. 2 is listed in compound common name, chemical formula and CAS number and the description architecture of the known member in the interior chloro-acetanilide herbicide group of the present patent application scope with table;

Fig. 3 is listed in compound common name, chemical formula and CAS number and the description architecture of the known member in the interior halogenation aliphatic series weedicide group of the present patent application scope with table;

Fig. 4 passes through flow pattern for explanation, realize the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst, wherein said contaminated water is that natural groundwater is streamed, and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is for whole dispersion and be included in original position device interior part (particle is or/and non-particulate) solid carrier or body material, according to the present invention, described original position device is the form than lower part of filling the active restraining mass of groundwater seepage (PRB) of ditch or wall construction continuously;

Fig. 5 passes through flow pattern for explanation, realize the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst, wherein said contaminated water is that natural groundwater is streamed, and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is whole dispersion and each interior part (particle is or/and non-particulate) solid carrier or the body material that is included in a plurality of original position devices, according to the present invention, described original position device is the form of filling out the active restraining mass of groundwater seepage (PRB) of well construction separately;

Fig. 6 passes through flow pattern for explanation, realize the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst, wherein said contaminated water is that natural groundwater is streamed, and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is for whole dispersion and be included in original position device interior part (particle is or/and non-particulate) solid carrier or body material, according to the present invention, described original position device or be the form of the part of underground water pumping and system for handling; With

Fig. 7 passes through intermittently or flow pattern for explanation; according to homogeneous phase or/and heterogeneous catalyst is realized the synoptic diagram of sectional view of three kinds of exemplary concrete structures of the exemplary concrete preferred embodiment of method of the present invention and system; wherein said contaminated water is (natural or/and pressurize) underground water; the surface water is or/and ground current form; and the described at least a electron transfer mediator of catalytically effective amount is to be included in the interior water-soluble granular form of the device of offing normal or/and the homogeneous catalyst of aqueous solution form; or/and be a whole dispersion and a part that is included in the heterogeneous catalyst of interior (particle is or/and non-particulate) solid carrier of the device of offing normal or body material form, the wherein said form of device of offing normal according to the present invention for the part of ground water processing reactor system.

The preferred embodiment explanation

The present invention relates to a kind of method and system thereof of water of catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.The halogenated organic compounds of these weedicide types is non-volatile particulate matter (almost whole) or liquid (some) down in room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, removable and soluble in water in water under common Pollutant levels (for example ppb-ppm scope), and in environmental science and the technical field particularly important of handling or remedy contaminated water.The present invention is applicable to (original position is or/and off normal) homogeneous phase or/and heterogeneous catalyst is handled this contaminated water, described contaminated water is various form, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its combination on the ground.

The method of the water of described catalytic treatment contaminated with halogenated organic compounds is included in the main process that under the reductive condition contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

The system of the water of described catalytic treatment contaminated with halogenated organic compounds comprises following major portion and function thereof: (a) at least a electron transfer mediator; (b) be used to comprise at least a (original position is or/and off normal) device of the described at least a electron transfer mediator of catalytically effective amount, be used under reductive condition described contaminated water being exposed to described at least a electron transfer mediator, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

Method of the present invention and system are utilized the chemical technology of phenomenon, mechanism and the contaminated water of method catalytic treatment of catalyzed chemical reaction type based on use, relate under reduction (being generally anaerobism or anoxic) condition, use at least a electron transfer mediator as the active oxidation reducing catalyst, will be in the halogenated organic compounds original position in the contaminated water or/and off normal homogeneous phase or/and heterogeneous catalyst degraded, conversion or transform (particularly by reductive dehalogenation (being generally dechlorination)) for not dangerous or/and the chemical substance of danger (poisonous) not too.Realization of the present invention causes the reduction of at least a halogenated organic compounds concentration in the contaminated water.

Usually under reduction (anaerobism or anoxic) condition, any basically electron transfer mediator that is used as the active oxidation reducing catalyst can be used for realizing method of the present invention and system.Preferred described at least a electron transfer mediator is selected from organometallic complex, its analogue, its derivative and any combination thereof that comes from porphyrin.The preferred described at least a organometallic complex that comes from porphyrin is selected from metal porphyrin complex, metal corrin complex compound, metal dihydride porphin phenol complex compound and any combination thereof.

Tetraphenylporphyrin [5,10,15,20-tetraphenyl-21H, 23H-porphines] [TPP]; With

The contaminated water of catalytic treatment relates to the halogenated organic compounds catalyzed degradation in contaminated water, transforms or change into not dangerous or/and Wei Xian chemical substance not too, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water, this realizes under reduction (anaerobism or anoxic) condition according to homogeneous catalysis or/and according to heterogeneous catalyst.According to homogeneous catalysis, the beginning of the described at least a electron transfer mediator (catalyzer) of described catalytically effective amount for by another kind of material load, matrixization, insertion or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in the whole contaminated water.According to heterogeneous catalyst; the described at least a electron transfer mediator (catalyzer) of described catalytically effective amount begin for by load, matrixization, insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material, be scattered in subsequently in (promptly being insoluble to) whole contaminated water.Usually the described at least a electron transfer mediator (catalyzer) that begins the fixed catalytically effective amount is scattered in (promptly being insoluble to) whole contaminated water similarly.But in implementation procedure of the present invention, according to the actual parameter and the condition of given heterogeneous catalyst chemical reaction system, electron transfer mediator any or various fixed can be partially soluble in the contaminated water at least.

The specific examples of this electron transfer mediator solid supported or matrix structure has the heterogeneous catalyst of diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type of being made up of pulverous diatomite support or matrix (the optional vermiculite that comprises), on or/and among mix as at least a (preferably coming from the organometallic complex type of the porphyrin) electron transfer mediator of catalyzer with as for example size of body electron donor(ED) or reductive agent and be about 5nm particle of zero-valent metal (ZVM) the nanometer size of about 600nm extremely.

It should be understood that unless otherwise indicated, otherwise application of the present invention is not limited to order or order and quantity details at process, step and the substep of the operation of following exemplary description, the method described in the drawings and Examples or realization; Or the system device of system, the inferior device of system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and type of material, composition, structure, arrangement, order and quantity details.The present invention can adopt the variety of way practice or carry out other embodiments.But process, step, substep and the system device similar or identical with the exemplary description of this paper, the inferior device of system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and material can be used for practice or test the present invention, the inferior device of process, step, substep and system device, system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and material that the exemplary description of this paper is suitable.

It will also be appreciated that unless otherwise defined or explanation, otherwise all scientific and technological words that use in the whole disclosure, term are or/and phrase is identical or similar with the implication of one skilled in the art's common sense of the present invention.The word of using in the whole disclosure, term and symbol are used for illustrative purposes, should not think to limit to the present invention.For example term herein " pollute (contaminated) " and " polluting (polluted) " synonym is with identical mutually, and term " pollutent (contaminants) " and " pollutent (pollutants) " mutual synonym are with identical.In addition, in above-mentioned background part, introduce, definition, describe or/and all scientific and technological words of giving an example, term or/and phrase is identical or be applicable to the preferred embodiments of the invention, embodiment similarly and the exemplary explanation of the claim of enclosing.Term " about " used herein is meant correlation ± 10%.In addition, phrase used herein " room temperature " be meant about 20 ℃ to about 25 ℃ temperature range.

The method of the water that can understand catalytic treatment contaminated with halogenated organic compounds of the present invention better with reference to following exemplary explanation and accompanying drawing and the exemplary preferred embodiment of system thereof, optional preferred embodiment, concrete structure and other and optional aspect, the process of feature or characteristic, step, substep and equipment and material, the system device, the inferior device of system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and material and operation and realization.In the exemplary explanation and accompanying drawing, identical numbering is meant identical system device, the inferior device of system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, chemical reagent, annex and material below whole.

Below of the present invention in the exemplary explanation, comprise and be enough to understand suitably " can " utilize and realize disclosed main or primary process, step and substep required for the present invention and the main or primary inferior device of system device, system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and material.Therefore, those of ordinary skills know easily or/and in relating to prior art of the present invention and technical literature available realization time important various possible preliminary of the present invention, intermediate, less important or/and optional process, step or/and substep or/and the explanation of system device, the inferior device of system, device, assembly, sub-component, mechanism, structure, composition and element and peripherals, effectiveness, annex, chemical reagent and material brief description only at the most in this article.

Therefore, according to the of the present invention first main aspect, a kind of method of water of catalytic treatment contaminated with halogenated organic compounds is provided, described method is included in the process that under the reductive condition contaminated water is exposed at least a electron transfer mediator of catalytically effective amount, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

According to the of the present invention second main aspect, a kind of system of water of catalytic treatment contaminated with halogenated organic compounds is provided, described system comprises: (a) at least a electron transfer mediator; (b) be used to comprise at least a (original position is or/and off normal) device of the described at least a electron transfer mediator of catalytically effective amount, be used under reductive condition described contaminated water being exposed to described at least a electron transfer mediator, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.

" analogue " of term theme used herein (parent) compound be meant its molecular structure separately structurally with the relevant or similar compounds of theme (parent) molecular structure of compounds, therefore expect that this compound and theme (parent) compound have similarly (physics or/and chemistry or/and biology) activity.

" derivative " of term theme used herein (parent) compound is meant the compound of its molecular structure separately derived from " chemical modification " of theme (parent) molecular structure of compounds, and therefore most of theme (parent) molecular structure of compounds remains unchanged or be complete in the molecular structure of each derivative compound.Adopt active mode to carry out the chemical modification of theme (parent) molecular structure of compounds, for example use synthetic organic chemistry method and technology to form the derivative of the active type of theme (parent) compound.Select or in addition, adopt passive mode to carry out the chemical modification of theme (parent) molecular structure of compounds as another kind, promptly use naturally occurring method and technology to form the derivative of the passive type of theme (parent) compound.For example by adding at least one substituting group or/and by changing the derive compound of each molecular structure of at least one substituting group to the molecular structure of theme (parent) compound (initiatively or/and passive).For example by the derive compound of each molecular structure of the molecule of (initiatively or/and passive) oxidation or hydrolysis theme (parent) compound.

The above-mentioned definition of analogue and derivative is applicable to the chlorotriazine weedicide group (Fig. 1), chloro-acetanilide herbicide group (Fig. 2) of exemplary description herein and the halogenation organic herbicide member in the halogenation aliphatic series weedicide group (Fig. 3).Particularly consider the halogen-containing analogue and the derivative of these halogenation organic herbicide compounds.

With the instruction of contaminated water treatment (remedy, purifying) field with use consistent original position device used herein to be meant in the process of catalytic treatment (remedy, purifying) method, physically (on the space) be located substantially on or be seated and on position, place or the position of the reality of contaminated water or within the device operated.Therefore, the original position device links to each other with relative measures hydrokinetics by being correlated with (identical usually) physics (space) position of original position device and contaminated water unanimity with contaminated water.

The device of offing normal used herein is meant in the process of catalytic treatment (remedy, purifying) method, physically (on the space) be located substantially on or be seated and beyond position, place or the position of the reality of contaminated water or away from the device of place operation.Therefore, off normal device and contaminated water links to each other with relative measures hydrokinetics by inconsistent with contaminated water with the device of offing normal (separating usually) physics (space) position is relevant.

As described in hereinafter exemplary, with reference to figure 4-7, in order to realize method of the present invention and system, be used to comprise catalytically effective amount as the exemplary original position device that is suitable for of the described at least a electron transfer mediator of heterogeneous catalyst for filling ditch or wall (for example original position device 20 (Fig. 4)) continuously or filling descend active restraining mass (PRB) form of water permeate at least in part or being the form of the part of underground water pumping and system for handling (for example original position device 32 (Fig. 6)) of well (for example original position device 30 (Fig. 5)) structure separately.What be used to comprise catalytically effective amount is a part (device 48 (Fig. 7) of for example offing normal) form of above-mentioned surface water treatment reactor system as homogeneous catalyst or/and as the exemplary device of offing normal that is suitable for of the described at least a electron transfer mediator of heterogeneous catalyst.

The system of the water that is used for the catalytic treatment contaminated with halogenated organic compounds of preferred the application of the invention of method of the water of catalytic treatment contaminated with halogenated organic compounds of the present invention realizes.Correspondingly, the system preference of the water of catalytic treatment contaminated with halogenated organic compounds of the present invention is used to realize the method for the water of catalytic treatment contaminated with halogenated organic compounds of the present invention.What also should fully understand is that hereinafter exemplary explanation is to be applicable to method of the present invention or/and system to form alone or in combination.

The service form of contaminated water:

The water that is polluted by above-mentioned halogenated organic compounds equally also is called " contaminated water " in this article, be various in multi-form any, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply with) on the ground or its combination on the ground.The contaminated water of many this forms for for example comprising the people or/and the water source of the tap water that animal directly or indirectly exposes or produce this water source.

The halogenated organic compounds that is suitable for:

In the halogenated organic compounds in the present patent application scope, chlorotriazine weedicide group, chloro-acetanilide herbicide group and halogenation aliphatic series weedicide group are three kinds of concrete well-known halogenation organic herbicide groups, and wherein universal performance or distinguishing characteristics or the character of each halogenation organic herbicide group by each halogenation organic herbicide member common chemical structure in this halogenation organic herbicide group defines.Fig. 1,2 and 3 usefulness table is listed in these the three kinds corresponding halogenation organic herbicide groups each compound common name, chemical formula and CAS number of known halogenation organic herbicide member and chemical structure is described.Other common chemical titles not too that among these known halogenation organic herbicide members each also has a for example CAS and IUPAC name, though unlisted in this article, appear in chemical literature and the related art.

Determine and illustrate as Fig. 1, chlorotriazine weedicide group be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein R ₁-R ₄Independently be selected from hydrogen atom [H] and organic substituent separately:

Therefore, R ₁-R ₄Independent separately for example is hydrogen or organic substituent, such as, but be not limited to alkyl (for example methyl, ethyl, sec.-propyl), cycloalkyl (for example cyclopropyl), cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid (for example acetate), ether, alkoxyl group, heteroaryl, aryl, heterolipid cyclic group etc.

With reference to figure 1, chlorotriazine weedicide group comprises following known halogenation organic herbicide: atrazine [C ₈H ₁₄CIN ₅], chlorazine [C ₁₁H ₂₀ClN ₅], cyanazine [C ₉H ₁₃ClN ₆], cyprazine [C ₉H ₁₄ClN ₅], Radix Glycyrrhizae Tianjin [C ₇H ₁₀ClN ₅O ₂], ipazine [C ₁₀H ₁₈ClN ₅], the green bristlegrass of going out Tianjin [C ₁₀H ₁₈ClN ₅O], the ring third blue or green Tianjin [C ₁₀H ₁₃ClN ₆], proglinazine[C ₈H ₁₂ClN ₅O ₂], propazine [C ₉H ₁₆ClN ₅], fourth Tianjin [C in addition ₉H ₁₆ClN ₅], simazine [C ₇H ₁₂ClN ₅], terbuthylazine [C ₉H ₁₆ClN ₅] and trietazine [C ₉H ₁₆ClN ₅].

Other the interior halogenated organic compounds of scope that are also included within the present patent application are halogen-containing analogue and the halogen-containing derivative of the halogenation organic herbicide member in the chlorotriazine weedicide group of above-mentioned exemplary description, the wherein R in the above-mentioned general chemical structure of chlorotriazine weedicide group ₁-R ₄As described herein separately.

Determine and explanation as Fig. 2, the chloro-acetanilide herbicide group be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein R ₁-R ₄Independently be selected from hydrogen atom [H] and organic substituent as indicated above separately:

With reference to figure 2, the chloro-acetanilide herbicide group comprises following known halogenation organic herbicide: acetochlor [C ₁₄H ₂₀ClNO ₂], alachlor [C ₁₄H ₂₀ClNO ₂], Butachlor technical 92 [C ₁₇H ₂₆ClNO ₂], metazachlor [C ₁₄H ₁₆ClN ₃O], metolachlor [C ₁₅H ₂₂ClNO ₂], S-metolachlor [C ₁₅H ₂₂ClNO ₂], the third careless amine [C ₁₇H ₂₆ClNO ₂], propachlor [C ₁₁H ₁₄ClNO], xylachlor [C ₁₃H ₁₈ClNO], butenachlor [C ₁₇H ₂₄ClNO ₂], delachlor [C ₁₅H ₂₂ClNO ₂], peace tower [C ₁₄H ₁₈ClNO ₃], ethachlor [C ₁₃H ₁₈ClNO ₂], propisochlor [C ₁₅H ₂₂ClNO ₂], prynachlor [C ₁₂H ₁₂ClNO], the violent grass [C that kills ₁₈H ₂₈ClNO ₂] and thiophene ether grass amine [C ₁₆H ₁₈ClNO ₂S].

Other the interior halogenated organic compounds of scope that are also included within the present patent application have halogen-containing analogue and the halogen-containing derivative of the halogenation organic herbicide member in the chloro-acetanilide herbicide group of above-mentioned exemplary description, the wherein R in the above-mentioned general chemical structure of chloro-acetanilide herbicide group ₁-R ₄As described herein separately.

Be the most widely used agrochemicals in chlorotriazine weedicide group (Fig. 1) (particularly triazine, for example atrazine and cyanazine) and the halogenation organic herbicide member in chloro-acetanilide herbicide group (Fig. 2) (particularly alachlor and metolachlor).This halogenation organic herbicide is commonly referred to chlorination organonitrogen weedicide (CONH), illustrates also to have nitrogen except halogens chlorine.

Determine and explanation as Fig. 3, halogenation aliphatic series weedicide group be meant and comprise have hereinafter shown in the halogenation organic herbicide of general chemical structure, wherein n is 1-4, and A, B, R ' and R ＂ independently are selected from hydrogen atom [H] and organic substituent separately, and wherein at least one among A, B, R ' and the R ＂ is halogen atom (being fluorine [F], chlorine [Cl], bromine [Br] or iodine [I]):

A-(C-R′-R＂) _n-B

Therefore, the halogenation organic herbicide member in halogenation aliphatic series weedicide group (Fig. 3) have carbon atom wherein in open chain with the general chemical structure of the continuous organic compound of at least one carbon atom that links to each other with halogen atom.Therefore, for example n is 1-4, is generally 1-2; A is halogen atom, hydrogen atom or alkyl; R ' and R ＂ independently are halogen atom, hydrogen atom or alkyl separately; B be hydrogen atom, halogen atom, alkyl or-(C=O)-W, wherein W be hydroxyl, haloalkyl (for example tri haloalkyl) or for example-C-(R ')=C-(R ＂)-C (=O)-OH, wherein R ' and R ＂ are as indicated above.

With reference to figure 3, halogenation aliphatic series weedicide group comprises following known halogenation organic herbicide: pentachloro-oxopentanoic acid [C ₅HCl ₅O ₃], chloropon [C ₃H ₃Cl ₃O ₂], dalapon [C ₃H ₄Cl ₂O ₂], tetrafluoro propionic acid [C ₃H ₂F ₄O ₂], TCA (trichoroacetic acid(TCA)) [C ₂HCl ₃O ₂], hexachloroacetone [C ₃Cl ₆O], methyl iodide [CH ₃I], monobromethane [CH ₃Br], monochloro acetate [C ₂H ₃ClO ₂] and SMA (chloracetic acid sodium) [C ₂H ₂ClNaO ₂].

Being also included within other halogenated organic compounds in the scope of the present patent application has halogen-containing analogue and the halogen-containing derivative of the halogenation organic herbicide member in the halogenation aliphatic series weedicide group of above-mentioned exemplary description, and wherein A, B, R ' and R ＂ and the n in the above-mentioned general chemical structure of halogenation aliphatic series weedicide group is as described herein separately.

The aliphatic saturated hydrocarbon that comprises straight chain and branched group described in term used herein " alkyl ".Preferred described alkyl has 1-20 carbon atom.No matter when state in this article that digital scope for example when " 1-20 ", means that this group (being alkyl in this case) comprises 1 carbon atom, 2 carbon atoms, 3 carbon atoms etc., is up to and comprises 20 carbon atoms.More preferably described alkyl is the medium sized alkyl with 1-10 carbon atom.Unless otherwise indicated, otherwise most preferably described alkyl is the low alkyl group with 1-4 carbon atom.Described alkyl is substituted or is not substituted.When being substituted, described substituting group for example is tri haloalkyl, cycloalkyl, thiazolinyl, alkynyl, aryl, heteroaryl, heterolipid cyclic group, halogen, hydroxyl, alkoxyl group, aryloxy, sulfydryl, thio alkoxy, thio-aryloxy, sulfinyl, alkylsulfonyl, cyano group, nitro, azo, alkylsulfonyl, sulfinyl, carbonyl, thiocarbonyl, ester, ether, carboxyl, thiocarboxyl group, thioether and amino.

All carbon monocycles or condensed ring (promptly sharing the adjacent right ring of carbon atom) group, π-electron system that wherein one or more rings do not have total conjugated described in term " cycloalkyl ".The example of cycloalkyl has but is not limited to cyclopropane, tetramethylene, pentamethylene, cyclopentenes, hexanaphthene, cyclohexadiene, suberane, cycloheptatriene and diamantane.Described cycloalkyl is substituted or is not substituted.

" thiazolinyl " is meant the alkyl of being made up of at least two carbon atoms and at least one carbon-to-carbon double bond.

" alkynyl " is meant the alkyl of being made up of at least two carbon atoms and at least one carbon-to-carbon three key.

" aryl " is meant that the full carbon monocycle or the condensed ring of the π-electron system with total conjugated encircle (promptly sharing the adjacent right ring of carbon atom) group more.The example of aryl has but is not limited to phenyl, naphthyl and anthryl.Described aryl is substituted or is not substituted.

" heteroaryl " is meant have one or more atoms in ring (for example nitrogen, oxygen and sulphur) and the monocycle of π-electron system or condensed ring (promptly sharing the ring of adjacent atom pairs) group with total conjugated.The example of heteroaryl is including, but not limited to pyrroles, furans, thiophene, imidazoles, oxazole, thiazole, pyrazoles, pyridine, pyrimidine, quinoline, isoquinoline 99.9 and purine.Described heteroaryl is substituted or is not substituted.When being substituted, described substituting group for example is alkyl, hydroxyalkyl, tri haloalkyl, cycloalkyl, thiazolinyl, alkynyl, aryl, heteroaryl, heterolipid cyclic group, halogen, hydroxyl, alkoxyl group, aryloxy, sulfydryl, thio alkoxy, thio-aryloxy, sulfinyl, alkylsulfonyl, cyano group, nitro, azo, alkylsulfonyl, sulfinyl and amino.

" heterolipid cyclic group " is meant have one or more atoms in the ring monocycle or the condensed ring group of (for example nitrogen, oxygen and sulphur).Described ring also can have one or more pairs of keys.But described ring does not have the π-electron system of total conjugated.Described heterolipid cyclic group is substituted or is not substituted.

" hydroxyl " is meant-the OH group.

" azo " group is meant-the N=N group.

" alkoxyl group " be meant as herein defined-the O-alkyl and-the O-cycloalkyl.

" aryloxy " be meant as herein defined-the O-aryl and-the O-heteroaryl.

" sulfydryl " is meant-the SH group.

" thio alkoxy " be meant as herein defined-the S-alkyl and-the S-cycloalkyl.

" thio-aryloxy " be meant as herein defined-the S-aryl and-the S-heteroaryl.

" carbonyl " be meant-C (=O)-the R group, wherein R is hydrogen, alkyl, thiazolinyl, cycloalkyl, aryl, heteroaryl (linking to each other by ring carbon) or heterolipid cyclic group (linking to each other by ring carbon) as herein defined.

" carboxylic acid group " be meant-R-C (=O)=the OH group, wherein R is alkyl, cycloalkyl or aryl as herein defined.

" halogen (base) " also is called " halogen " in this article, is meant fluorine, chlorine, bromine or iodine.

" trihalomethyl group " be meant-the CX group, and wherein X is halogen as herein defined.

" amino " is meant-NR ₁R ＂ group, wherein R ' and R ＂ are as defined herein.

" nitro " is meant-NO ₂Group.

" cyano group " is meant-C ≡ N group.

" ether " group is meant-R-O-R ' group, and wherein R and R ' are independent separately is alkyl as herein defined.

As described, the scope of the present patent application is specifically related to the three kinds of halogenation organic herbicide groups and wherein halogenation organic herbicide member, its halogen-containing analogue and the halogen-containing derivative and the combination thereof of above-mentioned exemplary description, as the particular type or the kind of the wideer and kind more commonly used of halogenated organic compounds.Described halogenation organic herbicide compound is non-volatile particulate matter (almost whole) or liquid (some) down in room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, removable and soluble in water in water under common Pollutant levels (for example ppb-ppm scope), and in the environmental science of handling or remedy contaminated water and technical field particularly important.

Method of the present invention and system utilize phenomenon, mechanism and the method for catalyzed chemical reaction type to come the chemical technology of the contaminated water of catalytic treatment based on use, relate under reduction (anaerobism or anoxic) condition, use at least a electron transfer mediator as the active oxidation reducing catalyst, will be in the halogenated organic compounds original position in the contaminated water or/and off normal, homogeneous phase or/and heterogeneous catalyst degraded, conversion or transform (particularly by reductive dehalogenation (being generally dechlorination)) for not dangerous or/and the chemical substance of danger (poisonous) not too.Realization of the present invention causes the reduction of at least a halogenated organic compounds concentration in contaminated water.

Electron transfer mediator:

" electron transfer mediator " used herein is the chemical substance as catalyzer or cocatalyst, has catalytic activity, and be transferred to electron acceptor(EA) from body electron donor(ED) or reductive agent by participation, mediation and accelerated electron, or/and pass through to stablize the intermediate forms of oxidation reducing agents, thereby the chemical reaction (for example reductive dehalogenation) that quickens (catalysis) redox (redox) type.Owing to carry and reciprocal electronics by these chemical substances, therefore specifically be used for by participate in, mediation and quicken that the electron transfer mediator that electronics is transferred to electron acceptor(EA) from electron donor(ED) or reductive agent also is called electron carrier or electronics is reciprocal.The explanation that makes halogenated organic compounds (beyond application range of the present invention) reductive dehalogenation (particularly zero-valent metal (ZVM) reductive dehalogenation), general mechanism (with reference to chemical equation (1) and (2)) and prior art instruction are provided in above background parts by the electron transfer mediator catalyst.

Usually under reduction (anaerobism or anoxic) condition, any basically electron transfer mediator that is used as the active oxidation reducing catalyst can be used for realizing method of the present invention and system.Preferred described at least a electron transfer mediator is selected from organometallic complex, its analogue, its derivative and any combination thereof that comes from porphyrin.The analogue of motif compound provided above and the definition of derivative are applicable to organometallic complex theme (parent) compound respective analogs and the derivative that comes from porphyrin.

" coming from the organometallic complex of porphyrin " used herein be meant neutral metal atom or metal ion and come from porphyrin or class come from the organometallic complex that forms between the member ring systems of porphyrin." come from porphyrin or class come from the member ring systems of porphyrin " used herein is meant wherein 5 yuan of systems that heterocycle connects by linking group in macrocyclic structure.Described linking group is saturated or/and undersaturated, and has saturated or/and undersaturated side chain, make in the system big ring with unsaturated linking group or/and between the side chain formation pi-conjugated wholly or in part.The member ring systems that described that come from porphyrin or class comes from porphyrin also preferably has enough non-conjugated electronics, to form covalent linkage or coordinate bond with metal.

What also should fully understand is, term used herein " come from the organometallic complex of porphyrin " and be included in neutral metal atom or metal ion and definition just now come from porphyrin or class come from the organometallic complex that forms between the analogue of member ring systems of porphyrin or the derivative.

About there are instruction widely [for example 79] in the origin of the organometallic complex that comes from porphyrin and a lot of physics, chemistry and biology character, feature and behavior, have wherein determined and studied thousands of kinds [for example 80,81].The organometallic complex that comes from porphyrin has some specific character, feature and behavior, make it be specially adapted in catalytic reduction dehalogenation (the being generally dechlorination) reaction system of homogeneous phase or heterogeneous electron transport mediation, be used as electron transfer mediator type catalyzer, under reduction (anaerobism or anoxic) condition, particularly in water, catalytic reduction dehalogenation halogenated organic compounds pollutent, described halogenated organic compounds pollutent for example is common halogenation organic herbicide, for example at three kinds of weedicide group (Fig. 1 of above-mentioned exemplary description, 2 and 3) the weedicide member in, particularly chlorination organonitrogen weedicide (CONH).

The organometallic complex that comes from porphyrin is: (1) is used for many reactions and has the effective redox catalyst of long-acting (long range) redox active; (2) has electrochemical activity with any central metal almost; (3) with the condition of the environmental correclation of various multi-form contaminated water (for example underground water, the surface water and water on the ground) under, the active catalyst in the aqueous solution; (4) higher stability carry out thereby can make to be reflected under the exacting terms, and the reaction of other types may not take place.

In order to realize method of the present invention and system, the preferred described at least a organometallic complex that comes from porphyrin is selected from metal porphyrin complex, metal corrin complex compound, metal dihydride porphin phenol complex compound and any combination thereof.The preferred described at least a organometallic complex that comes from porphyrin comprises at least a metal porphyrin complex.Metal porphyrin complex (being commonly referred to metalloporphyrin), be the organometallic complex that comes from porphyrin of metal ion and porphyrin part, the big ring of organic tetrapyrrole of serving as reasons and connecing and forming with four pyrroles's type rings of central metallic ions complexing by methane (methylene radical) bridging.Formation comprises the hither plane structure of the big ring of aromatics that is up to 22 conjugated pi electron, and according to [4n+2] aromaticity rule of Huckel, wherein 18 conjugated pi electron are mixed the delocalization path.The peripheral two keys of one or two of the porphyrin part of metalloporphyrin can carry out addition reaction to form metal porphyrin derivative, for example organometallic complex that comes from porphyrin of metal corrin or metal dihydride porphin phenols type.

The preferable alloy porphyrin complex comprises and the transition metal that is selected from following (originally being free alkali) porphyrin complexing:

The tetramethyl pyridine porphyrin also is called and is called [5,10,15,20-four (1-methyl-4-pyridine)-porphines], abbreviation herein and also be called [TMPyP];

Tetrahydroxy phenyl tetrazaporphin also is called and is called [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines], abbreviation herein and also be called [TP (OH) P];

Tetraphenylporphyrin also is called and is called [5,10,15,20-tetraphenyl-21H, 23H-porphines], abbreviation herein and also be called [TPP]; With

4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acids), abbreviation herein and also be called [TBSP].

Described transition metal for can with any basically transition metal of the above-mentioned porphyrin complexing that is used to form the corresponding metal porphyrin complex.Preferred described transition metal is selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].

Tetramethyl pyridine porphyrin-transition metal also is called and is called [5,10,15,20-four (1-methyl-4-pyridine)-porphines-transition metal], abbreviation herein and also be called [TMPyP-transition metal];

Tetrahydroxy phenyl tetrazaporphin-transition metal also is called and is called [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines-transition metal], abbreviation herein and also be called [TP (OH) P-transition metal];

Tetraphenylporphyrin-transition metal also is called and is called [5,10,15,20-tetraphenyl-21H, 23H-porphines-transition metal] [TPP-transition metal]; With

4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acid)-transition metal, abbreviation herein and also be called [TBSP-transition metal],

Above-mentioned [TMPyP-transition metal], [TP (OH) P-transition metal], [TPP-transition metal] and [TBSP-transition metal], preferred metal porphyrin complex or commercially availablely get or use open method and technology [for example 100,101,61] to synthesize by commercially available corresponding [TMPyP] that gets, [TP (OH) P], [TPP] and [TBSP], (free alkali) porphyrin and transition metal solution.

Be suitable for realizing that other exemplary metal porphyrin complexes of the present invention are selected from chlorophyll [magnesium (II) complex compound] and protoheme [iron (II) complex compound].Be suitable for realizing that exemplary metal corrin complex compound of the present invention is a vitamins B ₁₂[with the corrin part (porphyrin analogue) of cobalt (III) ion complexation].These other exemplary commercially available getting of metal porphyrin complex.

" at least a electron transfer mediator of catalytically effective amount " used herein is meant the amount (for example with volumetric molar concentration or the expression of quality (weight) ratio) of at least a electron transfer mediator (as the main catalyst component of homogeneous catalyst or heterogeneous catalyst) that contaminated water exposes, make that the effective catalysis of described at least a electron transfer mediator in contaminated water is reduced in the concentration of at least a halogenated organic compounds pollutent in the contaminated water under reduction (anaerobism or anoxic) condition.

Under reductive condition, come the contaminated water of catalytic treatment by at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount, relate to according to homogeneous catalysis, according to heterogeneous catalyst or according to its combination realize will be at the halogenated organic compounds catalyzed degradation in the contaminated water, transform or change into not dangerous or/and Wei Xian chemical substance not too, thereby be reduced in the concentration of at least a halogenated organic compounds in the contaminated water.

According to homogeneous catalysis, described at least a electron transfer mediator (catalyzer) begin for not by another kind of material load, matrixization, insertion or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in the whole contaminated water.

According to heterogeneous catalyst; described at least a electron transfer mediator (catalyzer) begin for by load, matrixization, insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material, be scattered in subsequently in (promptly being insoluble to) whole contaminated water.Usually beginning at least a electron transfer mediator of fixed (catalyzer) is scattered in (promptly being insoluble to) whole contaminated water similarly.But in implementation procedure of the present invention, according to the actual parameter and the condition of given heterogeneous catalyst chemical reaction system, electron transfer mediator any or various fixed can be partially soluble in the contaminated water at least.

In order to realize method of the present invention and system according to heterogeneous catalyst, the heterogeneous catalyst of any kind (preferably but not limited to particle) solid carrier or body material can be used for load, matrixization and fixing described at least a electron transfer mediator (catalyzer) basically usually.Suitable (particle is or/and the non-particulate) solid carrier or the exemplary type of body material are diatomite, soft silica, crystalline silica, silica gel, aluminum oxide, mineral, pottery, carbohydrate (for example agarose, sephadex), clay, plastics (for example polystyrene), matrix material and combination thereof.

As this transferee/applicant on July 13rd, 2006 disclosed being entitled as: disclosed among the pct international patent application publication number WO 2006/072944 of " Zero ValentMetal Composite Catalyst; Manufacturing; System And Method UsingThereof; For Catalytically Treating Contaminated Water (the zero-valent metal composite catalyst that is used for the contaminated water of catalytic treatment; its manufacturing; system and using method) ", the specific examples of this electron transfer mediator solid supported or matrix structure has the heterogeneous catalyst of diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type of being made up of pulverous diatomite support or matrix (the optional vermiculite that comprises), on or/and among mix as at least a (preferably coming from the organometallic complex type of the porphyrin) electron transfer mediator of catalyzer with as for example size of body electron donor(ED) or reductive agent and be about 5nm particle of zero-valent metal (ZVM) the nanometer size of about 600nm extremely.

It should be noted, after heterogeneous catalyst is handled contaminated water, the heterogeneous catalyst of electron transfer mediator solid supported or matrix structure type can be from being used to handle the given original position of contaminated water or the device of offing normal is removed, and recirculation is used to handle contaminated water.The heterogeneous catalyst that this recirculation can for example relate to electron transfer mediator solid supported or matrix structure type carries out cleaning process, relate to from solid carrier or matrix selectivity and remove the pollutent that is adsorbed, nondestructive ground is handled and processing solid carrier or matrix simultaneously.

Therefore, in order to realize method of the present invention and system according to homogeneous catalysis, the described at least a electron transfer mediator of the catalytically effective amount of the above definition that contaminated water exposed specifically be meant begin for not by another kind of material load, matrixization, insertion, insertion or/and the solid of catching (being generally particle) material, and become subsequently and can move freely and dissolve in the amount of at least a electron transfer mediator (catalyzer) in the whole contaminated water.

Therefore; select or in addition as another kind; in order to realize method of the present invention and system according to heterogeneous catalyst; the described at least a electron transfer mediator of the catalytically effective amount of the above definition that contaminated water exposed specifically be meant begin for by load, matrixization, insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material, be dispersed in the amount of at least a electron transfer mediator (catalyzer) in the whole contaminated water subsequently.

The catalytically effective amount of the described at least a electron transfer mediator that common contaminated water exposed is variable.The described at least a electron transfer mediator of the catalytically effective amount that contaminated water exposed is represented with the term volumetric molar concentration, corresponding to the mole number of at least a electron transfer mediator described in the contaminated water of unit volume (for example rising), and be designated as a mole electron transfer mediator/liter contaminated water.The catalytically effective amount of the described at least a electron transfer mediator that contaminated water exposed represents to be preferably about 10 with volumetric molar concentration ^-7To about 10 ^-3Mole electron transfer mediator/liter contaminated water, more preferably about 10 ^-6To about 10 ^-4Mole electron transfer mediator/liter contaminated water.The best catalytically effective amount of the described at least a electron transfer mediator that contaminated water exposed is expressed as about 10 with volumetric molar concentration ^-5Mole electron transfer mediator/liter contaminated water.

Perhaps the catalytically effective amount of the described at least a electron transfer mediator that contaminated water exposed with term quality (weight) than expression, corresponding to the ratio of the quality (weight) of the quality (weight) of described at least a electron transfer mediator (for example ' x ' quality (weight) unit) and at least a halogenated organic compounds pollutent in contaminated water (for example ' y ' quality (weight) unit).This quality (weight) is than the ratio that is designated as two numerals, x:y for example, no unit or dimension are expressly understood that the quality (weight) into electron transfer mediator is identical with the unit or the dimension of the quality (weight) of the quality (weight) of at least a halogenated organic compounds pollutent in contaminated water.The catalytically effective amount of at least a electron transfer mediator that contaminated water exposed is preferably about 1:1000 to about 1000:1 with the quality (weight) of at least a electron transfer mediator and at least a halogenated organic compounds pollutent in contaminated water than expression; More preferably about 1:100 is to about 100:1; Most preferably be about 1:10 to about 10:1.

Usually according to afore mentioned rules, under reduction (anaerobism or anoxic) condition, any basically electron transfer mediator as the active oxidation reducing catalyst can be used for realizing method of the present invention, and the catalytically effective amount of the described at least a electron transfer mediator that common contaminated water exposed is variable.The actual type of the described at least a electron transfer mediator that contaminated water exposed and catalytically effective amount depend on Several Parameters, and these parameters can be categorized as one-level, secondary and three grades of parameters.

Exemplary one-level parameter is type, quantity, concentration and physicochemical property, feature and the behavior of target (known or/and suspect) the halogenated organic compounds pollutent in contaminated water, for example chemical structure, chemically reactive, solvability.Physicochemical property, feature and behavior that other one-level parameters are described at least a electron transfer mediator, for example chemical structure, active, the solvability of chemistry (catalysis).In order to realize the present invention, preferably attempt physicochemical property, feature and the behavior of described at least a electron transfer mediator relevant or related with physicochemical property, feature and the behavior of target halogenated organic compounds pollutent in contaminated water.

Exemplary secondary parameters is volume (representing with cumulative volume or quality representation or with volume or mass velocity) and physical chemistry and hydrokinetics (flowing) character, feature and the behavior of contaminated water.These secondary parameters specifically depend on the form of contaminated water, for example are underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), ground water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its array configuration.

Temperature, pH, pressure and gradient thereof that three grades of exemplary parameters are contaminated water.Other three grades of parameters are to be present in that wait to be exposed to catalytically effective amount described at least a electron transfer mediator and contaminated water direct neighbor other are known or/and possible material or type of material, quantity, concentration and physicochemical property, feature and behavior, for example chemical structure, chemically reactive, solubleness.

Contaminated water is exposed to electron transfer mediator:

Usually contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount according to forming in homogeneous phase or well-known various mode in heterogeneous catalytic reaction system field or the method any.For example according to homogeneous catalysis or/and according to heterogeneous catalyst (separately by intermittent mode or pass through separately flow pattern), contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount, is used to form corresponding homogeneous phase of each pattern or heterogeneous catalytic reaction system.

By the given homogeneous phase of intermittence or flow pattern operation or the phenomenon that the heterogeneous catalytic reaction system can be utilized the catalyzed chemical reaction type, mechanism and method are come the contaminated water of catalytic treatment, relate under reduction (anaerobism or anoxic) condition, use described at least a electron transfer mediator as the active oxidation reducing catalyst, will be in the halogenated organic compounds original position in the contaminated water or/and off normal, homogeneous phase is or/and the heterogeneous catalyst degraded, conversion or transform (particularly by reductive dehalogenation (being generally dechlorination)) for not dangerous or/and the chemical substance of danger (poisonous) not too.

Hereinafter represent contaminated water is exposed to several exemplary concrete optimal way of the described at least a electron transfer mediator of catalytically effective amount.What should fully understand is, the realization of method of the present invention and system is not limited to the concrete optimal way of following exemplary exposure, because can use other modes of the homogeneous phase that forms intermittent mode or flow pattern type or heterogeneous catalytic reaction system described contaminated water to be exposed to the described at least a electron transfer mediator of catalytically effective amount.

Homogeneous catalysis:

For any passing through intermittently or flow pattern, according to homogeneous catalysis contaminated water is exposed to the exemplary concrete optimal way of the described at least a electron transfer mediator of catalytically effective amount hereinafter described, the described at least a electron transfer mediator of described catalytically effective amount begin for not by another kind of material load, matrixization, insertion or/and the solid of catching (being generally particle) material.When being exposed to contaminated water, the described at least a electron transfer mediator of catalytically effective amount becomes and can move freely and dissolve in the whole contaminated water.

Partly or entirely the described at least a electron transfer mediator of catalytically effective amount promptly uses with the form of mixtures " former state " of the independent solid of common exsiccant (being generally particle) material or several solid (being generally particle) material with solid (being generally particle) form.Select or in addition as another kind, before being exposed to contaminated water, under appropriate condition (temperature, pH, mixing), partly or entirely the described at least a electron transfer mediator of catalytically effective amount is dissolved in one or more suitable (water-based is or/and organic) solvents, subsequently with the solution form, promptly use with the solution form of independent solid (the being generally particle) material of dissolved or with the solution form of the mixture of several solids of dissolved (being generally particle) material.

Will discuss immediately as following, the suitable solvent that is used to dissolve given electron transfer mediator specifically depends on water-soluble or water-insoluble electron transfer mediator.Hereinafter provide for exemplary suitable solvent and appropriate condition under each situation.

The electron transfer mediator solubleness that is used to form the homogeneous catalytic reaction system is considered:

For any passing through intermittently or flow pattern, according to homogeneous catalysis contaminated water is exposed to the exemplary concrete optimal way of the described at least a electron transfer mediator of catalytically effective amount hereinafter described, each electron transfer mediator (begin for not by another kind of material load, matrixization, insertion or/and the solid of catching (being generally particle) material) is exposed to contaminated water subsequently, need become and in whole contaminated water, to move freely, to form intermittence or flow pattern homogeneous catalytic reaction system hereinafter described with solvable.

Usually any amount of described at least a electron transfer mediator is dissolved in or is insoluble to pure or clean (unpolluted) water (promptly not being the pending contaminated water of the present invention), for example distillatory deionization filtered water.Be exposed to contaminated water if will be dissolved in those electron transfer mediators of pure or clean water usually, then prediction or test are learnt and fully are dissolved in the contaminated water.Equally, be exposed to contaminated water if will be insoluble to those electron transfer mediators of pure or clean water, expection or test are learnt insoluble or maximum insufficient being dissolved in the contaminated water.

Significantly, the dissolution degree of the given electron transfer mediator in contaminated water or shortage solubleness depend primarily on: (a) type of given electron transfer mediator, quantity, concentration and physicochemical property, feature and behavior; (b) volume of contaminated water and physical chemistry and hydrokinetics (flowing) character, feature, behavior, condition (particularly temperature, pH, pressure and gradient thereof) and form for example are underground water, the surface water, ground water or its array configuration; (c) being present in direct vicinity, to be exposed to other of contaminated water of given electron transfer mediator known or/and possible material or type of material, quantity, concentration and physicochemical property, feature and behavior, for example chemical structure, chemically reactive, solubleness.

In various electron transfer mediators mentioned above, great majority (but of course not whole) are insoluble to pure or clean water, and if be exposed to contaminated water, expection or test are learnt insoluble or maximum insufficient being dissolved in the contaminated water.The organometallic complex electron transfer mediator (catalyzer) of (its any be suitable for use as usually realization the inventive method) that for example well-known [for example 79] great majority (but not being whole) come from porphyrin is insoluble to pure or clean water usually, if and were exposed to contaminated water, would expect insoluble or maximum insufficient being dissolved in the contaminated water.

Water-soluble electron transfer mediator:

By intermittence or flow pattern, according to homogeneous catalysis, wherein all any or multiple electron transfer mediator or all electron transfer mediators of the described at least a electron transfer mediator of catalytically effective amount are dissolved in pure or clean water, and expection or test are learnt and fully are dissolved in the contaminated water, then any or multiple water-soluble electron transfer mediator is with the particle form of form alone or in combination, promptly uses with the independent particulate matter of common exsiccant or the form of mixtures former state of several particulate matters.Select or in addition as another kind, before being exposed to contaminated water, under appropriate condition (temperature, pH, mixing), any or multiple water-soluble electron transfer mediator is dissolved in to form pure or clean (unpolluted) water (for example distillatory deionization filtered water) alone or in combination, subsequently with the solution form, promptly with the solution form of the independent particulate matter of dissolved or the solution form of the mixture of several particulate matters of dissolved use.

For any or multiple water-soluble electron transfer mediator or all water-soluble electron transfer mediators of the described at least a electron transfer mediator that makes catalytically effective amount is dissolved in pure or clean (unpolluted) water (for example distillatory deionization filtered water), exemplary preferred appropriate condition is corresponding to room temperature (about 20 ℃ to about 25 ℃ of temperature); PH is preferably about 1 to about 14; More preferably about 5 to about 9, most preferably is about 6 to about 8; Mix.

As mentioned and hereinafter described, by intermittence or flow pattern, according to homogeneous catalysis, be specially adapted to realize that the exemplary water-soluble electron transfer mediator (catalyzer) of the inventive method is aforesaid tetramethyl pyridine porphyrin-transition metal [5,10,15,20-four (1-methyl-4-pyridine)-porphines-transition metal] [TMPyP-transition metal] metal porphyrin complex and aforesaid tetrahydroxy phenyl tetrazaporphin-transition metal [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines-transition metal] [TP (OH) P-transition metal] metal porphyrin complex, wherein preferred described transition metal is selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].

In above-mentioned exemplary appropriate condition (room temperature; PH is about 5 to about 9; Mix) in the scope, above-mentioned [TMPyP-transition metal] metal porphyrin complex is dissolved in pure or clean water usually, and expection or test are learnt and fully be dissolved in the contaminated water.In above-mentioned exemplary appropriate condition (room temperature; PH is greater than about 7.5; Mix) in the scope, above-mentioned [TP (OH) P-transition metal] metal porphyrin complex is dissolved in pure or clean water usually, and expection or test are learnt and fully be dissolved in the contaminated water.

Therefore, any or multiple above-mentioned [TMPyP-transition metal] electron transfer mediator is or/and [TP (OH) P-transition metal] electron transfer mediator form ground promptly is used to be exposed to contaminated water with the independent particulate matter of common exsiccant or the form of mixtures former state of several particulate matters with particle form alone or in combination.Select or in addition as another kind, before being exposed to contaminated water, in above-mentioned appropriate condition (temperature, pH, mixing) scope, any or multiple these metal porphyrin complex type electron transfer mediators are dissolved in to form pure or clean (unpolluted) water (for example distillatory deionization filtered water) alone or in combination, subsequently with the solution form, promptly with the solution form of the independent particulate matter of dissolved or the solution form of the mixture of several particulate matters of dissolved use to be exposed to contaminated water.

The water-insoluble electron transfer mediator:

By intermittence or flow pattern, according to homogeneous catalysis, wherein all any or multiple electron transfer mediator or all electron transfer mediators of the described at least a electron transfer mediator of catalytically effective amount are insoluble to pure or clean water, and expection or test are learnt insoluble or maximum insufficient being dissolved in the contaminated water, subsequently before being exposed to contaminated water, in appropriate condition (room temperature for example, mix) under, any or multiple water-insoluble electron transfer mediator is dissolved in to form the suitable organic solvent that contains alone or in combination, subsequently with the solution form, promptly with the solution form of the independent particulate matter of dissolved or the solution form of the mixture of several particulate matters of dissolved use.

The exemplary suitable organic solvent that contains is selected from: the aqueous solution that comprises one or more miscible organic solvents of miscible amount; The organic solvent that comprises the water of miscible amount; Pure organic solvent; The solution of the organic solvent that two or more are miscible; And miscible combination.Usually any in various basically organic solvent and the miscible combination thereof can be used for dissolving given water-insoluble electron transfer mediator.Given water-insoluble electron transfer mediator contains the solubleness in the organic solvent or learns or in lab investigation from the prior art instruction concrete.

As mentioned and hereinafter described, by intermittence or flow pattern, according to homogeneous catalysis, be specially adapted to realize that the exemplary water-insoluble electron transfer mediator (catalyzer) of the inventive method is aforesaid tetraphenylporphyrin-transition metal [5,10,15,20-tetraphenyl-21H, 23H-porphines-transition metal] [TPP-transition metal] metal porphyrin complex, wherein preferred described transition metal is selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].In above-mentioned exemplary appropriate condition scope, these [TPP-transition metal] metal porphyrin complexes are insoluble to pure or clean water usually, and expection or test is learnt insoluble or maximum insufficient being dissolved in the contaminated water.

Therefore, before being exposed to contaminated water, under appropriate condition (for example room temperature, mixing), any or multiple above-mentioned [TPP-transition metal] electron transfer mediator is dissolved in to form above-mentioned exemplary suitable a kind of in the organic solvent of containing alone or in combination, subsequently with the solution form, promptly use, to be exposed to contaminated water with the solution form of independent solid (the being generally particle) material of dissolved or with the solution form of the mixture of several solids of dissolved (being generally particle) material.

The particle form of described at least a electron transfer mediator that is prepared catalytically effective amount is or/and the process mentioned above of solution form, therefore when contaminated water is exposed to electron transfer mediator, each electron transfer mediator solution becomes must can move freely and dissolve in the whole contaminated water, to form as mentioned and intermittence hereinafter described or flow pattern homogeneous catalytic reaction system.

,,, as mentioned below contaminated water is exposed wherein or/and after the solution form in the above-mentioned particle form of the described at least a electron transfer mediator of preparation catalytically effective amount according to homogeneous catalysis by intermittently or flow pattern.

Intermittent mode:

Pass through intermittent mode, according to homogeneous catalysis, with any or multiple particle form mentioned above of the described at least a electron transfer mediator of catalytically effective amount or/and the solution form adds to the contaminated water of one batch of fixing or constant number (volume or quality).Contaminated water perhaps fixing with one batch or constant number (volume or quality) adds to any or multiple particle form of described at least a electron transfer mediator of catalytically effective amount or/and the solution form.

In each of this two kinds of exemplary concrete preferred embodiments, in the contaminated water of each batch, carry out various homogeneous catalytic reaction processes and come homogeneous catalysis to handle the contaminated water of this batch.This process for exposing or mode are used in particular for the underground water that is polluted by halogenated organic compounds mentioned above, the surface water, water or its combination on the ground that homogeneous catalysis is handled the fixing or constant number of each batch.In addition, this process for exposing or mode can be used for operating the homogeneous catalysis chemical reactor of batch type, and this reactor obviously is applicable to realization the present invention.

Flow pattern:

By flow pattern, according to homogeneous catalysis, with any or multiple particle form mentioned above of the described at least a electron transfer mediator of catalytically effective amount or/and the solution form adds to (natural or/and pressurization) contaminated current.Any or the multiple particle form of described at least a electron transfer mediator that perhaps will (natural or/and pressurization) contaminated current adds to catalytically effective amount is or/and the solution form.

In each of this two kinds of exemplary concrete preferred embodiments, in the contaminated water of mobile, carry out various homogeneous catalytic reaction processes and come homogeneous catalysis to handle the contaminated water of mobile.This process for exposing or mode are used in particular for carrying out homogeneous catalysis and handle the underground water that is polluted by halogenated organic compounds mentioned above of various liquid forms, the surface water, water or its combination on the ground.In addition, this process for exposing or mode can be used for operating the homogeneous catalysis chemical reactor of mobile or fluidisation type, and this reactor obviously is applicable to realization the present invention.

Heterogeneous catalyst:

For any passing through intermittently or flow pattern, is exposed to the exemplary concrete optimal way of the described at least a electron transfer mediator of catalytically effective amount according to heterogeneous catalyst, with contaminated water hereinafter described, the described at least a electron transfer mediator of described catalytically effective amount begin for by load, matrixization, insert, mix or/and catch and be fixed on usually on (particle is or/and non-particulate) solid carrier or the body material or/and within solid (being generally particle) material.When being exposed to contaminated water, solid carrier or body material are scattered in (promptly being insoluble to) whole contaminated water subsequently.Usually the described at least a electron transfer mediator that begins the fixed catalytically effective amount becomes similarly and is scattered in (promptly being insoluble to) whole contaminated water.But in implementation procedure of the present invention, according to the actual parameter and the condition of given heterogeneous catalyst chemical reaction system, electron transfer mediator any or various fixed can be partially soluble in the contaminated water at least.

Usually all the described at least a electron transfer mediator of catalytically effective amounts is with the particle form of one or more electron transfer mediator solid supported or matrix structure, promptly uses with the independent particulate matter of common exsiccant or the form of mixtures " former state " of several particulate matters.In order to realize method of the present invention, the specific examples of this electron transfer mediator solid supported or matrix structure has the heterogeneous catalyst of diatomite/zero-valent metal mentioned above (ZVM)/electron transfer mediator matrix material type.

Intermittent mode:

Pass through intermittent mode, according to homogeneous catalysis, any or multiple electron transfer mediator solid supported mentioned above of the described at least a electron transfer mediator of catalytically effective amount or matrix structure are added to the contaminated water of one batch of fixing or constant number (volume or quality).Contaminated water perhaps fixing with one batch or constant number (volume or quality) adds to any or multiple electron transfer mediator solid supported or the matrix structure of the described at least a electron transfer mediator of catalytically effective amount.

Flow pattern:

By flow pattern,, any or multiple electron transfer mediator solid supported or the matrix structure mentioned above of the described at least a electron transfer mediator of catalytically effective amount added to (natural or/and pressurization) contaminated current according to homogeneous catalysis.Perhaps (natural or/and pressurization) contaminated current are added to any or multiple electron transfer mediator solid supported or the matrix structure of the described at least a electron transfer mediator of catalytically effective amount.

Concentrating on the environmental science of handling or remedy contaminated water and technical field interested especially is by flow pattern, according to heterogeneous catalyst, realizes the above-mentioned exemplary concrete preferred embodiment of method of the present invention and system.More particularly, (remedy in catalytic treatment, purifying) in the process of method, any or the multiple electron transfer mediator solid supported mentioned above or the matrix structure that comprise the described at least a electron transfer mediator that uses catalytically effective amount for example are included in the original position device that is arranged in the contaminated water of mobile (for example form of the part of active restraining mass (PRB) form of groundwater seepage or underground water pumping and system for handling) or/and be included in and be physically located at or be seated and at the initial position of contaminated water, outside place or the position or away from the initial position of contaminated water, the heterogeneous catalyst of diatomite/zero-valent metal (the ZVM)/electron transfer mediator matrix material type in the device of offing normal of place or position operation (for example catalyzed chemical reaction device).

Exemplary concrete preferred embodiment for this concrete heterogeneous catalyst flow pattern type that realizes method of the present invention and system, preferred process for exposing or mode make that (natural or/and pressurization) contaminated current (for example are the contaminated underground water of mobile, the surface water, on the ground water or its array configuration) natural or/and pressurization ground contact with electron transfer mediator solid supported or matrix structure physical chemistry and flows within it and pass through this electron transfer mediator, and electron transfer mediator solid supported or the maintenance of matrix structure are included in original position or/and in the device of offing normal.

In addition, exemplary concrete preferred embodiment for this concrete heterogeneous catalyst flow pattern type that realizes method of the present invention and system, wherein said (natural or/and pressurization) contaminated current are specially the contaminated underground water of mobile (underground water zone for example, water reservoir or aqueous stratum) form, preferred process for exposing or mode make natural or/and pressurization ground flow in electron transfer mediator solid supported that comprises or matrix structure and the volumetric flow rate of (natural or/and pressurization) contaminated current of passing through is equal to or greater than natural or/and pressurization ground at least by ground or directly around the volumetric flow rate of the contaminated current of the material mobile of electron transfer mediator solid supported that comprises or matrix structure (natural or/and pressurization).Therefore, the perviousness (to the contaminated underground water of mobile) of feasible electron transfer mediator solid supported that comprises of preferred process for exposing or mode or matrix structure is equal to or greater than ground or direct around the electron transfer mediator solid supported that comprises or the perviousness (to the contaminated underground water of mobile) of matrix structured material at least.

The exemplary concrete preferred embodiment of the heterogeneous catalyst flow pattern type of aforementioned realization method of the present invention and system is specially adapted to the various exemplary concrete preferred embodiment (hereinafter further describing and be shown in Fig. 4-7) of system, and wherein said electron transfer mediator solid supported or matrix structure are included at least a (original position is or/and off normal) device of the one or more positions that are positioned at the whole system that is used to process or handle contaminated water.

Reductive condition in contaminated water:

(promptly relative under reduction (anaerobism or anoxic) condition with oxidizing condition, reductive condition is preponderated in pending contaminated water and in the whole contaminated water), for by intermittently or flow pattern, according to homogeneous catalysis, or/and, carry out contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount by intermittently or flow pattern, realize every kind of above-mentioned exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst.

Well-known as association area of the present invention, for example when relating to redox (redox) chemical reaction (particularly reductive dehalogenation), phrase " reductive condition " typically refers to such condition that exists, wherein at least partial oxidation reduction (redox) chemical reaction phenomenon, mechanism or/and the energy of process derived from the electrochemical reduction of one or more (easily oxidized) materials (chemical substance).At aqueous environment for example is that the common example of dominant especially reductive condition is nitrate reduction condition, reductibility manganese reductive condition, the ferrous reductive condition of reductibility, reducible sulfur reductive condition and reductibility methylene radical reductive condition in the contaminated water of underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), ground water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its array configuration.Each example of reductive condition is meant such condition that exists, wherein at least partial oxidation reduce chemical reacting phenomenon, mechanism or/and the energy of method alone or in combination form ground derived from the electrochemical reduction of one or more corresponding (easily oxidized) materials (chemical substance).More particularly, described chemical substance is for example for comprising nitrate radical [NO respectively ₃ ^-] or nitrate [NO ₃] (the Mn for example or/and manganese ^{+ 4}) or manganese [Mn] or/and iron (Fe for example ^{+ 3}Or Fe ^{+ 2}) or iron [Fe] or/and sulfate radical [SO ₄ ^-2] or vitriol [SO ₄] or/and carbonic acid gas [CO ₂] or one or more (comparatively easily oxidized) materials (chemical substance) of carbonic acid gas.

In aqueous environment, for example be the contaminated water of underground water, the surface water, ground water or its array configuration, " oxidizing condition " typically refers to such condition that exists, wherein at least partial oxidation reduction (redox) chemical reaction phenomenon, mechanism or/and the energy of method derived from the electrochemical oxidation of one or more (more easily being reduced) materials (chemical substance), based on free (unreacted) molecular oxygen [O of the dissolved in contaminated water ₂] existence and reaction.The redox chemistry reaction that drives compared with needs and the reduction that under reductive condition, takes place, dissolved oxygen [O ₂] the redox chemistry significant reaction thermodynamics that drives of the needs of type and the oxidation that takes place under oxidizing condition is favourable.But, in these aqueous environments, to the needs of free (unreacted) molecular oxygen of dissolved with consume usually very big and fast.Exhausting of natural free (unreacted) molecular oxygen finally causes in these aqueous environments above-mentioned reductive condition to be preponderated.

In order to realize method of the present invention and system, natural existence in contaminated water is or/and produce aforesaid reductive condition by mankind's activity (mankind).Preponderate and think and then need in contaminated water, artificially not produce reductive condition usually when being enough to make effectively phenomenon, mechanism and the method for (homogeneous phase or heterogeneous) catalytic reduction dehalogenation reaction of electron transport mediation to make halogenated organic compounds pollutent catalytic reduction dehalogenation in the contaminated water when reductive condition in contaminated water is natural.But, when reductive condition in contaminated water is natural when not preponderating or thinking that phenomenon, mechanism and the method for (homogeneous phase or heterogeneous) catalytic reduction dehalogenation reaction of being not enough to utilize the electron transport mediation makes halogenated organic compounds pollutent catalytic reduction dehalogenation in the contaminated water, then need in contaminated water, artificially produce reductive condition usually.Therefore, under latter event, method of the present invention and system also are included in the artificial process that produces reductive condition in the contaminated water.

Body electron donor(ED) or reductive agent:

The described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, by contaminated water being exposed at least a body electron donor(ED) or the reductive agent artificial reductive condition that produces in contaminated water.Perhaps, comprised at least a body electron donor(ED) or reductive agent heterogeneous catalyst (heterogeneous catalyst of for example above-mentioned diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type) artificial reductive condition that produces in contaminated water by using as the electron transfer mediator solid supported or the matrix structure type of the part of heterogeneous catalyst structure or composition.

Briefly say, can under reduction (anaerobism or anoxic) condition, can be used for realizing method of the present invention and system by any basically body electron donor(ED) or the reductive agent of reduction electron transfer mediator.Say that briefly at least a body electron donor(ED) of any or all or reductive agent are dissolved in or are insoluble in the contaminated water.Specifically, in the body electron donor(ED) or reductive agent of the following stated, metal element is insoluble in the contaminated water usually, but compound is dissolved in the contaminated water.

Preferred described at least a body electron donor(ED) or reductive agent comprise metal element (zero-valent metal).Preferred described body electron donor(ED) or reductive agent metal element (zero-valent metal) chosen from Fe [Fe ⁰], lithium [Li ⁰], sodium [Na ⁰], potassium [K ⁰], beryllium [Be ⁰], magnesium [Mg ⁰], titanium [Ti ⁰] and any mixture.Perhaps, described body electron donor(ED) or reductive agent compound are selected from citric acid titanium (III) [Ti (OC (CH ₂COOH) ₂COOH], POTASSIUM BOROHYDRIDE [KBH ₄], sodium borohydride [NaBH ₄], lithium hydride [LiH], potassium hydride KH [KaH], sodium hydride [NaH], boron trihydride [BH ₃], three aluminum hydride [AlH ₃], hydrazine [H ₂NNH ₂], triphenylphosphate [PPh ₃], V-Brite B [Na ₂S ₂O ₄] and any combination.

Say that briefly the described at least a body electron donor(ED) that contaminated water exposed or the amount of reductive agent are variable.The described at least a body electron donor(ED) that contaminated water exposed or the amount of reductive agent are represented with volumetric molar concentration, corresponding to the mole number of at least a body electron donor(ED) described in the contaminated water of unit volume (for example rising) or reductive agent, and be designated as mole body electron donor(ED) or reductive agent/liter contaminated water.When the described at least a body electron donor(ED) that contaminated water exposed or the amount of reductive agent are represented with volumetric molar concentration, be preferably about 10 ^-4To about 1.0 moles of body electron donor(ED)s or reductive agent/liter contaminated water, more preferably about 10 ^-3To about 10 ^-1Mole body electron donor(ED) or reductive agent/liter contaminated water.The described at least a body electron donor(ED) that contaminated water exposed or the optimal number of reductive agent are expressed as about 10 with volumetric molar concentration ^-2Mole body electron donor(ED) or reductive agent/liter contaminated water.

Contaminated water is exposed to body electron donor(ED) or reductive agent:

Briefly say, contaminated water is exposed to described at least a body electron donor(ED) or reductive agent, the artificial reductive condition that produces in contaminated water according in the well-known in the art various different modes consistent any with homogeneous phase that forms previously described intermittent mode or flow pattern or heterogeneous catalytic reaction system.As indicated above, in order to realize method of the present invention and system, the described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, contaminated water is exposed at least a body electron donor(ED) or reductive agent.According to by intermittently or flow pattern, according to homogeneous catalysis, by intermittently or flow pattern, according to heterogeneous catalyst realize the previously described exemplary concrete preferred embodiment of method of the present invention determine the described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, contaminated water is exposed to the practical ways of at least a body electron donor(ED) or reductive agent, and consistent with it.

For example in order to realize method of the present invention and system according to homogeneous catalysis or according to heterogeneous catalyst (passing through intermittent mode separately), the described at least a electron transfer mediator that a collection of contaminated water is exposed to catalytically effective amount just before or/and during or/and just, described at least a body electron donor(ED) or reductive agent are added to the contaminated water of the fixing or constant number (volume or quality) of this batch.Perhaps the described at least a electron transfer mediator that a collection of contaminated water is exposed to catalytically effective amount just before or/and during or/and just, a collection of contaminated water fixing or constant number (volume or quality) is added at least a body electron donor(ED) or reductive agent.

For example in order to realize method of the present invention and system according to homogeneous catalysis or according to heterogeneous catalyst (passing through flow pattern separately), the described at least a electron transfer mediator that contaminated current is exposed to catalytically effective amount just before or/and during or/and just, described at least a body electron donor(ED) or reductive agent are added to (natural or/and pressurization) contaminated current.Perhaps the described at least a electron transfer mediator that contaminated current is exposed to catalytically effective amount just before or/and during or/and just, (natural or/and pressurization) contaminated current are added at least a body electron donor(ED) or reductive agent.

Preferably in contaminated water natural existence or/and artificially produce reductive condition, only make in the contaminated water halogenated organic compounds contaminant species by described at least a electron transfer mediator (catalyzer) catalytic reduction, and can be present in the contaminated water or/and the uncontamination thing material (for example oxygen) in the contaminated water of next-door neighbour not by described at least a electron transfer mediator (catalyzer) catalytic reduction.

The time of the catalytic reduction dehalogenation reaction or time length:

Briefly say, for each of the above-mentioned exemplary concrete preferred embodiment that realizes method of the present invention and system, under reductive condition, contaminated water being exposed to time of described at least a electron transfer mediator of catalytically effective amount or time length (for example hour, day, week etc.) depends on one-level mentioned above, secondary and three grades of parameters of given intermittence or flow pattern homogeneous phase or heterogeneous catalytic reaction system.Specifically, the type that relates to the described at least a electron transfer mediator of target in contaminated water (known or/and suspect) halogenated organic compounds pollutent and catalytically effective amount, quantity, concentration and physicochemical property, feature and behavior, the volume and physical chemistry and hydrokinetics (flowing) character that also relate to contaminated water, feature and behavior and form for example are underground water (underground water zone for example, water reservoir or aqueous stratum), the surface water (river for example, the lake, the pond, pond or surface water water reservoir), ground water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its array configuration.

As indicated above, the system of the water of catalytic treatment contaminated with halogenated organic compounds of the present invention comprises following major portion and function thereof: (a) at least a electron transfer mediator; (b) be used to comprise at least a (original position is or/and off normal) device of the described at least a electron transfer mediator of catalytically effective amount, be used under reductive condition described contaminated water being exposed to described at least a electron transfer mediator, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.Use system of the present invention to cause the reduction of at least a halogenated organic compounds concentration in the contaminated water.

In order to realize method of the present invention and system, in the process of catalytic treatment (remedy, purifying) method, the original position device basically physically (on the space) be positioned at or be seated and on position, place or the position of the reality of contaminated water or within operation.Therefore, the original position device links to each other with corresponding device thereof hydrokinetics by being correlated with (identical usually) physics (space) position of original position device and contaminated water unanimity with contaminated water.In the process of catalytic treatment (remedy, purifying) method, off normal device basically physically (on the space) be positioned at or be seated and beyond position, place or the position of the reality of contaminated water or away from the place operation.Therefore, off normal device and contaminated water links to each other with corresponding device thereof hydrokinetics by inconsistent with contaminated water with the device of offing normal (separating usually) physics (space) position is relevant.

Refer again to Fig. 4-7, wherein explanation is used to comprise the exemplary original position that is suitable for and the device of offing normal as the described at least a electron transfer mediator of the catalytically effective amount of heterogeneous catalyst.The original position device is the continuous form (PRB) of descending the active restraining mass of water permeate at least in part of filling ditch or wall (for example original position device 20 (Fig. 4)) or filling well (for example original position device 30 (Fig. 5)) structure separately, or is the form (for example original position device 32 (Fig. 6)) of the part of underground water pumping and system for handling.Be used to comprise as homogeneous catalyst or/and the device of offing normal that is suitable for as the described at least a electron transfer mediator of the catalytically effective amount of heterogeneous catalyst exemplary is the form (device 48 (Fig. 7) of for example offing normal) of the part of water processing reactor system on the ground.

Used herein with in the instruction in contaminated groundwater treatment (remedy, purifying) field with use the active restraining mass of consistent perviousness (PRB) to be meant the sealing or the open design of for example filling ditch, wall or individual well, or provide passive and dam and the contaminated phreatic structure of in-situ treatment.The osmotically active restraining mass is characterised in that to have the infiltration area that comprises or produce active treatment zone; described infiltration area comprises the high activity material; the described at least a electron transfer mediator (as heterogeneous catalyst) of the catalytically effective amount of part (particle is or/and non-particulate) solid carrier or body material form for example; and the also optional activity that comprises not too is or/and non-active material; by pollutent directly is exposed to active material, guiding is dammed and is remedied or purifying groundwater pollutant plumage (being dense specific underground water zone or district of pollutent).

Ideally, PRB provides the preferred flowing-path of contaminated underground water by active material and other materials that may exist, as with the halogenated organic compounds catalyzed degradation in the contaminated water, transform or change into not dangerous or/and Wei Xian chemical substance not too, this material comes out from restraining mass, and the destructiveness to natural groundwater stream is minimum simultaneously.Usually make contaminated Groundwater Flow by PRB by natural (pressure or the current) gradient that flows, still, what PRB was interior is configured in the upstream or/and the pumping flow process in downstream also can be used for finishing the setting of PRB.PRB can be along or/and cross the permanent or semipermanent device form in the moving path of pollutent plume and install.Perhaps PRB (inactivation) active catalyst material that can easily be convenient to use up and other materials that may exist removes or/and the form of the part of displaced reaction in device structure or configuration is installed.

Fig. 4 is the explanation flow pattern that passes through as indicated above, realizes the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst.Contaminated water is that natural groundwater is streamed; and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is for whole dispersion and be included in original position device interior part (particle is or/and non-particulate) solid carrier or body material, and described original position device is the form than lower part of filling the active restraining mass of groundwater seepage (PRB) of ditch or wall construction continuously.

As shown in Figure 4, by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity (in 10, represent with the irregular form of filling) underground water 10 that pollutes, natural flowing (in 10, representing) between the subterranean zone under the end face district 16 14 by pointing to right-hand arrow.Described at least a electron transfer mediator (as heterogeneous catalyst) the 18 whole dispersions of catalytically effective amount and being included in the original position device 20, described original position device is the form than lower part of filling the active restraining mass of perviousness (PRB) 22 of ditch or wall construction continuously, and its higher part 24 is filled inactive filler 26.

The described at least a electron transfer mediator 18 of catalytically effective amount is constructed and be used to comprise to original position device 20, and can under reduction (anaerobism or anoxic) condition, natural contaminated underground water (10 add 12) stream be exposed to the described at least a electron transfer mediator 18 of catalytically effective amount.In addition, by flow pattern, according to heterogeneous catalyst structure and operation original position device 20.In the contaminated underground water of mobile (10 add 12), carry out various heterogeneous catalytic reaction processes and come heterogeneous catalyst to handle the contaminated underground water of mobile (10 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated underground water (10 add 12).Therefore, come out the mobile underground water 10 of (to right-hand) through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12 from original position device 20.

Fig. 5 is the explanation flow pattern that passes through as indicated above, realizes the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst.Contaminated water is that natural groundwater is streamed; and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is whole dispersion and each interior part (particle is or/and non-particulate) solid carrier or the body material that is included in a plurality of original position devices, the active restraining mass (PRB) of groundwater seepage that described original position device is respectively done for oneself and filled well construction separately.

As shown in Figure 5, the underground water 10 that is polluted by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity is natural flowing (in 10, representing by pointing to right-hand arrow) between the subterranean zone under the end face district 16 14.Described at least a electron transfer mediator (as heterogeneous catalyst) the 18 whole dispersions of catalytically effective amount and being included within a plurality of (for example 6) original position device 30 each, described original position device is the active restraining mass (PRB) of groundwater seepage of filling well construction separately.

Each structure in the original position device 30 and be used to comprise the described at least a electron transfer mediator 18 of catalytically effective amount, and can under reduction (anaerobism or anoxic) condition, natural contaminated underground water (10 add 12) stream be exposed to the described at least a electron transfer mediator 18 of catalytically effective amount.In addition, by flow pattern, according in heterogeneous catalyst structure and the operation original position device 30 each.In the contaminated underground water of mobile (10 add 12), carry out various heterogeneous catalytic reaction processes and come heterogeneous catalyst to handle the contaminated underground water of mobile (10 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated underground water (10 add 12).Therefore, come out the mobile underground water 10 of (to right-hand) through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12 from original position device 30.

Fig. 6 is the explanation flow pattern that passes through as indicated above, realizes the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst.Contaminated water is groundwater flow form natural and pressurization; and the described at least a electron transfer mediator (as heterogeneous catalyst) of catalytically effective amount is for whole dispersion and be included in part (particle is or/and non-particulate) solid carrier or body material in the original position device, described original position device or be the form of the part of underground water pumping and system for handling.

As shown in Figure 6, except any possible natural stream (in 10, represent by pointing to right-hand single arrow), the underground water 10 that is polluted by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity also send device 36 pumpings (in 10 by water pump, have two groups of arrows to point to water pump separately and send device 36), in pressurized flow between the subterranean zone under the end face district 16 14.Described at least a electron transfer mediator (as heterogeneous catalyst) the 18 whole dispersions of catalytically effective amount and being included in the original position device 32, described original position device is the middle portion of underground water pumping and system for handling (36,32 and 40).

Send device 36 pumpings by the water pump that is positioned at underground water pumping and system for handling (36,32 and 40) than lower part, with (10 the add 12) pumping of contaminated underground water and pressurized stream to and send the volume and the inclusion 34 of device 36 by water pump.Subsequently with contaminated underground water (10 add 12) pumping and pressurization is upwards flowed, is flow to and original position device 32 by being included in the middle portion that is positioned at underground water pumping and system for handling (36,32 and 40) in the described at least a electron transfer mediator (as heterogeneous catalyst) 18 of catalytically effective amount.Subsequently will through (remedying or purifying) underground water 10 pumpings of catalytic treatment and pressurization be upwards flowed, is flow to and the volume and the inclusion 38 of the treated water collection/passage chamber 40 of higher part by being positioned at underground water pumping and system for handling (36,32 and 40).With after the underground water 10 of catalytic treatment come out by the top of treated water collection/passage chamber 40 (as described) at 42.

The described at least a electron transfer mediator 18 of catalytically effective amount is constructed and be used to comprise to original position device 32, and can under reduction (anaerobism or anoxic) condition, the stream of the natural of contaminated underground water (10 add 12) and pressurization be exposed to the described at least a electron transfer mediator 18 of catalytically effective amount.In addition, by flow pattern, according to heterogeneous catalyst structure and operation original position device 32.In the contaminated underground water of mobile (10 add 12), carry out various heterogeneous catalytic reaction processes and come heterogeneous catalyst to handle the contaminated underground water of mobile (10 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated underground water (10 add 12).Therefore, the mobile underground water 42 that comes out from the top of treated water collection/passage chamber 40 is through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12.

Fig. 7 pass through intermittence or flow pattern for explanation is as indicated above, according to homogeneous phase or/and heterogeneous catalyst is realized the synoptic diagram of sectional view of the exemplary concrete preferred embodiment of method of the present invention and system.Contaminated water be natural or/and the underground water, the surface water of pressurization or/and current form on the ground.The described at least a electron transfer mediator of catalytically effective amount is to be included in the interior water-soluble granular form of the device of offing normal or/and the homogeneous catalyst of aqueous solution form; part (particle is or/and the non-particulate) solid carrier or/and whole dispersion and being included in is offed normal in the device or the heterogeneous catalyst of body material form, the wherein said device of offing normal is the form of the part of water processing reactor system on the ground.

First kind of configuration:

According to first kind of configuration shown in Figure 7, except any possible natural stream (in 10, represent with pointing to right-hand single arrow), the underground water 10 (for example underground water zone, water reservoir or aqueous stratum) that is polluted by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity all send device 46 pumpings (in 10 by water pump, have two groups of arrows to point to water pump separately and send device 46), in pressurized flow between the subterranean zone under the end face district 16 14.

In first kind of configuration, partly or entirely the described at least a electron transfer mediator of catalytically effective amount is to be included in water-soluble granular forms in the device 48 of offing normal or/and the homogeneous catalyst 18 of aqueous solution form, and the described device of offing normal is the form of the part of water processing reactor system 50 on the ground.In this case, by intermittent mode or by flow pattern, according to homogeneous catalysis structure and the operation device 48 of offing normal.Select or in addition as another kind; partly or entirely the described at least a electron transfer mediator of catalytically effective amount is whole dispersion and is included in interior part (particle is or/and the non-particulate) solid carrier of the device of offing normal or the heterogeneous catalyst 18 of body material form, the described form of device for the part of ground water processing reactor system 50 of offing normal.In this case, by intermittent mode or by flow pattern, according to heterogeneous catalyst structure and the operation device 48 of offing normal.

By water transfer line (pipe) 52 with contaminated underground water (10 add 12) from water pump send device 46 pumpings and pressurized stream to and send the volume and the inclusion 44 of device 46 by water pump, the device 48 of offing normal to ground water processing reactor system 50 is exposed to the homogeneous phase form subsequently or/and the described at least a electron transfer mediator catalyzer 18 of the catalytically effective amount of heterogeneous form.To come out from ground water processing reactor system 50 (as at as described in 54) through (remedying or purifying) underground water 10 of catalytic treatment subsequently.

The device 48 of offing normal is constructed and is used to comprise homogeneous phase or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form, and can under reduction (anaerobism or anoxic) condition, the natural of contaminated underground water (10 add 12) and the stream that pressurizes be exposed to the homogeneous phase form or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form.In addition, by intermittently or flow pattern, according to homogeneous phase or/and heterogeneous catalyst structure and operation are offed normal device 48.Intermittently or carry out various homogeneous phases in the contaminated underground water of mobile (10 add 12) or/and the heterogeneous catalytic reaction process is come homogeneous phase heterogeneous catalyst is handled the contaminated underground water of mobile (10 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated underground water (10 add 12).Therefore, the underground water 54 that will come out from ground water processing reactor system 50 is through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12.

Second kind of configuration:

According to second kind of configuration shown in Figure 7, the surface water 56 (for example river, lake, pond, pond or surface water water reservoir are represented with 58 herein usually) that is polluted by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity is positioned at end face district 16.

In second kind of configuration, partly or entirely the described at least a electron transfer mediator of catalytically effective amount is to be included in water-soluble granular forms in the device 48 of offing normal or/and the homogeneous catalyst 18 of aqueous solution form, and the described device of offing normal is the form of the part of water processing reactor system 50 on the ground.In this case, by intermittent mode or by flow pattern, according to homogeneous catalysis structure and the operation device 48 of offing normal.Select or in addition as another kind; partly or entirely the described at least a electron transfer mediator of catalytically effective amount is whole dispersion and is included in part (particle is or/and non-particulate) solid carrier in the device 48 of offing normal or the heterogeneous catalyst 18 of body material form, and the described device of offing normal is the form of the part of water processing reactor system 50 on the ground.In this case, by intermittent mode or by flow pattern, according to heterogeneous catalyst structure and the operation device 48 of offing normal.

Except any possible natural stream (in 56, representing) with pointing to two right-hand arrows, by water transfer line (pipe) 60 also with the contaminated surface water (56 the add 12) Congjiang, lake, pond, pond or 58 pumpings of surface water water reservoir and pressurized stream to the device 48 of offing normal of water processing reactor system 50 on the ground, be exposed to the homogeneous phase form subsequently or/and the described at least a electron transfer mediator catalyzer 18 of the catalytically effective amount of heterogeneous form.To come out from above-mentioned ground water processing reactor system 50 (as described) through (remedying or purifying) surface water 56 of catalytic treatment subsequently at 54.

The device 48 of offing normal is constructed and is used to comprise homogeneous phase or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form, and can under reduction (anaerobism or anoxic) condition, the natural of the contaminated surface water (56 add 12) and the stream that pressurizes be exposed to the homogeneous phase form or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form.In addition, by intermittently or flow pattern, according to homogeneous phase or/and heterogeneous catalyst structure and operation are offed normal device 48.Intermittently or carry out various homogeneous phases in the contaminated surface water of mobile (56 add 12) or/and the heterogeneous catalytic reaction process is come homogeneous phase heterogeneous catalyst is handled the contaminated surface water of mobile (56 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated surface water (56 add 12).Therefore, the surface water 56 that will come out from ground water processing reactor system 50 is through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12.

The third configuration:

According to the third configuration shown in Figure 7, (existed by the halogenated organic compounds pollutent 12 of the above exemplary description of any kind and quantity, but not expression in 62 in Fig. 7) the ground water 62 that pollutes (for example the source, above-mentioned ground or the supply of water water reservoir or dwelling house or commercial potable water on the ground represented with 64 herein usually) is positioned in the end face district 16 and the top.

In the third configuration, partly or entirely the described at least a electron transfer mediator of catalytically effective amount is to be included in water-soluble granular forms in the device 48 of offing normal or/and the homogeneous catalyst 18 of aqueous solution form, and the described device of offing normal is the form of the part of water processing reactor system 50 on the ground.In this case, by intermittent mode or by flow pattern, according to homogeneous catalysis structure and the operation device 48 of offing normal.Select or in addition as another kind; partly or entirely the described at least a electron transfer mediator of catalytically effective amount is whole dispersion and is included in part (particle is or/and non-particulate) solid carrier in the device 48 of offing normal or the heterogeneous catalyst 18 of body material form, and the described device of offing normal is the form of the part of water processing reactor system 50 on the ground.In this case, by intermittent mode or by flow pattern, according to heterogeneous catalyst structure and the operation device 48 of offing normal.

By water transfer line (pipe) 66 with contaminated ground water (62 add 12) from source, the ground of ground water water reservoir or dwelling house or commercial potable water or supply with 64 pumpings and pressurized stream to the device 48 of offing normal of water processing reactor system 50 on the ground, be exposed to the homogeneous phase form subsequently or/and the described at least a electron transfer mediator catalyzer 18 of the catalytically effective amount of heterogeneous form.To come out from ground water processing reactor system 50 (as described) through (remedying or purifying) ground of catalytic treatment water 62 subsequently at 54.

The device 48 of offing normal is constructed and is used to comprise homogeneous phase or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form, and can under reduction (anaerobism or anoxic) condition, the natural of contaminated ground water (62 add 12) and the stream that pressurizes be exposed to the homogeneous phase form or/and the described at least a electron transfer mediator 18 of the catalytically effective amount of heterogeneous form.In addition, by intermittently or flow pattern, according to homogeneous phase or/and heterogeneous catalyst structure and operation are offed normal device 48.Intermittently or carry out various homogeneous phases in the contaminated ground of the mobile water (62 add 12) or/and the heterogeneous catalytic reaction process is come homogeneous phase heterogeneous catalyst is handled the contaminated surface water of mobile (56 add 12), thereby be reduced in the concentration of at least a halogenated organic compounds pollutent 12 in the contaminated ground water (62 add 12).Therefore, the ground water 62 that will come out from ground water processing reactor system 50 is through catalytic treatment (remedying or purifying), to reduce the concentration of at least a halogenated organic compounds pollutent 12.

It should be noted, shown in Fig. 4-7, for in the above-mentioned exemplary concrete preferred embodiment that realizes method of the present invention and system any, by intermittently or flow pattern, according to homogeneous catalysis, or/and by intermittently or flow pattern, according to heterogeneous catalyst, (promptly relative under reduction (anaerobism or anoxic) condition with oxidizing condition, reductive condition is preponderated in whole pending contaminated water), contaminated water is exposed to the described at least a electron transfer mediator of catalytically effective amount.

Mentioned above as the front, natural existence in contaminated water is or/and produce reductive condition by mankind's activity (mankind).When reductive condition in contaminated water is natural when preponderating and thinking that being enough to effectively utilize phenomenon, mechanism and the method for (homogeneous phase or heterogeneous) catalytic reduction dehalogenation reaction of electron transport mediation makes halogenated organic compounds pollutent catalytic reduction dehalogenation in the contaminated water, then need in contaminated water, artificially not produce reductive condition usually.But, when reductive condition in contaminated water is natural when not preponderating or thinking that phenomenon, mechanism and the method for (homogeneous phase or heterogeneous) catalytic reduction dehalogenation reaction of being not enough to effectively utilize the electron transport mediation makes halogenated organic compounds pollutent catalytic reduction dehalogenation in the contaminated water, then need in contaminated water, artificially produce reductive condition usually.Therefore, under latter event, shown in Fig. 4-7, realize that any above-mentioned exemplary concrete preferred embodiment of method of the present invention and system also is included in the artificial process that produces reductive condition in the contaminated water.

Mentioned above as the front, the described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, by contaminated water being exposed at least a body electron donor(ED) or the reductive agent artificial reductive condition that produces in contaminated water.Perhaps comprised at least a body electron donor(ED) or reductive agent heterogeneous catalyst (heterogeneous catalyst of for example above-mentioned diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type) artificial reductive condition that produces in contaminated water as the electron transfer mediator solid supported or the matrix structure type of the part of heterogeneous catalyst structure or composition by using.

According to by intermittently or flow pattern, according to homogeneous catalysis, or by intermittently or flow pattern, realize that the previously described exemplary concrete preferred embodiment of method of the present invention is determined and consistent with it according to heterogeneous catalyst, the described at least a electron transfer mediator that contaminated water is exposed to catalytically effective amount just before or/and during or/and just, contaminated water is exposed to the practical ways of at least a body electron donor(ED) or reductive agent.

Usually shown in Fig. 4-7, for passing through intermittently or flow pattern, realize any above-mentioned exemplary concrete preferred embodiment of method of the present invention and system according to heterogeneous catalyst, after heterogeneous catalyst is handled contaminated water, the heterogeneous catalyst 18 of electron transfer mediator solid supported or matrix structure type can be from the original position device of the association that is used to handle contaminated water (original position device 20 (Fig. 4) for example, original position device 30 (Fig. 5), original position device 32 (Fig. 6)), the device (device 48 (Fig. 7) of for example offing normal) of offing normal is removed, and recirculation is used to handle contaminated water.This recirculation can for example comprise that the heterogeneous catalyst 18 with electron transfer mediator solid supported or matrix structure type carries out cleaning course, comprise that selectivity is removed the pollutent that is adsorbed from solid carrier or matrix, nondestructive ground is handled and processing solid carrier or matrix simultaneously.

Above the method for the present invention of exemplary description and system are specially adapted to the water of catalytic treatment contaminated with halogenated organic compounds, and wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof.But, method of the present invention and system are applicable to the water that catalytic treatment is polluted by the halogenated organic compounds of other types or kind usually, and the halogenated organic compounds of described other types or kind is not limited to halogenation organic herbicide, its halogen-containing analogue or its halogen-containing derivative.

After investigating following examples (these embodiment will limit to the present invention), the novel and of the present invention aspect of above exemplary description of the present invention and feature and advantage thereof become apparent to those skilled in the art.In addition, mentioned above and each embodiment of following claim part the present invention for required protection and aspect in following examples, can find experiment support.

Embodiment

Refer now to following examples (embodiment 1-4),, the present invention is described in nonrestrictive mode in conjunction with above-mentioned explanation.

Atrazine [C ₈H ₁₄ClN ₅] be the halogenation organic herbicide member of the most well-known exemplary chlorination organonitrogen weedicide (CONH) type of chlorotriazine weedicide group (Fig. 1).Background parts is described as mentioned, the degraded product of atrazine and halogen-containing (particularly chlorine) thereof is the most widely used agrochemicals in various forms of water, and be the most general, lasting, confirmation or potentially dangerous (poisonous), undesirable pollutent, described various forms of water are underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply with) on the ground or its array configuration on the ground for example.Therefore, handle or remedy the concern that the water that is polluted by atrazine enjoys environmental science and the technical field of being devoted to handle or remedy contaminated water.

Following examples 1-4 based on by intermittent mode, according to homogeneous catalysis, use different metal porphyrin complex type electron transfer mediator (homogeneous phase) catalyzer and dissimilar body electron donor(ED) or reductive agents, the water that catalytic treatment is polluted by atrazine (as the exemplary CONH type of halogenation organic herbicide water pollutant).Embodiment 1-4 clearly illustrates the realization of the present invention of above exemplary description.

Material and experimental technique

Water:

Distillatory deionization filtered water is produced by Milli-Q desalt system, all uses distillatory deionization filtered water in the text.

Atrazine-water pollutant:

Atrazine, 99%, derive from Agan Chemicals, Ashdod, Israel.

The water that is polluted by atrazine:

By an amount of atrazine being dissolved in the distillatory deionization filtered water, preparation concentration is the liquid storage of the water that is polluted by atrazine of 28mg, 12mg or 2.8mg atrazine/premium on currency, respectively corresponding to 28ppm, 12ppm or 2.8ppm atrazine/contaminated water (under used condition, the maxima solubility of atrazine in water is about 28mg/ liter (28ppm)).

Electron transfer mediator (homogeneous phase) catalyzer:

(free alkali) porphyrin: tetramethyl pyridine porphyrin [5,10,15,20-four (1-methyl-4-pyridine)-porphines] [TMPyP]; Tetrahydroxy phenyl tetrazaporphin [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines] [TP (OH) P]; With 4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acid) [TBSP], derive from Aldrich.

Metal porphyrin complex: tetramethyl pyridine porphyrin-nickel [5,10,15,20-four (1-methyl-4-pyridine)-porphines-nickel] [TMPyP-Ni]; Tetrahydroxy phenyl tetrazaporphin-cobalt [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines-cobalt] [TP (OH) P-Co]; Tetramethyl pyridine porphyrin-cobalt [5,10,15,20-four (1-methyl-4-pyridine)-porphines-cobalt] [TMPyP-Co]; With 4,4 ', 4 ＂, 4 " '-(porphines-5; 10,15,20-four bases) four (Phenylsulfonic acid)-cobalts [TBSP-Co], use open method and technology [61; 100,101], synthesize by corresponding [TMPyP], [TP (OH) P] and [TBSP] (free alkali) porphyrin and transition metal solution.

At pH is under the 5-9, and by synthetic [TMPyP-Ni] metal porphyrin complex is dissolved in the distillatory deionization filtered water, preparation concentration is the moisture liquid storage of [TMPyP-Ni] metal porphyrin complex of 2mM.This liquid storage is used for embodiment 1, is used to provide [TMPyP-Ni] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

Sodium hydroxide [NaOH] solution by adding AG in advance with pH regulator to greater than 7.5, by synthetic [TP (OH) P-Co] metal porphyrin complex is dissolved in the distillatory deionization filtered water, preparation concentration is the moisture liquid storage of [TP (OH) P-Co] metal porphyrin complex of 2mM.This liquid storage is used for embodiment 2, is used to provide [TP (OH) P-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

At pH is under the 5-9, and by synthetic [TMPyP-Co] metal porphyrin complex is dissolved in the distillatory deionization filtered water, preparation concentration is the moisture liquid storage of [TMPyP-Co] metal porphyrin complex of 2mM.This liquid storage is used for embodiment 3, is used to provide [TMPyP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

Sodium hydroxide [NaOH] solution by adding AG in advance with pH regulator to greater than 7, by synthetic [TBSP-Co] metal porphyrin complex is dissolved in the distillatory deionization filtered water, preparation concentration is the moisture liquid storage of [TBSP-Co] metal porphyrin complex of 2mM.This liquid storage is used for embodiment 4, is used to provide [TBSP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

Body electron donor(ED) or reductive agent:

Use the Zero-valent Iron [Fe of open method and technology [102] synthesis of nano size particles form ⁰].Before use, the exsiccant zero-valent iron particle is stored in the anaerobic room that comprises oxygen-free atmosphere that (USA), this atmosphere is by the nitrogen [N with 95/5 mole or intrinsic standoff ratio for Coy Laboratory Products, MI ₂] gas and hydrogen [H ₂] mixture of gas forms.In embodiment 1, Zero-valent Iron is as body electron donor(ED) or reductive agent.

Use citric acid titanium (III) [Ti (OC (CH of open method and technology [102,96] synthesis of aqueous solution form ₂COOH) ₂COOH].In bottle, sealing, and store down in-20 ℃ is until use with the solution five equilibrium of citric acid titanium (III) in 660mM tris damping fluid (pH is 8.2) of 250mM of preparation.In embodiment 2,3 and 4, citric acid titanium (III) is as body electron donor(ED) or reductive agent.

Homogeneous catalysis batch reactor (as exemplary original position device):

In embodiment 1 and 2, use 500ml (0.5 liter) glass beaker down in room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere.Have automatically the track wobbler of (mixing) speed control by glass beaker is fixed on (the TS-600 type derives from MRC, Israel) on, the inclusion in each glass beaker (batch reactor) is mixed.

In embodiment 3 and 4, use outfit down in room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere

The 40ml of-transparent organic silicon seal cap (0.04 liter) vial (the about 25ml reaction soln of dress usually).By vial being fixed on the track wobbler, the inclusion in each vial (batch reactor) is mixed.When the experiment beginning, the reaction soln of in each vial (batch reactor), packing into, many parts of the same form.

For embodiment 1-4 each, under the oxygen-free atmosphere condition, use above-mentioned identical anaerobic room to prepare glass beaker or vial intermittent mode reaction system.

Analytic process:

In the intermittent mode homogeneous catalytic reaction process of embodiment 1-4, use GC and GC/MS to monitor " unique " atrazine catalytic reduction dechlorination reaction product N of atrazine and formation in the water that is polluted by atrazine ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2, the concentration of 4-diamines is over time.

GC is HP5890.GC/MS is Varian, and Saturn 2000.For GC and GC/MS, the GC post of use is J﹠amp; W Scientific-DB5 capillary column, long 30 meters, internal diameter 0.25mm, and 0.25 micron of film bed thickness.For GC and GC/MS, the GC program is: following 2 minutes in 160 ℃; 8 ℃/minute to 205 ℃ of temperature rising gradients; Kept 1 minute.

For GC and GC/MS analytic process, obtain and the preparation sample with glass beaker or vial (batch reactor), and use above-mentioned identical anaerobic room preparation standard reference coupon.By each " ongoing " catalyzed reaction and the sample that obtains different time by the duplicate that these ongoing catalyzed reactions are identical separately.

In embodiment 3 and 4, for each sampling spot, GC and GC/MS analytic process comprise opens (thereby sacrifice) at least two vials (batch reactor), uses 5ml methylene dichloride [99.8% subsequently; Sigma-Aldrich] as extraction solvent, extracted organic phase from the aqueous reaction solution that is included in each vial.Organic phase with extraction is transferred to the gas-chromatography pipe and analyzes the atrazine pollutent or/and the existence of its degraded product subsequently.

As the standard reference material of GC and GC/MS analytic process, according to the synthetic N that hereinafter summarizes ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamine reactant product:

Above-mentioned synthetic corresponding to be used for synthetic its 2, the improving one's methods of open method [103] of 4-di amino-6-methyl-s-triazine analogue.

Embodiment 1

The water that comes catalytic treatment to be polluted by intermittent mode, according to homogeneous catalysis by atrazine:

[TMPyP-Ni] electron transfer mediator catalyzer, Zero-valent Iron [Fe ⁰] the body electron donor(ED)

Experimentation

Under room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, carry out embodiment 1.

Take out 500ml (0.5 liter) from the liquid storage of the water that polluted by atrazine, add in the empty glass beaker (batch reactor), the starting point concentration that atrazine is provided is 12mg atrazine/liter contaminated water, i.e. 12ppm atrazine/contaminated water.

In the water that is polluted by atrazine in glass beaker (batch reactor), reductive condition is natural, and do not preponderate phenomenon, mechanism and the method for (homogeneous phase) catalytic reduction dehalogenation of being not enough to effectively utilize the electron transport mediation handled atrazine pollutent in the contaminated water.Therefore, by being exposed to zero-valent iron particle before at once by the water that atrazine pollutes at [TMPyP-Ni] metal porphyrin complex electron transfer mediator (homogeneous catalyst) that will be exposed to catalytically effective amount, the artificial reductive condition that produces in the water that is polluted by atrazine as body electron donor(ED) or reductive agent by the water that atrazine pollutes.

For this reason, will about 2g (" butt ") Zero-valent Iron [Fe ⁰] particle of nanometer size adds to the water that is polluted by atrazine that is contained in the glass beaker (batch reactor), and the concentration of about 4g (0.071mol) zero-valent iron particle (body electron donor(ED) or reductive agent)/liter water that is polluted by atrazine is provided.

Then, from 2mM[TMPyP-Ni] take out suitable volume the metal porphyrin complex liquid storage, add to the 0.5 liter of water that is polluted by atrazine and zero-valent iron particle that is contained in the glass beaker (batch reactor), make that [TMPyP-Ni] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyst concentration is about 0.014mM in the water that is polluted by atrazine.

Full time or duration in reaction, be set in the track wobbler of 150rpm by glass beaker being fixed on mixing velocity, be blended in the inclusion in the glass beaker (batch reactor) continuously, promptly comprise as the zero-valent iron particle of body electron donor(ED) or reductive agent and the water that is polluted by atrazine of [TMPyP-Ni] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

Regularly take out sample and carry out GC and GC/MS analysis from the water that is polluted by atrazine of intermittent mode homogeneous catalysis reductibility dechlorination reaction, the mixing of inclusion temporarily stops in the glass beaker between sampling date (batch reactor), continues subsequently.

Experimental result

Embodiment 1 obtains the results are shown in following table 1.

Table 1. is under room temperature and normal atmosphere, be implemented in the intermittent mode homogeneous catalysis reductibility dechlorination reaction of atrazine in the water that is polluted by atrazine by [TMPyP-Ni] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer with as the zero-valent iron particle of body electron donor(ED) or reductive agent, record in time (hour) and the normalization method concentration of the atrazine that becomes.

Time (hour)	Normalized atrazine concentration
Time (hour)	Normalized atrazine concentration	1.25	1
24	0.18	1.25	1
24	0.18	48	0.06
72	0.04	48	0.06

The result of table 1 shows that after 24 hours and 72 hours, the initial atrazine concentration in the water that is polluted by atrazine descends respectively greater than 80% with greater than 95%.

By the GC of embodiment 1 and GC/MS analytical results as seen, the unique atrazine catalytic reduction dechlorination reaction product that forms in intermittent mode homogeneous catalytic reaction process is defined as N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2, the 4-diamines [be also referred to as: 2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine].Therefore, the atrazine in the water that is polluted by atrazine is following carries out catalyzed degradation, conversion or transformation:

The atrazine reaction product

Atrazine catalytic reduction dechlorination reaction product N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2, the 4-diamines is for more hydrophobic, and compares with the parent compound atrazine, expects not too removable and soluble in water.In addition, expect that this non-chlorinated organic cpd is not dangerous or at least not too dangerous, therefore, more friendly to environment than atrazine.

Atrazine degraded product N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2, the 4-diamines was present in accessory a kind of obtaining [37,38] in three kinds of photodissociation degraded products that form in the process of the atrazine on the soil surface as ultraviolet photolysis in the past.The method of the photodegradation atrazine of instructing in the document and process are confined to be present in the atrazine on the soil surface especially, and obviously different by the water that atrazine (as just an example of the halogenated organic compounds of halogenation organic herbicide type) pollutes with catalytic treatment of the present invention.

Embodiment 2

[TP (OH) P-Co] electron transfer mediator catalyzer, citric acid titanium (III) body electron donor(ED)

Experimentation

Under room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, carry out embodiment 2.

Take out 500ml (0.5 liter) volume from the liquid storage of the water that polluted by atrazine, add in the empty glass beaker (batch reactor), the starting point concentration that atrazine is provided is 12mg atrazine/liter contaminated water, i.e. 12ppm atrazine/contaminated water.

In the water that is polluted by atrazine in glass beaker (batch reactor), reductive condition is natural, and do not preponderate phenomenon, mechanism and the method for (homogeneous phase) catalytic reduction dehalogenation of being not enough to effectively utilize the electron transport mediation handled atrazine pollutent in the contaminated water.Therefore, by will be exposed to citric acid titanium (III) [Ti (OC (CH before at once at [TP (OH) P-Co] the metal porphyrin complex electron transfer mediator (homogeneous catalyst) that will be exposed to catalytically effective amount by the water that atrazine pollutes as body electron donor(ED) or reductive agent by the water that atrazine pollutes ₂COOH) ₂COOH], the artificial reductive condition that produces in the water that is polluted by atrazine.

For this reason, the bottle of the solution of citric acid titanium (III) in 660mM tris damping fluid (pH is 8.2) that a plurality of (being stored in-20 ℃) is equipped with the 250mM of preparation rises to room temperature.Then therefrom take out about 36ml volume, add to 0.5 liter of water that is polluted by atrazine that is contained in the glass beaker (batch reactor), make that the concentration of citric acid titanium (III) (body electron donor(ED) or reductive agent) is about 0.014M in the water that is polluted by atrazine.

Then, from 2mM[TP (OH) P-Co] take out suitable volume the metal porphyrin complex liquid storage, add to the 0.5 liter of water that is polluted by atrazine and citric acid titanium (III) that is contained in the glass beaker (batch reactor), make that [TP (OH) P-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyst concentration is about 0.014mM in the water that is polluted by atrazine.

Full time or duration in reaction, be set in the track wobbler of 150rpm by glass beaker being fixed on mixing velocity, be blended in the inclusion in the glass beaker (batch reactor) continuously, promptly comprise as the citric acid titanium (III) of body electron donor(ED) or reductive agent and the water that is polluted by atrazine of [TP (OH) P-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

Regularly take out GC and GC/MS sample and analyze from the water that is polluted by atrazine of intermittent mode homogeneous catalysis reductibility dechlorination reaction, the mixing of inclusion temporarily stops in the glass beaker between sampling date (batch reactor), continues subsequently.

Experimental result

Embodiment 2 obtains the results are shown in following table 2.

Table 2. is under room temperature and normal atmosphere, be implemented in the intermittent mode homogeneous catalysis reductibility dechlorination reaction of atrazine in the water that is polluted by atrazine by [TP (OH) P-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer with as the citric acid titanium (III) of body electron donor(ED) or reductive agent, record in time (hour) and the normalization method concentration of the atrazine that becomes.

Time (hour)	Normalized atrazine concentration
Time (hour)	Normalized atrazine concentration	0	1.000
1.25	0.268	0	1.000
1.25	0.268	2	0.100
4	0.056	2	0.100
4	0.056	6	0.029
8	0.024	6	0.029
8	0.024	10	0.014
12	0.011	10	0.014
12	0.011	48	0.000

The result of table 2 shows, after 2 hours, and the initial atrazine density loss 90% in the water that is polluted by atrazine.After 12 hours and 48 hours, the initial atrazine concentration in the water that is polluted by atrazine descends about 99% and about 100% (promptly complete) respectively.

By the GC of embodiment 2 and GC/MS analytical results as seen, the unique atrazine catalytic reduction dechlorination reaction product that forms in intermittent mode homogeneous catalytic reaction process is defined as N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine].Obviously, compare with embodiment 1, in embodiment 2, relate to different metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer and different body electron donor(ED) or reductive agents, similarly reacting under the condition, adopt with shown in the foregoing description 1 and the identical or similar mode of discussion make the atrazine in the water that is polluted by atrazine carry out catalyzed degradation, conversion or transformation.

Embodiment 3

[TMPyP-Co] electron transfer mediator catalyzer, citric acid titanium (III) body electron donor(ED)

Experimentation

Under room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, carry out embodiment 3.

From the suitable liquid storage of the water that polluted by atrazine, take out 25ml (0.025 liter), add in the empty 40ml glass beaker (batch reactor), make that the starting point concentration of atrazine is 28mg atrazine/liter contaminated water, i.e. 28ppm atrazine/contaminated water.Repeat this process, prepare at least two vials (batch reactor) and be used for taking a sample separately.

In the water that is polluted by atrazine in vial (batch reactor), reductive condition is natural, and do not preponderate (homogeneous phase) catalytic reduction dehalogenation phenomenon, mechanism and the method that are not enough to effectively utilize the electron transport mediation handled atrazine pollutent in the contaminated water.Therefore, by will be exposed to citric acid titanium (III) [Ti (OC (CH before at once at [TMPyP-Co] metal porphyrin complex electron transfer mediator (homogeneous catalyst) that will be exposed to catalytically effective amount by the water that atrazine pollutes as body electron donor(ED) or reductive agent by the water that atrazine pollutes ₂COOH) ₂COOH], the artificial reductive condition that produces in the water that is polluted by atrazine.

For this reason, the bottle of the solution of citric acid titanium (III) in 660mM tris damping fluid (pH is 8.2) that a plurality of (being stored in-20 ℃) is equipped with the 250mM of preparation rises to room temperature.Then therefrom take out 0.75ml, add to the water that is polluted by atrazine that is contained in each vial (batch reactor), make that the concentration of citric acid titanium (III) (body electron donor(ED) or reductive agent) is about 0.0073M in the water that is polluted by atrazine.Subsequently by to each vial (batch reactor) in, adding a small amount of concentrated NaOH solution value that the pH regulator of solution is extremely required (for example 8.5).

Then, from 2mM[TMPyP-Co] take out suitable volume the metal porphyrin complex liquid storage, add in each vial (batch reactor) that the water that polluted by atrazine and citric acid titanium (III) are housed, make that [TMPyP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyst concentration is about 0.013mM in the water that is polluted by atrazine.Seal vial this moment, and be transferred to the track wobbler.

Full time or duration in reaction, be set in the track wobbler of 150rpm by each vial being fixed on mixing velocity, be blended in the inclusion in each vial (batch reactor) continuously, promptly comprise as the citric acid titanium (III) of body electron donor(ED) or reductive agent and the water that is polluted by atrazine of [TMPyP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

For each sampling spot, from each of at least two vials of the water that is polluted by atrazine that intermittent mode homogeneous catalysis reductibility dechlorination reaction is housed, regularly obtain GC or GC/MS analytical sample.The mixing of inclusion only temporarily stops when removing sampling jug in the vial (batch reactor), continues subsequently to stir.Use the 5ml methylene dichloride as extraction solvent, extracted organic phase from the aqueous reaction solution that is included in each vial.The atrazine pollutent is or/and the existence of its degraded product in the organic phase of subsequent analysis extraction.

Experimental result

Embodiment 3 obtains the results are shown in following table 3.

Table 3. is under room temperature and normal atmosphere, by the intermittent mode homogeneous catalysis reductibility dechlorination reaction of atrazine in [TMPyP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer and the water realizing being polluted as the citric acid titanium (III) of body electron donor(ED) or reductive agent by atrazine, record in time (hour) and the normalization method concentration of the atrazine that becomes.

Time (hour)	Normalized atrazine concentration
Time (hour)	Normalized atrazine concentration	0.0	1.000
0.25	0.36	0.0	1.000
0.25	0.36	0.5	0.14
1.0	0.07	0.5	0.14
1.0	0.07	2.0	0.05
3.0	0.00	2.0	0.05
3.0	0.00	4.0	0.00

The result of table 3 shows, after 0.5 hour, and the initial atrazine density loss about 85% in the water that is polluted by atrazine.After 2.0 hours and 3.0 hours, the initial atrazine concentration in the water that is polluted by atrazine descends about 95% and about 100% (promptly complete) respectively.

By the GC of embodiment 3 and GC/MS analytical results as seen, the unique atrazine catalytic reduction dechlorination reaction product that forms in intermittent mode homogeneous catalytic reaction process is defined as N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine].Obviously, in embodiment 3, adopt with shown in the foregoing description 1 and 2 and the identical or similar mode of discussion make the atrazine in the water that is polluted by atrazine carry out catalyzed degradation, conversion or transformation.

Embodiment 4

[TBSP-Co] electron transfer mediator catalyzer, citric acid titanium (III) body electron donor(ED)

Experimentation

Under room temperature (about 20 ℃ to about 25 ℃) and normal atmosphere, carry out embodiment 4.

From the suitable liquid storage of the water that polluted by atrazine, take out 25ml (0.025 liter), add in the empty 40ml vial (batch reactor), make that the starting point concentration of atrazine is 12mg atrazine/liter contaminated water, i.e. 12ppm atrazine/contaminated water.Repeat this process, prepare at least two vials (batch reactor) and be used for taking a sample separately.

In the water that is polluted by atrazine in vial (batch reactor), reductive condition is natural does not preponderate and handles atrazine pollutent in the contaminated water so that be not enough to effectively utilize (homogeneous phase) catalytic reduction dehalogenation phenomenon, mechanism and the method for electron transport mediation.Therefore, by will be exposed to citric acid titanium (III) [Ti (OC (CH before at once at [TBSP-Co] metal porphyrin complex electron transfer mediator (homogeneous catalyst) that will be exposed to catalytically effective amount by the water that atrazine pollutes as body electron donor(ED) or reductive agent by the water that atrazine pollutes ₂COOH) ₂COOH], the artificial reductive condition that produces in the water that is polluted by atrazine.

For this reason, the bottle of the solution of citric acid titanium (III) in 660mMtris damping fluid (pH is 8.2) of the 250mM that a plurality of (being stored in-20 ℃) prepared rises to room temperature.Then therefrom take out 0.75ml, add to the water that is polluted by atrazine that is contained in each vial (batch reactor), make that the concentration of citric acid titanium (III) (body electron donor(ED) or reductive agent) is about 0.0073M in the water that is polluted by atrazine.Subsequently by to each vial (batch reactor) in, adding a small amount of concentrated NaOH solution value that the pH regulator of solution is extremely required (for example 9.5).

Then, from 2mM[TBSP-Co] take out suitable volume the metal porphyrin complex liquid storage, add in each vial (batch reactor) that the water that polluted by atrazine and citric acid titanium (III) are housed, make that [TBSP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyst concentration is about 0.056mM in the water that is polluted by atrazine.Seal vial this moment, and be transferred to the track wobbler.

Full time or duration in reaction, be set in the track wobbler of 150rpm by each vial being fixed on mixing velocity, be blended in the inclusion in each vial (batch reactor) continuously, promptly comprise as the citric acid titanium (III) of body electron donor(ED) or reductive agent and the water that is polluted by atrazine of [TBSP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer.

For each sampling spot, from each of at least two vials of the water that is polluted by atrazine that intermittent mode homogeneous catalysis reductibility dechlorination reaction is housed, regularly obtain GC or GC/MS analytical sample.The mixing of inclusion only temporarily stops when removing sampling jug in the vial (batch reactor), continues subsequently to stir.Use the 5ml methylene dichloride as extraction solvent, extracted organic phase from the aqueous reaction solution that is contained in each vial.The atrazine pollutent is or/and the existence of its degraded product in the organic phase of subsequent analysis extraction.

Experimental result

The result that embodiment 4 obtains shows, under room temperature and normal atmosphere, intermittent mode homogeneous catalysis reductibility dechlorination reaction by atrazine in [TBSP-Co] metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer and the water realizing being polluted as the citric acid titanium (III) of body electron donor(ED) or reductive agent by atrazine, after 22 hours, the initial atrazine density loss about 83% in the water that is polluted by atrazine.

By the GC of embodiment 4 and GC/MS analytical results as seen, the unique atrazine catalytic reduction dechlorination reaction product that forms in intermittent mode homogeneous catalytic reaction process is defined as N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine].Obviously, in embodiment 4, adopt with shown in the foregoing description 1,2 and 3 and the identical or similar mode of discussion make the atrazine in the water that is polluted by atrazine carry out catalyzed degradation, conversion or transformation.

By the result of the foregoing description 1-4 as seen, identical total reaction takes place transform, promptly atrazine is converted into N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine], relate to different metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer, or/and different body electron donor(ED) or reductive agent, under similar conditioned response, the total reaction typical case of the water that catalytic treatment polluted by atrazine and unique is proposed forcefully.

In addition, owing under these conditions (by different metal porphyrin complex electron transfer mediator (homogeneous phase) catalyzer or/and different body electron donor(ED) or reductive agents), only form unique atrazine catalytic reduction dechlorination reaction product, i.e. N ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine], illustrate to have very high selectivity, do not produce can desirably not influence reaction mechanism with relevant path or/and ecological system or/and its organic other materials or/and other harmful or influential reaction product.

The mass balance of the reaction system of embodiment 1-4:

For the mass balance of the reaction system of studying the foregoing description 1-4, be catalyzed degradation, conversion or the transformation that 28mg, 12mg or 2.8mg atrazine/premium on currency (respectively corresponding to 28ppm, 12ppm or 2.8ppm atrazine/contaminated water) detect the atrazine in the water that is polluted by atrazine down three kinds of different concentration.Because unique atrazine catalytic reduction dechlorination reaction product N that supposition forms in the process of intermittent mode homogeneous catalytic reaction ², N ⁴-diethyl-6-methyl isophthalic acid, 3,5-triazine-2,4-diamines [2, two (ethylamino)-6-methyl-s-triazine of 4-or methylated s-triazine] has lower solubleness (consider based on theory, but the solubleness of two kinds of materials in water being all lower) than parent atrazine, discovery is under higher concentration (for example 28ppm atrazine/contaminated water), because methylated s-triazine reaction product partly precipitated, fail to reclaim and be used for analyzing, therefore some quality loss are arranged.The high quality loss is high more more for mass balance explanation atrazine concentration, and under minimum starting point concentration (being 2.8ppm atrazine/contaminated water), finds complete mass balance.The gap of this explanation between complete mass balance and measurement result may be because concentration effect.

Compare with methylated s-triazine reaction product, the aforementioned difference of parent atrazine herbicidal solubleness is useful from the angle of environment, because less dissolving (promptly than low solubility) means methylated s-triazine reaction product more limited transmission or mobility in underground water (for example underground water zone, water reservoir or aqueous stratum) or in the whole underground water.When combining with the high theoretical product degradation, the behavior and high reaction preference provide cleaner handling or remedy with effective means by the water of halogenated organic compounds (for example atrazine) pollution.

Exemplary as mentioned description and illustrating is based on owing to have the main aspect of novelty and creationary above-mentioned exemplary description or/and because these aspects, the present invention has some benefits and favourable aspect, feature and feature.

The present invention is applicable to and handles or remedy the water that is polluted by the halogenation organic herbicide of broad concentration range.

The present invention is applicable to that (original position or off normal) homogeneous phase or heterogeneous catalyst handle by the compound polluted water of halogenation organic herbicide, wherein said contaminated water is various form, for example underground water (for example underground water zone, water reservoir or aqueous stratum), the surface water (for example river, lake, pond, pond or surface water water reservoir), ground water (for example source, the ground of water water reservoir or dwelling house or commercial potable water or supply on the ground) or its array configuration.In addition, the present invention is at the industrial contaminated water that is applicable to these forms of processing big (industry) amount or volume.

The present invention relates to redox (redox) (homogeneous phase or heterogeneous) the catalyzed chemical reaction method of the dehalogenation type of more stable electron transport mediation, described method is carried out under the envrionment conditions of wide region, be subjected to the influence degree minimum of the considerable change of reaction parameter (pH and temperature), and irrelevant with nutrient utilization.These aspects and the relevant various restrictions formation sharp contrasts of biotechnology that are used to handle or remedy the water that is polluted by the halogenation organic herbicide.

Various dissimilar electron transfer mediators can be used for realizing the present invention.In addition, one or more electron transfer mediators can be fixed on (particle is or/and non-particulate) solid carrier or the body material or/and within, be dispersed in subsequently in the whole contaminated water.

The dissimilar natural existence that relates to various body electron donor(ED)s or reductive agent is or/and the synthetical reductive condition can be used for realizing the present invention.

The present invention can be combined with the reductive dehalogenation technology that is used to handle or remedy zero-valent metal (ZVM) type of the water that is polluted by the halogenation organic herbicide.

The dehalogenation redox catalysis chemical method of electron transport mediation is simpler, relate to one or more electron transfer mediators and react under (anaerobism or anoxic) condition, with the conversion of halogenation organic herbicide pollutent, transform or be degraded to not dangerous or/and Wei Xian compound not too in reduction.

The dehalogenation redox catalysis chemical method of electron transport mediation faster.After contaminated water is exposed to electron transfer mediator, with halogenation organic herbicide pollutent transform fully, change or be degraded to not dangerous or/and not too Wei Xian compound only need a few hours or a couple of days usually.

After heterogeneous catalyst was handled contaminated water, the heterogeneous catalyst of electron transfer mediator solid supported or matrix structure type can be from being used to handle the given original position of contaminated water or the device of offing normal is removed, and recirculation is used to handle contaminated water once more.This recirculation of catalyzer means that the method relative cost of the water that processing is polluted by the halogenation organic herbicide is lower.

Based on having novelty and creationary above-mentioned aspect and useful and favourable aspect, feature and feature, the present invention has successfully solved and has been devoted to handle or remedy by the shortcoming and the restriction of known technology at present in the environmental science of the compound polluted water of halogenation organic herbicide and the technical field, and having relaxed scope, wherein said contaminated water is underground water, the surface water, ground water or its array configuration.In addition, industrial application of the present invention can be to continue using confirmation or potentially dangerous but the agriculture field of very effective halogenation organic herbicide (particularly chlorination organonitrogen weedicide (CONH)) provides legal and environment amenable mode.

It should be understood that for the sake of clarity, of the present invention described in the context of independent embodiment aspect some and feature also can in independent embodiment, make up and provide.On the contrary, for for simplicity, also can provide separately or provide with any suitable subgroup form of closing in each side of the present invention described in the context of independent embodiment and feature.

All publications, patent and the patent application mentioned in this manual are attached to herein by quoting in full, and are attached to herein by reference as the concrete and independent record of each publication, patent and patent application.In addition, any reference in this application quotes or determines and should not think to admit that these reference can be used as prior art of the present invention.

Though described the present invention in conjunction with specific embodiments and embodiment, obvious many surrogates, improvement and variation it will be apparent to those skilled in the art that.Therefore, expection comprises aim and interior all these surrogates, improvement and the variation of wide region that drops on appended claims.

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Claims

1. the method for the water of a catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof, described method is included at least a electron transfer mediator that under the reductive condition described contaminated water is exposed to catalytically effective amount, thereby is reduced in the concentration of at least a halogenated organic compounds in the contaminated water.

2. the process of claim 1 wherein that described contaminated water is the form that is selected from underground water, the surface water, ground water and combination thereof.

3. the process of claim 1 wherein that described chlorotriazine weedicide has following general chemical structure:

R wherein ₁-R ₄Independently be selected from hydrogen atom and organic substituent separately.

4. the method for claim 3, wherein said organic substituent is selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

5. the process of claim 1 wherein that described chlorotriazine weedicide is selected from atrazine [C ₈H ₁₄ClN ₅], chlorazine [C ₁₁H ₂₀ClN ₅], cyanazine [C ₉H ₁₃ClN ₆], cyprazine [C ₉H ₁₄ClN ₅], Radix Glycyrrhizae Tianjin [C ₇H ₁₀ClN ₅O ₂], ipazine [C ₁₀H ₁₈ClN ₅], the green bristlegrass of going out Tianjin [C1 ₀H ₁₈ClN ₅O], the ring third blue or green Tianjin [C ₁₀H ₁₃ClN ₆], proglinazine[C ₈H ₁₂ClN ₅O ₂], propazine [C ₉H ₁₆ClN ₅], fourth Tianjin [C in addition ₉H ₁₆ClN ₅], simazine [C ₇H ₁₂ClN ₅], terbuthylazine [C ₉H ₁₆ClN ₅] and trietazine [C ₉H ₁₆ClN ₅].

6. the process of claim 1 wherein that described chloro-acetanilide herbicide has following general chemical structure:

7. the method for claim 6, wherein said organic substituent is selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

8. the process of claim 1 wherein that described chloro-acetanilide herbicide is selected from acetochlor [C ₁₄H ₂₀ClNO ₂], alachlor [C ₁₄H ₂₀ClNO ₂], Butachlor technical 92 [C ₁₇H ₂₆ClNO ₂], metazachlor [C ₁₄H ₁₆ClN ₃O], metolachlor [C ₁₅H ₂₂ClNO ₂], S-metolachlor [C ₁₅H ₂₂ClNO ₂], the third careless amine [C ₁₇H ₂₆ClNO ₂], propachlor [C ₁₁H ₁₄ClNO], xylachlor [C ₁₃H ₁₈ClNO], butenachlor [C ₁₇H ₂₄ClNO ₂], delachlor [C ₁₅H ₂₂ClNO ₂], peace tower [C ₁₄H ₁₈ClNO ₃], ethachlor [C ₁₃H ₁₈ClNO ₂], propisochlor [C ₁₅H ₂₂ClNO ₂], prynachlor [C ₁₂H ₁₂ClNO], the violent grass [C that kills ₁₈H ₂₈ClNO ₂] and thiophene ether grass amine [C1 ₆H ₁₈ClNO ₂S].

9. the process of claim 1 wherein that described halogenation aliphatic series weedicide has following general chemical structure:

A-(C-R′-R＂) _n-B

Wherein:

N is 1-4; With

A, B, R ' and R ＂ independently are selected from hydrogen atom and organic substituent separately,

Wherein at least one is a halogen atom among A, B, R ' and the R ＂.

10. the method for claim 9, wherein said organic substituent is selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

11. the process of claim 1 wherein that described halogenation aliphatic series weedicide is selected from pentachloro-oxopentanoic acid [C ₅HCl ₅O ₃], chloropon [C ₃H ₃Cl ₃O ₂], dalapon [C ₃H ₄Cl ₂O ₂], tetrafluoro propionic acid [C ₃H ₂F ₄O ₂], TCA (trichoroacetic acid(TCA)) [C ₂HCl ₃O ₂], hexachloroacetone [C ₃Cl ₆O], methyl iodide [CH ₃I], monobromethane [CH ₃Br], monochloro acetate [C ₂H ₃ClO ₂] and SMA (chloracetic acid sodium) [C ₂H ₂ClNaO ₂].

12. the process of claim 1 wherein that described halogenated organic compounds is selected from non-volatile particulate matter, liquid and combination thereof.

13. the process of claim 1 wherein that described at least a electron transfer mediator is the organometallic complex that comes from porphyrin.

14. the method for claim 13, the wherein said organometallic complex that comes from porphyrin are selected from metal porphyrin complex, metal corrin complex compound, metal dihydride porphin phenol complex compound and any combination thereof.

15. the method for claim 14, wherein said metal porphyrin complex comprise and the transition metal that is selected from following (originally being free alkali) porphyrin complexing:

Tetraphenylporphyrin [5,10,15,20-tetraphenyl-21H, 23H-porphines] [TPP]; With

16. the method for claim 15, wherein said transition metal are selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].

17. the method for claim 14, wherein said metal porphyrin complex is selected from

Tetramethyl pyridine porphyrin-nickel [5,10,15,20-four (1-methyl-4-pyridine)-porphines-nickel] [TMPyP-Ni];

Tetrahydroxy phenyl tetrazaporphin-cobalt [5,10,15,20-four (4-hydroxy phenyl)-21H, 23H-porphines-cobalt] [TP (OH) P-Co];

Tetramethyl pyridine porphyrin-cobalt [5,10,15,20-four (1-methyl-4-pyridine)-porphines-cobalt] [TMPyP-Co];

4,4 ', 4 ＂, 4 " '-(porphines-5,10,15,20-four bases) four (Phenylsulfonic acid)-cobalts [TBSP-Co];

And combination.

18. the method for claim 14, wherein said metal porphyrin complex is selected from chlorophyll and protoheme.

19. the method for claim 14, wherein said metal corrin complex compound is a vitamins B ₁₂[with the corrin part (porphyrin analogue) of cobalt (III) ion complexation].

20. the process of claim 1 wherein and realize described exposure according to homogeneous catalysis, heterogeneous catalyst or its combination.

21. the method for claim 20, wherein according to described heterogeneous catalyst, described at least a electron transfer mediator by load, matrixization, insert, mix or/and catch and be fixed on usually on the solid carrier that is dispersed in subsequently in the whole contaminated water or the body material or/and within.

22. the method for claim 21, wherein said solid carrier or body material are selected from diatomite, soft silica, crystalline silica, silica gel, aluminum oxide, mineral, pottery, carbohydrate, clay, plastics, matrix material and combination thereof.

23. the method for claim 20, wherein according to described heterogeneous catalyst, described at least a electron transfer mediator is the part of electron transfer mediator solid supported or matrix structure, and described structure is the heterogeneous catalyst of diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type.

24. the process of claim 1 wherein that the volumetric molar concentration of described at least a electron transfer mediator of the described catalytically effective amount that described contaminated water exposed is about 10 ^-7To about 10 ^-3Mole electron transfer mediator/liter contaminated water.

25. the process of claim 1 wherein that the volumetric molar concentration of described at least a electron transfer mediator of the described catalytically effective amount that described contaminated water exposed is about 10 ^-6To about 10 ^-4Mole electron transfer mediator/liter contaminated water.

26. the process of claim 1 wherein that the volumetric molar concentration of described at least a electron transfer mediator of the described catalytically effective amount that described contaminated water exposed is about 10 ^-5Mole electron transfer mediator/liter contaminated water.

27. the method for claim 1, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 1000:1 of about 1:1000.

28. the method for claim 1, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 100:1 of about 1:100.

29. the method for claim 1, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 10:1 of about 1:10.

30. the process of claim 1 wherein and carry out described exposure according to homogeneous catalysis, to form in the described pattern any homogeneous catalytic reaction system by intermittent mode or flow pattern.

31. the method for claim 30, wherein the described at least a electron transfer mediator of part or all of described catalytically effective amount uses with solid form.

32. the method for claim 30, wherein the described at least a electron transfer mediator of part or all of described catalytically effective amount uses with the solution form.

33. the process of claim 1 wherein and carry out described exposure according to heterogeneous catalyst, to form in the described pattern any heterogeneous catalytic reaction system by intermittent mode or flow pattern.

34. the method for claim 33, wherein the described at least a electron transfer mediator of whole described catalytically effective amounts uses with solid form.

35. the process of claim 1 wherein in the natural existence of reductive condition described in the contaminated water or/and artificial the generation.

36. the method for claim 35 wherein artificially produces described reductive condition by contaminated water being exposed at least a body electron donor(ED) or reductive agent.

37. the method for claim 35 wherein comprises the electron transfer mediator solid supported of at least a body electron donor(ED) or reductive agent by use or the heterogeneous catalyst of matrix structure type artificially produces described reductive condition.

38. the method for claim 36, wherein said at least a body electron donor(ED) or reductive agent comprise metal element (zero-valent metal).

39. the method for claim 38, wherein said metal element chosen from Fe [Fe ⁰], lithium [Li ⁰], sodium [Na ⁰], potassium [K ⁰], beryllium [Be ⁰], magnesium [Mg ⁰], titanium [Ti ⁰] and any mixture.

40. the method for claim 36, wherein said at least a body electron donor(ED) or reductive agent are selected from citric acid titanium (III) [Ti (OC (CH ₂COOH) ₂COOH], POTASSIUM BOROHYDRIDE [KBH ₄], sodium borohydride [NaBH ₄], lithium hydride [LiH], potassium hydride KH [KaH], sodium hydride [NaH], boron trihydride [BH ₃], three aluminum hydride [AlH ₃], hydrazine [H ₂NNH ₂], triphenylphosphate [PPh ₃], V-Brite B [Na ₂S ₂O ₄] and any combination.

41. the method for claim 36, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-4To about 1.0 moles of body electron donor(ED)s or reductive agent/liter contaminated water.

42. the method for claim 36, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-3To about 10 ^-1Mole body electron donor(ED) or reductive agent/liter contaminated water.

43. the method for claim 36, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-2Mole body electron donor(ED) or reductive agent/liter contaminated water.

44. the process of claim 1 wherein that comprising the system of at least a device that described at least a electron transfer mediator and being used to comprises the described at least a electron transfer mediator of described catalytically effective amount by use carries out described exposure.

45. the method for claim 44, wherein said at least a device comprises the original position device, in the process of the described contaminated water of catalytic treatment, described original position device be physically located at basically or be seated and position, place or the position of the reality of contaminated water or within operation.

46. the method for claim 45, wherein said original position device is a form of descending the permeable active restraining mass of water at least in part.

47. the method for claim 46, the wherein said permeable active restraining mass of water that descends at least in part is to be selected from the form that successive is filled ditch or wall construction and independent filling well construction.

48. the method for claim 46, the wherein said form that to descend the permeable active restraining mass of water at least in part be the part of underground water pumping and system for handling.

49. the method for claim 44, wherein said at least a device comprises the device of offing normal, in the process of the described contaminated water of catalytic treatment, the described device of offing normal is physically located at basically or is seated and beyond position, place or the position of the reality of contaminated water or away from position, place or the position operation of the reality of contaminated water.

50. the method for claim 49, wherein said at least a device is the part of the device of offing normal of ground water reactor form.

51. the system of the water of a catalytic treatment contaminated with halogenated organic compounds, wherein said halogenated organic compounds is selected from chlorotriazine weedicide, chloro-acetanilide herbicide, halogenation aliphatic series weedicide, its halogen-containing analogue, its halogen-containing derivative and combination thereof, and described system comprises:

(a) at least a electron transfer mediator; With

(b) at least a device, described device are used to comprise the described at least a electron transfer mediator of catalytically effective amount, are used for making under reductive condition described contaminated water to be exposed to described at least a electron transfer mediator.

52. the system of claim 51, wherein said contaminated water are the form that is selected from underground water, the surface water, ground water and combination thereof.

53. the system of claim 51, wherein said chlorotriazine weedicide has following general chemical structure:

54. the system of claim 53, wherein said organic substituent are selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

55. the system of claim 51, wherein said chlorotriazine weedicide is selected from atrazine [C ₈H ₁₄ClN ₅], chlorazine [C ₁₁H ₂₀ClN ₅], cyanazine [C ₉H ₁₃ClN ₆], cyprazine [C ₉H ₁₄ClN ₅], Radix Glycyrrhizae Tianjin [C ₇H ₁₀ClN ₅O ₂], ipazine [C ₁₀H ₁₈ClN ₅], the green bristlegrass of going out Tianjin [C ₁₀H ₁₈ClN ₅O], the ring third blue or green Tianjin [C ₁₀H ₁₃ClN ₆], proglinazine[C ₈H ₁₂ClN ₅O ₂], propazine [C ₉H ₁₆ClN ₅], fourth Tianjin [C in addition ₉H ₁₆ClN ₅], simazine [C ₇H ₁₂ClN ₅], terbuthylazine [C ₉H ₁₆ClN ₅] and trietazine [C ₉H ₁₆ClN ₅].

56. the system of claim 51, wherein said chloro-acetanilide herbicide have following general chemical structure:

57. the system of claim 56, wherein said organic substituent are selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

58. the system of claim 51, wherein said chloro-acetanilide herbicide is selected from acetochlor [C ₁₄H ₂₀ClNO ₂], alachlor [C ₁₄H ₂₀ClNO ₂], Butachlor technical 92 [C ₁₇H ₂₆ClNO ₂], metazachlor [C ₁₄H ₁₆ClN ₃O], metolachlor [C ₁₅H ₂₂ClNO ₂], S-metolachlor [C ₁₅H ₂₂ClNO ₂], the third careless amine [C ₁₇H ₂₆ClNO ₂], propachlor [C ₁₁H ₁₄ClNO], xylachlor [C ₁₃H ₁₈ClNO], butenachlor [C ₁₇H ₂₄ClNO ₂], delachlor [C ₁₅H ₂₂ClNO ₂], peace tower [C ₁₄H ₁₈ClNO ₃], ethachlor [C ₁₃H ₁₈ClNO ₂], propisochlor [C ₁₅H ₂₂ClNO ₂], prynachlor [C ₁₂H ₁₂ClNO], the violent grass [C that kills ₁₈H ₂₈ClNO ₂] and thiophene ether grass amine [C ₁₆H ₁₈ClNO ₂S].

59. the system of claim 51, wherein said halogenation aliphatic series weedicide has following general chemical structure:

A-(C-R′-R＂) _n-B

Wherein:

N is 1-4; With

Wherein at least one is a halogen atom among A, B, R ' and the R ＂.

60. the system of claim 59, wherein said organic substituent are selected from alkyl, cycloalkyl, cyano group alkyl, thiazolinyl, alkynyl, carboxylic acid, ether, alkoxyl group, heteroaryl, aryl and assorted alicyclic group.

61. the system of claim 51, wherein said halogenation aliphatic series weedicide is selected from pentachloro-oxopentanoic acid [C ₅HCl ₅O ₃], chloropon [C ₃H ₃Cl ₃O ₂], dalapon [C ₃H ₄Cl ₂O ₂], tetrafluoro propionic acid [C ₃H ₂F ₄O ₂], TCA (trichoroacetic acid(TCA)) [C ₂HCl ₃O ₂], hexachloroacetone [C ₃Cl ₆O], methyl iodide [CH ₃I], monobromethane [CH ₃Br], monochloro acetate [C ₂H ₃ClO ₂] and SMA (chloracetic acid sodium) [C ₂H ₂ClNaO ₂].

62. the system of claim 51, wherein said halogenated organic compounds is selected from non-volatile particulate matter, liquid and combination thereof.

63. the system of claim 51, wherein said at least a electron transfer mediator is the organometallic complex that comes from porphyrin.

64. the system of claim 63, the wherein said organometallic complex that comes from porphyrin are selected from metal porphyrin complex, metal corrin complex compound, metal dihydride porphin phenol complex compound and any combination thereof.

65. the system of claim 64, wherein said metal porphyrin complex comprise and the transition metal that is selected from following (originally being free alkali) porphyrin complexing:

Tetraphenylporphyrin [5,10,15,20-tetraphenyl-21H, 23H-porphines] [TPP]; With

66. the system of claim 65, wherein said transition metal are selected from cobalt [Co], nickel [Ni], iron [Fe], zinc [Zn] and copper [Cu].

67. the system of claim 64, wherein said metal porphyrin complex is selected from:

And combination.

68. the system of claim 64, wherein said metal porphyrin complex is selected from chlorophyll and protoheme.

69. the system of claim 64, wherein said metal corrin complex compound is a vitamins B ₁₂[with the corrin part (porphyrin analogue) of cobalt (III) ion complexation].

70. the system of claim 51 wherein realizes described exposure according to homogeneous catalysis, heterogeneous catalyst or its combination.

71. the system of claim 70, wherein according to described heterogeneous catalyst, described at least a electron transfer mediator by load, matrixization, insert, mix or/and catch and be fixed on usually on the solid carrier that is dispersed in subsequently in the whole contaminated water or the body material or/and within.

72. the system of claim 71, wherein said solid carrier or body material are selected from diatomite, soft silica, crystalline silica, silica gel, aluminum oxide, mineral, pottery, carbohydrate, clay, plastics, matrix material and combination thereof.

73. the system of claim 70, wherein according to described heterogeneous catalyst, described at least a electron transfer mediator is the part of electron transfer mediator solid supported or matrix structure, and described structure is the heterogeneous catalyst of diatomite/zero-valent metal (ZVM)/electron transfer mediator matrix material type.

74. the system of claim 51, wherein the volumetric molar concentration of the described at least a electron transfer mediator of the described catalytically effective amount that contaminated water exposed is about 10 ^-7To about 10 ^-3Mole electron transfer mediator/liter contaminated water.

75. the system of claim 51, wherein the volumetric molar concentration of the described at least a electron transfer mediator of the described catalytically effective amount that contaminated water exposed is about 10 ^-6To about 10 ^-4Mole electron transfer mediator/liter contaminated water.

76. the system of claim 51, wherein the volumetric molar concentration of the described at least a electron transfer mediator of the described catalytically effective amount that contaminated water exposed is about 10 ^-5Mole electron transfer mediator/liter contaminated water.

77. the system of claim 51, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 1000:1 of about 1:1000.

78. the system of claim 51, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 100:1 of about 1:100.

79. the system of claim 51, wherein contaminated water is exposed to the described at least a electron transfer mediator of described catalytically effective amount, the quality (weight) of at least a halogenated organic compounds in described at least a electron transfer mediator and the contaminated water is than being extremely about 10:1 of about 1:10.

80. the system of claim 51 wherein by intermittent mode or flow pattern, is carried out described exposure according to homogeneous catalysis, to form in the described pattern any homogeneous catalytic reaction system.

81. the system of claim 80, wherein the described at least a electron transfer mediator of part or all of described catalytically effective amount uses with solid form.

82. the system of claim 80, wherein the described at least a electron transfer mediator of part or all of described catalytically effective amount uses with the solution form.

83. the system of claim 51 wherein by intermittent mode or flow pattern, is carried out described exposure according to heterogeneous catalyst, to form in the described pattern any heterogeneous catalytic reaction system.

84. the system of claim 83, wherein the described at least a electron transfer mediator of whole described catalytically effective amounts uses with solid form.

85. the system of claim 51, wherein in contaminated water natural existence or/and artificially produce described reductive condition.

86. the system of claim 85 wherein artificially produces described reductive condition by contaminated water being exposed at least a body electron donor(ED) or reductive agent.

87. the system of claim 85 wherein comprises the electron transfer mediator solid supported of at least a body electron donor(ED) or reductive agent by use or the heterogeneous catalyst of matrix structure type artificially produces described reductive condition.

88. the system of claim 86, wherein said at least a body electron donor(ED) or reductive agent comprise metal element (zero-valent metal).

89. the system of claim 88, wherein said metal element chosen from Fe [Fe ⁰], lithium [Li ⁰], sodium [Na ⁰], potassium [K ⁰], beryllium [Be ⁰], magnesium [Mg ⁰], titanium [Ti ⁰] and any mixture.

90. the system of claim 86, wherein said at least a body electron donor(ED) or reductive agent are selected from citric acid titanium (III) [Ti (OC (CH ₂COOH) ₂COOH], POTASSIUM BOROHYDRIDE [KBH ₄], sodium borohydride [NaBH ₄], lithium hydride [LiH], potassium hydride KH [KaH], sodium hydride [NaH], boron trihydride [BH ₃], three aluminum hydride [AlH ₃], hydrazine [H ₂NNH ₂], triphenylphosphate [PPh ₃], V-Brite B [Na ₂S ₂O ₄] and any combination.

91. the system of claim 86, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-4To about 1.0 moles of body electron donor(ED)s or reductive agent/liter contaminated water.

92. the system of claim 86, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-3To about 10 ^-1Mole body electron donor(ED) or reductive agent/liter contaminated water.

93. the system of claim 86, the volumetric molar concentration of wherein said at least a body electron donor(ED) or reductive agent is about 10 ^-2Mole body electron donor(ED) or reductive agent/liter contaminated water.

94. the system of claim 51, wherein said at least a device comprises the original position device, in the process of the described contaminated water of catalytic treatment, described original position device be physically located at basically or be seated and on position, place or the position of the reality of contaminated water or within operation.

95. the system of claim 94, wherein said original position device is a form of descending the permeable active restraining mass of water at least in part.

96. the system of claim 95, the wherein said permeable active restraining mass of water that descends at least in part is to be selected from the form that successive is filled ditch or wall construction and independent filling well construction.

97. the system of claim 95, the wherein said form that to descend the permeable active restraining mass of water at least in part be the part of underground water pumping and system for handling.

98. the system of claim 51, wherein said at least a device comprises the device of offing normal, in the process of the described contaminated water of catalytic treatment, the described device of offing normal is physically located at basically or is seated and beyond position, place or the position of the reality of contaminated water or away from position, place or the position operation of the reality of contaminated water.

99. the system of claim 98, wherein said at least a device is the part of the device of offing normal of ground water reactor form.