CN103951026B - A kind of with manganese dioxide for arsenious method in catalyst air oxidation solution - Google Patents
A kind of with manganese dioxide for arsenious method in catalyst air oxidation solution Download PDFInfo
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- CN103951026B CN103951026B CN201410200439.9A CN201410200439A CN103951026B CN 103951026 B CN103951026 B CN 103951026B CN 201410200439 A CN201410200439 A CN 201410200439A CN 103951026 B CN103951026 B CN 103951026B
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Abstract
The present invention relates to the treatment technology of a kind of arsenic-containing waste water, particularly relate to a kind of with manganese dioxide for catalysis as catalyst, arsenious method in low cost, high efficiency catalytic air oxidation solution.The present invention is with MnO2For catalyst, controlling trivalent arsenic solution temperature is 30 90 DEG C, and blasts air in trivalent arsenic solution under agitation, reacts 1 4h, can complete the oxidation of arsenic in solution.The present invention has that process is simple, the advantage of the repeatable utilization of low cost, high efficiency, environmental friendliness, catalyst, solves the problem that the efficiency in the presence of current trivalent arsenic oxidation technology is low, cost is high, catalyst is difficult to reclaim.Present invention process process is simple, equipment investment is little, without expensive reagent in oxidizing process, it is easy to heavy industrialization is applied.
Description
Technical field
The present invention relates to the treatment technology of a kind of arsenic-containing waste water, particularly relating to one with manganese dioxide for catalysis is
Arsenious method in catalyst, low cost, high efficiency catalytic air oxidation solution.
Background technology
Arsenic is a kind of to human body and the carcinogen of the toxic effect of other organism, and its acute poisoning lethal dose is
0.2-0.6g.China is to be polluted one of the most serious country by arsenic in the world.Statistics shows, there are about more than 2,000 ten thousand
People is exposed in drinking-water, air-dried food and the room air that arsenic pollutes.Relative to Solid Arsenic material, arsenic is at water
Migrating very fast in body, its harm is the biggest, thus, most of arsenic pollute or arsenic poisoning event is all dirty by water body
Dye causes.
Result of study shows, the toxicity of As (III) be far above As (V), about about 60 times.The migration of As (III)
Property the most relatively As (V) is much higher, and this makes As (III) the rapidest to the contamination of environment.Existing dearsenification skill
Art, the either precipitation method, or absorption method, it is much larger than As (III) to the removing ability of As (V).Therefore,
As (III) is oxidized to one of the process steps necessary that As (V) is arsenic-containing waste water.
It is broadly divided into three classes: efficient oxidation, photochemical catalytic oxidation and biological oxidation according to its oxidation mechanism.
Efficient oxidation is to use strong oxidizer that As (III) is oxidized to As (V), and relatively common oxidant is dioxygen
Water, potassium permanganate, sodium hypochlorite and δ-MnO2Deng.Patent CN102616859A describes a kind of use
δ-MnO2Method arsenious in oxidation solution, at 20-30 DEG C, when pH is 2-4, adds
0.2-0.4g/Lδ-MnO2Can trivalent arsenic in complete oxidation solution, owing to the program is in acid condition, adopt
With δ-MnO2Use as oxidant, then certainly exist δ-MnO2High consume, low recovery, prepare simultaneously
High-purity δ-MnO2Cost be that comparison is high, so while efficient oxidation method efficiency is high, but its cost is the most relatively
High.Photocatalysis oxidation technique is to utilize photochemical catalyst to absorb luminous energy the most under certain conditions with specific wavelength
Release, makes oxygen in water ionize, and then makes As (III) be aoxidized.Current research is confined to light more and urges
Then agent absorption ultraviolet light is released energy and is realized the catalysis oxidation of As (III), for absorbing visible ray and discharging energy
The effect of amount oxidation As (III) is unsatisfactory.Biological oxidation has environmental protection, the advantage of non-secondary pollution, it has also become
One focus of arsenic oxidation, but owing to it is inefficient, the most under test, such as patent CN
101993835A describes a kind of employing Thiobacillus ferrooxidans and processes high arsenic gold concentrate ore pulp, by bacterium solution: ore deposit
Slurry=1:10 volume ratio adds Thiobacillus ferrooxidans liquid, aoxidizes under the conditions of 30-45 DEG C.The oxidation of arsenic to be made
Rate, up to more than 90%, needs 4-5 days.Therefore, existing trivalent arsenic method for oxidation or cost height, or
Efficiency is low, this application having had a strong impact on dearsenic technique and popularization.In order to cut operating costs, researcher tastes
Pilot production air aoxidizes the trivalent arsenic in solution, but due to dynamic (dynamical) problem so that the oxidation of arsenic is the most slow
Slowly.To this end, seldom use the oxidation protocol of single air, use mixed oxidization most of the time, such as patent
CN102603052A just uses the air mixed gas with chlorine or ozone as oxidant.Consequently, it is possible to
Although solving the problem that oxidation efficiency is low, but processing cost rising the most therewith, especially with the situation of chlorine,
Enterprise has in the face of the etching problem of equipment.Additionally, there is document to report, Cu2+、Ni2+、Co2+、Ag+
And Mn2+Can be as catalyst during trivalent arsenic in air oxidation solution, wherein with Ag+Effect best, but
Its use cost is higher, and the oxidization time that remaining ion needs is longer, and effect is the most poor.Although it addition, these
Metal ion has certain catalytic action, but it joins in solution, not only can change solution composition, even
Foul solution, and be used only once, reclaim more difficulty, cause relatively costly.Therefore, industry is urgent
Need to develop the trivalent arsenic method for oxidation of a kind of low cost, to reduce environmental protection cost, promote the removing of arsenic in solution,
Thus realize economic benefit and the situation of social benefit doulbe-sides' victory.
Summary of the invention
It is an object of the invention to solve that the efficiency in the presence of current trivalent arsenic oxidation technology is low and cost high
Problem, it is provided that a kind of process is simple, the repeatable profit of low cost, high efficiency, environmental friendliness, catalyst
The arsenious method of catalytic air oxidation.
In research process, inventor finds MnO2In addition to can be as the effect of oxidant, may also function as
The arsenious effect of catalytic air oxidation, and this catalytic action can be the most effective at wider pH.In acidity
Under system, except adding MnO2Outward, a certain amount of Cu is added2+Or Ni2+, certain concerted catalysis can be played
Effect, but under alkaline system, effect is the most obvious；It is simultaneously introduced Cu2+Or Ni2+, may change molten
Liquid composition or foul solution, so that subsequent treatment process becomes complicated.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, including under
State step:
By MnO2It is 0.05-0.2:1 with arsenious mol ratio, by MnO2Add containing in arsenious solution
And mix, simultaneously blast oxygen-containing gas toward containing in arsenious solution, after stirring, completing reaction, filtration,
Filter residue is MnO2, filtrate is oxidated solution；During reaction, control reaction temperature and be 30-90 DEG C.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, described
MnO2Particle mean size≤10um, specific surface area >=5m2/g。
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, described contains
In arsenious solution, arsenious concentration is >=20ug/L.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, described contains
In carrier of oxygen, the percentage by volume of oxygen is ＞ 20%；It is preferably air.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, blasts and contains
During carrier of oxygen, coutroi velocity is 0.1-2.5L/min.In course of reaction, the consumption of oxygen-containing gas is more than or equal to reason
4-8 times of opinion consumption.Described theoretical amount is that trivalent arsenics all in solution are oxidized to pentavalent arsenic requisite oxygen by oxygen
The consumption of gas.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, stirring
Time, control mixing speed is 100-400r/min.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, during reaction
Between control as 1-4h.
The present invention is a kind of with manganese dioxide for arsenious method in catalyst air oxidation solution, described contains
The pH value of arsenious solution is preferably 7-14.
Present invention one is urged with manganese dioxide for arsenious method one in catalyst air oxidation solution
Changing arsenious method in air oxidation solution, install gas distribution grid in reactor additional, this is conducive to quickening
The oxidation of arsenic.
Principle and advantage
From thermodynamically saying, in air oxidation solution, trivalent arsenic is feasible, but owing to its reaction energy gesture is higher,
The dynamics making this oxidation reaction is poor, causes reaction speed slower.The present invention finds through lot of experiments,
Reaction system introduces MnO2As catalyst, can effectively solve the slow-footed problem of air oxidation trivalent arsenic,
Its principle is:
(1) what in the solution, oxygen molecule was slow with trivalent arsenic ionic reaction main reason is that oxygen molecule and trivalent
Act between arsenic ion and being controlled by diffusion process, and MnO2Particle surface rich in substantial amounts of hydroxyl radical free radical and
Abundant active site position so that it has the strongest suction-operated to oxygen molecule in solution and trivalent arsenic ion, this
One characteristic makes MnO2Particle surface becomes the effecting reaction platform of oxygen molecule and trivalent arsenic ionic interaction；
(2)MnO2Stable in physicochemical property, it all not readily dissolves in the range of wider pH, this make its
Acid all have preferable catalytic effect to air oxidation trivalent arsenic in alkaline solution.Meanwhile, it is also easy to from solution
Middle separation and reusing.
The present invention uses air as oxidant, uses MnO2Particle, as catalyst, overcomes prior art
Present in cost height, etching apparatus, change solution composition or foul solution, catalyst be difficult to recycling
A difficult problem.
Compared with patent CN102616859A, MnO of the present invention2Consumption well below CN
δ-MnO in 102616859A2Consumption (by MnO2Calculating with arsenious mol ratio, its ratio is
34.47-689.4:1), it is additionally, since δ-MnO2Making oxidant to use, its consumption is necessarily much larger than this
Bright, prepare high-purity δ-MnO simultaneously2Cost necessarily far above the present invention.The present invention is to MnO2Crystal formation do not have
There is particular/special requirement, so MnO in its raw material sources relatively CN102616859A2It is easy to get, it is most important that,
MnO in the present invention2Use as catalyst, with the reaction of CN102616859A in reaction mechanism
There is the difference of essence in mechanism；Using air as oxidant, its cost is inevitable high-purity well below using simultaneously
δ-MnO2Cost.Compared with the technology of patent CN102603052A, the present invention uses air as oxygen
Agent, by rational catalyst and the selection of consumption thereof, successfully achieves high efficiency oxidation trivalent arsenic, this
Not only improve reduction production cost, again will not etching apparatus, this is to have very much for large-scale industrialization application
Profit." the Cu reported with existing document2+、Ni2+、Co2+、Ag+And Mn2+Can be as in air oxidation solution
Catalyst during trivalent arsenic " technology compares, and is to deposit with cationic form in the solution owing to above-mentioned technology uses
Catalyst, then this technology will necessarily exist that " change solution composition or foul solution, catalyst is difficult to back
Receive recycling " difficult problem, the present invention uses MnO2Particle as catalyst, the most neutral or alkaline bar
Under part, all can realize arsenious efficient oxidation (especially under the conditions of alkalescence), cation will not be introduced simultaneously
Impurity, and MnO used2Particle after filtering can also recycling, this not only overcomes in prior art and adopts
The problem brought as catalyst with metal cation, is also extensive, the work of high efficiency, low cost simultaneously
Industryization application provides necessary condition.
The present invention is compared with prior art in a word, has the advantage that
(1) present device requires simple, without especial equipment requirements, it is easy to accomplish industrialization.
(2) present invention process oxidation efficiency height, low cost.
(3) environmental friendliness of the present invention, raw material are easy to get, and catalyst can reclaim and reuse, technique mistake
Non-secondary pollution problem in journey.
Detailed description of the invention
Embodiment 1:
First trivalent arsenic pH value of solution is adjusted to 11.5 (arsenious concentration is 2.4g/L in solution), open
Stirring and be warming up to 50 DEG C, mixing speed is 200r/min, then adds MnO in solution2(granularity is
3.6um, specific surface area are 11.2m2/ g), the MnO of addition2Arsenious mol ratio is with raw material liq
0.12:1；(in course of reaction, the consumption of air is equal to reason finally to blast air according to the flow velocity of 0.3L/min
4.5 times of opinion consumption), after reaction 1.5h, filter, filter residue is MnO2(washing, dried reuse), filter
Liquid is oxidated solution, and in oxidated solution, arsenious concentration is less than or equal to 88ug/L, calculates: the oxygen of arsenic
Rate is up to more than 95%.
Embodiment 2:
First being adjusted by trivalent arsenic pH value of solution to 9.2 (arsenious concentration is 2.4g/L in solution), unlatching is stirred
Mixing and be warming up to 80 DEG C, mixing speed is 300r/min, then adds MnO in solution2(granularity be 6.5um,
Specific surface area is 7.8m2/ g), the MnO of addition2Arsenious mol ratio is 0.18:1 with raw material liq；
(in course of reaction, the consumption of air is equal to theoretical amount finally to blast air according to the flow velocity of 0.48L/min
5 times), after reaction 2h, filter, filter residue is MnO2(washing, dried reuse), after filtrate is for oxidation
Liquid, in oxidated solution arsenious concentration be less than or equal to 38ug/L, calculate: the oxygenation efficiency of arsenic up to
More than 98%.
Embodiment 3:
First trivalent arsenic pH value of solution is adjusted to 12.1 (arsenious concentration is 2.4g/L in solution), open
Stirring and be warming up to 60 DEG C, mixing speed is 250r/min, then adds MnO in solution2(granularity is
1.2um, specific surface area are 27.6m2/ g), the MnO of addition2Arsenious mol ratio is with raw material liq
0.16:1；(in course of reaction, the consumption of air is equal to finally to blast air according to the flow of 0.36L/min
7 times of theoretical amount), after reaction 1h, filter, filter residue is MnO2(washing, dried reuse), filter
Liquid is oxidated solution, and in oxidated solution, arsenious concentration is less than or equal to 124ug/L, calculates: arsenic
Oxygenation efficiency is up to more than 94%.
Embodiment 4:
First being adjusted by trivalent arsenic pH value of solution to 7 (arsenious concentration is 0.36g/L in solution), unlatching is stirred
Mixing and be warming up to 75 DEG C, mixing speed is 300r/min, then adds MnO in solution2(granularity be 8.4um,
Specific surface area is 5.8m2/ g), the MnO of addition2Arsenious mol ratio is 0.08:1 with raw material liq；
(in course of reaction, the consumption of air is equal to theoretical amount finally to blast air according to the flow velocity of 0.48L/min
4 times), after reaction 5h, filter, filter residue is MnO2(washing, dried reuse), after filtrate is for oxidation
Liquid, in oxidated solution, arsenious concentration is less than or equal to 5ug/L, calculates: the oxygenation efficiency of arsenic is up to 98%
Above.
Embodiment 5:
First being adjusted by trivalent arsenic pH value of solution to 1.2 (arsenious concentration is 7.3g/L in solution), unlatching is stirred
Mixing and be warming up to 65 DEG C, mixing speed is 350r/min, then adds MnO in solution2(granularity be 1.2um,
Specific surface area is 27.6m2/ g), the MnO of addition2Arsenious mol ratio is 0.06:1 with raw material liq,
(in course of reaction, the consumption of air is equal to theoretical amount finally to blast air according to the flow velocity of 0.8L/min
6.5 times), after reaction 3.5h, filter, filter residue is MnO2(washing, dried reuse), filtrate is oxygen
Liquid after change, in oxidated solution, arsenious concentration is less than or equal to 76ug/L, calculates: the oxygenation efficiency of arsenic can
Reach more than 95%.
Embodiment 6:
First being adjusted by trivalent arsenic pH value of solution to 4.6 (arsenious concentration is 7.3g/L in solution), unlatching is stirred
Mixing and be warming up to 35 DEG C, mixing speed is 250r/min, then adds MnO in solution2(granularity be 6.5um,
Specific surface area is 7.8m2/ g), the MnO of addition2Arsenious mol ratio is 0.12:1 with raw material liq；
(in course of reaction, the consumption of air is equal to theoretical amount finally to blast air according to the flow velocity of 1.2L/min
5 times), after reaction 4h, filter, filter residue is MnO2(washing, dried reuse), filtrate is oxidated solution,
In oxidated solution, arsenious concentration is less than or equal to 392ug/L, calculates: the oxygenation efficiency of arsenic is up to 92%
Above.
Claims (5)
1., with manganese dioxide for an arsenious method in catalyst air oxidation solution, its feature exists
In:
By MnO2It is 0.05-0.2:1 with arsenious mol ratio, by MnO2Add containing in arsenious solution
And mix, simultaneously blast air toward containing in arsenious solution, after stirring, completing reaction, filter, filter
Slag is MnO2, filter residue reuse scrubbed, dried；Filtrate is oxidated solution；During reaction, control reaction temperature
Degree is for 30-90 DEG C；
Described MnO2Particle mean size≤10um, specific surface area >=5m2/g；
The described pH value containing arsenious solution is 7-14；
When blasting oxygen-containing gas, coutroi velocity is 0.1-2.5L/min；In course of reaction, the consumption of oxygen-containing gas
More than or equal to theoretical amount 4-8 times；Described theoretical amount is that trivalent arsenics all in solution are oxidized to five by oxygen
The consumption of oxygen needed for valency arsenic.
One the most according to claim 1 is with manganese dioxide for trivalent in catalyst air oxidation solution
The method of arsenic, it is characterised in that: described containing in arsenious solution, arsenious concentration is >=20ug/L.
One the most according to claim 1 with manganese dioxide for catalyst air oxidation solution in three
The method of valency arsenic, it is characterised in that: during stirring, control mixing speed is 100-400r/min.
One the most according to claim 1 with manganese dioxide for catalyst air oxidation solution in three
The method of valency arsenic, it is characterised in that: the reaction time controls as 1-4h.
One the most according to claim 1 with manganese dioxide for catalyst air oxidation solution in three
The method of valency arsenic, it is characterised in that: install gas distribution grid in reactor additional.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104522442A (en) * | 2014-12-19 | 2015-04-22 | 暨南大学 | Method for treating trivalent arsenic ions in liquid food |
| CN113754040A (en) * | 2021-09-23 | 2021-12-07 | 南京大学 | Method for oxidizing trivalent arsenic in water body by using micro/nano activated carbon powder |
| CN114854992B (en) * | 2022-05-24 | 2024-03-15 | 江西理工大学 | Method for separating arsenic and antimony from arsenic caustic sludge leaching solution by deep oxidation |
| CN115043481A (en) * | 2022-06-23 | 2022-09-13 | 江西理工大学 | Method for oxidizing As (III) in water body by using supported manganese-based catalyst |
| CN115074542B (en) * | 2022-06-23 | 2024-03-15 | 江西理工大学 | Method for separating arsenic and antimony in arsenic alkali residue by catalytic oxidation leaching process |
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| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102531249A (en) * | 2011-12-29 | 2012-07-04 | 同济大学 | Method for removing As(III) by photocatalytic oxidation and coagulation |
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| CN103319060A (en) * | 2013-06-17 | 2013-09-25 | 长江水利委员会长江科学院 | Microwave induced catalytic oxidation immobilization treatment method for arsenic in sediments |
| CN103566947A (en) * | 2012-08-07 | 2014-02-12 | 北京三聚环保新材料股份有限公司 | Normal-temperature dearsenic agent as well as preparation method thereof |
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- 2014-05-13 CN CN201410200439.9A patent/CN103951026B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508479A (en) * | 2009-02-13 | 2009-08-19 | 中南大学 | Oxidation method for trivalent arsenic in solution |
| CN102531249A (en) * | 2011-12-29 | 2012-07-04 | 同济大学 | Method for removing As(III) by photocatalytic oxidation and coagulation |
| CN102616859A (en) * | 2012-03-21 | 2012-08-01 | 沈阳农业大学 | Preparation method of delta-type manganese dioxide and application of delta-type manganese dioxide to removal of trivalent arsenic from water through oxidation |
| CN103566947A (en) * | 2012-08-07 | 2014-02-12 | 北京三聚环保新材料股份有限公司 | Normal-temperature dearsenic agent as well as preparation method thereof |
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