WO2015025250A1

WO2015025250A1 - Method for uptaking a spilled liquid

Info

Publication number: WO2015025250A1
Application number: PCT/IB2014/063911
Authority: WO
Inventors: Stefan Maurer; Riichiro Kimura; Andrei-Nicolae PARVULESCU; Julia PETRY; Lorenz Siggel; Ulrich Müller
Original assignee: Basf Se; Basf China Company Limited
Priority date: 2013-08-22
Filing date: 2014-08-14
Publication date: 2015-02-26

Abstract

The present invention relates to a method for at least partly uptaking a spilled liquid comprising at least one liquid hydrocarbon, the method comprising the step of contacting the at least one liquid hydrocarbon with a binder agent comprising at least one porous metal-organic framework material, wherein the at least one metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion, wherein the at least one organic com- pound is based on imidazole, which is unsubstituted or substituted with one or more substituents independently selected from the group consisting of C_1-6 alkyl, phenyl and benzyl. The invention further relates to the use of such a binder agent for at least partly uptaking the liquid.

Description

Method for uptaking a spilled liquid

Description

The present invention relates to a method for at least partly uptaking a spilled liquid comprising at least one liquid hydrocarbon, the method comprising the step of contacting the at least one liquid hydrocarbon with a binder agent. The invention further relates to the use of such a binder agent for at least partly uptaking the liquid.

Spilled hydrocarbons, especially oil spills in the sea, rivers, lakes or groundwater pose a strong threat towards the environment. US government estimates around 706 million gallons of waste oil entering the environment each year from pipelines, oil rigs or storage tanks. Such spills can be caused by e.g. accidents, breakdown of equipment, natural disasters and deliberate and illegal dumping of oil into water.

Particularly the BP oil rig disaster (Deepwater horizon) in the Gulf of Mexico attracted intense research efforts from both academia and industry. Commonly used methods include mechanical extraction, combustion and chemical degradation. Owing to the economy and efficiency for oil spill cleanup, mechanical extraction by sorption materials is regarded as one of the most desirable choices for the recovery of oil [J. Wang, Y. Zheng, A. Wang, Chemical Engineering Journal 213 (2012) 1-7].

Many sorption materials such as inorganic mineral materials [C. Teas, S. Kalligeros, F. Zanikos, S. Stournas, E. Lois, G. Anastopoulos, Investigation of the effectiveness of absorbent materials in oil spills clean up, Desalination 140 (2001 ) 259-264], synthetic materials [X.M. Zhou, C.Z. Chuai, Synthesis and characterization of a novel high-oilabsorbing resin, J. Appl. Polym. Sci. 1 15 (2010) 3321-3325] and natural materials have been widely studied for the removal of spilled oil. However, these materials still have limitations such as low oil sorption capacity, limited availability at larger scale, high costs, or poor reusability.

For example spongy graphene [H. Bi, X. Xie, K. Yin, Y. Zhou, S. Wan, L. He, F. Xu, F. Banhart, L. Sun, R. S. Ruoff, Adv. Funct. Mater. 22 (2012) 4421^1425] which shows exceptional high uptake capacities compared to previously reported adsorbents together with good recyclability is only available in mg scale.

Very recently a porous polymer (covalent porphyrine framework) showing also promising properties towards absorbance of organics was published [X.-S. Wang, J. Liu, J. M. Bonefont, D.-Q. Yuan, P. K. Thallapally, S. Ma, Chem. Commun. 49 (2013) 1533-1535] claiming highest adsorp- tive capacities. This material however relies on highly sensitive Yamamoto coupling to build up the porous framework, making its scale up impossible on an industrial basis. The take up of liquids using porous metal-organic framework material ("MOF") in general is known from EP 1 702 925 A1 . Also specific metal-organic framework materials are described for the uptake of hydrocarbons and alcohols in H. Wu et al., Chem. Rev. 1 12 (2012), 836-868. Fluorous metal-organic framework material for oil spill cleanup is described in C. Yang et al., J. Am. Chem. Soc. 133 (201 1 ), 18094-18097.

However there is a need for more advanced metal-organic framework materials for the uptake of liquids comprising hydrocarbons for the spill uptake in order to overcome at least partly disadvantages relating to the total amount of uptaken hydrocarbon, accessibility of higher amounts of material (industrial scale), moisture/water stability, and recovery of binder agent (recycling).

Accordingly an object of the present invention is to provide a method for the uptake of a liquid comprising at least one hydrocarbon using a metal-organic framework material (MOF) having at least partly better properties as described above.

The object is achieved by a method for at least partly uptaking a spilled liquid comprising at least one liquid hydrocarbon, the method comprising the step of

(a) contacting the spilled liquid comprising at least one liquid hydrocarbon with a binder agent comprising at least one porous metal-organic framework material, wherein the at least one metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion, wherein the at least one organic compound is based on imidazole, which is un- substituted or substituted with one or more substituents independently selected from the group consisting of Ci-6 alkyl, phenyl and benzyl.

The object is further achieved by the use of a binder agent comprising at least one porous metal-organic framework material for at least partly uptaking a liquid comprising at least one liquid hydrocarbon, wherein the at least one metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion and wherein the at least one organic compound is based on imidazole, which is unsubstituted or substituted with one or more substituents independently selected from the group consisting of Ci-6 alkyl, phenyl and benzyl.

Surprisingly, it has been found that the porous metal-organic framework material described herein shows exceptional good properties, such as hydrophobicity, defined structure and pore diameter distribution resulting in favorable uptake kinetics towards liquids, high stability towards temperature and moisture.

Below preferred embodiments are described being preferred for both, the method of the present invention as well as the use of the present invention.

In general, in case the term "comprise" or "comprising" is used this also refers to "consisting of. The term "liquid" means the liquid state under standard conditions of 20°C and 1023 mbar. According to the present invention the binder agent comprises at least one porous metal- organic framework material. Thus the binder agent comprises one or more, like two three or four, metal-organic framework materials. However preferably, only one metal-organic framework material is comprised. It is also possible that the binder material consists of at least one porous metal-organic framework material, i.e. the binder material is the metal-organic framework material or a mixture of metal-organic framework materials.

The binder agent can also comprise further sorbent material and/or additives. Suitable sorbent materials are activated charcoal or zeolites.

A number of inorganic compounds can be used as additives. Non-limiting examples include titanium dioxide, hydrated titanium dioxide, hydrated alumina or other aluminum-containing binders, mixtures of silicon and aluminum compounds, silicon compounds, clay minerals, alkoxysilanes, and amphiphilic substances.

Other conceivable additives are in particular oxides, of silicon, of aluminum, of boron, of phosphorus, of zirconium and/or of titanium are preferably used. Of particular interest also is silica. Oxides of magnesium and of beryllium and clays, for example montmorillonites, kaolins, benton- ites, halloysites, dickites, nacrites and anauxites, may furthermore be used. Tetraalkoxysilanes are particularly used as additives in the present invention. Specific examples are tetramethox- ysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, the analogous tetraalkoxy- titanium and tetraalkoxyzirconium compounds and trimethoxy-, triethoxy-, tripropoxy- and tribu- toxyaluminum, tetramethoxysilane and tetraethoxysilane being particularly preferred.

In addition, organic viscosity-enhancing substances and/or hydrophilic polymers, e.g. cellulose or polyacrylates may be used as additives. The organic viscosity-enhancing substance used may likewise be any substance suitable for this purpose. Those preferred are organic, in particular hydrophilic polymers, e.g., cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene and polytetrahydrofuran.

Amines or amine-like compounds, for example tetraalkylammonium compounds or aminoalco- hols, and carbonate-containing substances, such as calcium carbonate, may be used as further additives. Such further additives are described in EP-A 0 389 041 , EP-A 0 200 260 and WO 95/19222.

The porous metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion. The metal-organic framework material can also consist of one or more than one metal ions, where more than one ion can differ from each other by chemical nature and/or charge. Also one or more, like two, three or four, organic compounds are possible. Most preferably, the porous metal-organic framework material consists of one metal ion and one organic compound. Such metal-organic framework material can be prepared according to methods known in the art. Examples can be found in WO 2007/131955 A1 or WO 2013/005160 A1 . Preferably, the at least one metal ion is selected from the group of metals consisting of copper, iron, aluminum, zinc, magnesium, zirconium, titanium, vanadium, molybdenum, tungsten, indium, calcium, strontium, cobalt, nickel, platinum, rhodium, ruthenium, palladium, scandium, yttrium, a lanthanide, manganese and rhenium. More preferably, the at least one metal ion is Zn²⁺.

According to the present invention the at least one organic compound is based on imidazole, which is unsubstituted or substituted with one or more (preferably one or two, more preferably one) substituents independently selected from the group consisting of Ci-6 alkyl, phenyl and benzyl.

The term Ci-6 alkyl refers to an alkyl chain having one to six carbon atoms. The alkyl group can be straight-chained or branched. Examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, sec- butyl, tert.-butyl, n-pentyl, n-hexyl. Preferred group is methyl and ethyl. Even more preferred is methyl.

In one aspect the imidazole is unsubstituted. In another aspect the imidazole is substituted. Preferred substituents are methyl, ethyl, phenyl, benzyl. More preferred is methyl, ethyl, and benzyl. Even more preferred is methyl. A preferred substitution is in 2-position of the imidazole.

Even more preferred is the at least one organic compound 2-methylimidazole, 2-ethylimidazole, 2-benzylimidazole or a deprotonated form thereof (i.e. the imidazolate).

The term "based on" means that imidazole, which can also be partly or fully deprotonated (anion), is used. Thus the metal-organic framework material may have all imidazolates in deprotonated form or only part of them.

According to the present invention, the spilled liquid comprises at least one liquid hydrocarbon. Thus the spilled liquid can comprise one or more liquid hydrocarbons. It can also consist of one or more liquid hydrocarbons. The liquid can comprise further components, like solids or resolved gases, especially gaseous hydrocarbons.

According to the present invention, the liquid is preferably in form of a pool of liquid. The uptake of a pool of liquids is described in EP 1 702 925 A1 .

The liquid can comprise or consist of liquid aliphatic hydrocarbons like hexane, heptane or octane. Further possible hydrocarbons are aromatic hydrocarbons, like benzene or naphthene or aliphatic and aromatic hydrocarbons, like toluene.

Preferably, the at least one liquid hydrocarbon is gasoline, diesel or an oil, like mineral oil or crude oil, especially crude oil. Preferably, the at least one liquid hydrocarbon is spilled oil. Crude oil typically represents a mixture of a very large number of different hydrocarbons; the most commonly found molecules are alkanes (paraffins, linear or branched), cycloalkanes, aromatic hydrocarbons, or more complicated chemicals like asphaltenes. Each crude oil variety has a unique mix of molecules, which define its physical and chemical properties, like color and viscosity.

Preferably, the liquid is at least one liquid hydrocarbon mixed with water. Even more preferably, the liquid is at least one liquid hydrocarbon mixed with sea water. Also possible are rivers, lakes or groundwater. Preferably the spills are caused by accidents, breakdown of equipment, natural disasters and deliberate and illegal dumping of oil into water.

According to the present invention, the binder agent and/or the at least one metal-organic framework material can be separated from the above mixture. This process is known as solidifying. Solidifiers are composed of dry hydrophobic polymers that both adsorb and absorb. They clean up oil spills by changing the physical state of spilled oil from liquid to a semi-solid or a rubber-like material that floats on water. Solidifiers are insoluble in water, therefore the removal of the solidified oil is easy and the oil will not leach out. Solidifiers have been proven to be relatively non-toxic to aquatic and wild life and have been proven to suppress harmful vapors commonly associated with hydrocarbons such as Benzene, Xylene, Methyl Ethyl, Acetone and Naphtha. The reaction time for solidification of oil is controlled by the surface area or size of the polymer as well as the viscosity of the oil. Some solidifier product manufactures claim the solidified oil can be disposed of in landfills, recycled as an additive in asphalt or rubber products, or burned as a low ash fuel. A solidifier called C.I. Agent (manufactured by C.I. Agent Solutions of Louisville, Kentucky) is being used by BP in granular form, as well as in Marine and Sheen Booms at Dauphin Island and Fort Morgan, Alabama, to aid in the Deepwater Horizon oil spill cleanup.

Preferably, the at least one metal-organic framework material is in form of shaped bodies. This also applies to the complete binder agent. The preparation of shaped bodies is described for example in WO-A 03/102000 or WO-A 2006/050898. Further methods are known in the art. A shaped body can contain further additives or consists of the at least one metal-organic framework material (binder agent).

The conversion step of molding, shaping or forming and the like may be achieved by any method known to an expert to achieve agglomeration of a powder, a suspension or a paste-like mass.

In general, the following main pathways can be discerned: (i) briquetting, i.e. mechanical pressing of the powdery material, with or without binders and/or other additives, (ii) granulating (pelletizing), i.e. compacting of moistened powdery materials by subjecting it to rotating movements, and (iii) sintering, i.e. subjecting the material to be compacted to a thermal treatment. Specifically, the molding step is preferably performed by using at least one method selected from the following group: briquetting by piston presses, briquetting by roller pressing, binderless briquetting, briquetting with binders, pelletizing, compounding, melting, extruding, co-extruding, spinning, deposition, foaming, spray drying, coating, granulating, in particular spray granulating or granulating according to any process known within the processing of plastics or any combination of at least two of the aforementioned methods.

The molding may be affected by extrusion in conventional extruders, for example such that result in extrudates having a diameter of, usually, from about 1 to about 10 mm, in particular from about 1 ,5 to about 5 mm. Such extrusion apparatuses are described, for example, in Ullmann's Enzylopadie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et seq., 1972. In addition to the use of an extruder, an extrusion press is preferably also used for molding.

The preferred process of molding is performed at elevated pressure, i.e. by pressing of the MOF containing powder. The pressure may range from atmospheric pressure to several 100 bar. Also elevated temperatures (ranging from room temperature to 300 °C) or in a protective atmosphere (noble gases, nitrogen or mixtures thereof) are suitable. Any combination of these conditions is possible as well.

The conditions under which the pressing may be accomplished depend on, e.g. the press, the filling height, the press capacity, and the form of the shaped body.

Preferred shaped bodies are granulates and extrudates.

Preferably, the contacting is carried out by pouring the at least one binder agent onto the liquid. The contacting can be carried out by, e.g., placing metal-organic framework (MOF) material in containment booms (temporary floating barrier used to contain an oil spill); the metal-organic framework material can be included in dissolvable packs (spill response bags) or in fabric that allow passage of oil/water (contacting); MOF films, MOF/textile nets; Pumping water/oil over an oil bed; also MOF Powder spraying is possible.

Preferably, the at least one metal-organic framework is contained in containment booms or dissolvable packs.

Preferably, the at least one metal-organic framework material is recycled after step (a). Examples

1 . Synthesis of MOF material

1 .1 Synthesis of Basolite Z1200 (Zinc-lmidazolate, ZIF-8)

A solution of zink sulfate hepta-hydrate (800 g) in deionized water (2666 g) was prepared. In a separate vessel a second solution was prepared by adding 2-methylimidazole (456 g) to water (2666 g). To the second solution methanol (2222 g) was added within one hour. After allowing the second solution to stir for 1 .25 h solution 1 was added to solution 2 over a period of 1 hour and 10 minutes. During the addition of zinc sulfate solution to the imidazole solution, a white suspension was formed. The resulting suspension was stirred for 1 hour and 15 minutes at 27°C with a stirring speed of 90 mirr¹. To that suspension NaOH solution (50 wt-%, 444 g) was added slowly keeping the temperature below 30 °C. After stirring the suspension for another 1 hour and 15 minutes the content of the vessel was released on a filter and washed ten times with deionized water until the conductivity of the filtrate was below 100 (+/- 50) μθ. For each washing step 1 I of deionized water were used. The water was layered over the material for one hour and afterwards sucked through the filter cake. The wet filter cake was dried in a circulating air oven for 24 h at 120 °C. 600 g of Basolite Z1200 were obtained exhibiting a Langmuir surface area of 1804 m²/g.

The water uptake (water isotherm at 25 °C up to 85 % relative humidity) of that material is less than 1 weight-%.

1 .2 Synthesis of Basolite A520 (Aluminum Fumarate)

Fumaric acid (333 g) was added to a solution of 688 g 50% aqueous sodium hydroxide in 4578 g of water. In a second vessel aluminum sulfate * 14 H2O (907 g) was dissolved in 4095 g water. Solution 1 (fumaric acid/NaOH/h O) was added to solution 2 (Al-sulfate/h O) under stirring at room temperature during 40 min. The resulting suspension was heated up to 60 °C within 30- 40 min. and kept at this temperature for 1 .5 h. The white precipitate was filtered and washed with distilled water until the conductivity of the water was lower than 150 με. After drying at 120 °C for 16 h 378 g Basolite A520 was obtained with a Langmuir surface area of 1314 m²/g.

The water uptake (water isotherm at 25 °C up to 85 % relative humidity) of that material is up to 46 weight-%.

1 .3 Synthesis of IR-MOF-8 (Zinc naphthalene-2,6-dicarboxylate)

Synthesis is carried out according to Methods described in US 7 534 303 B2.

The water uptake (water isotherm at 25 °C up to 85 % relative humidity) of that material is up to 15 weight-%.

1 .4 Synthesis of A100 (Aluminum therephthalate)

Synthesis is carried out according to Methods described in US 7 534 303 B2.

The water uptake (water isotherm at 25 °C up to 85 % relative humidity) of that material is up to 1 1 weight-%. 1 .5 Synthesis of Cu-isophtalic acid MOF

Synthesis is carried out according to Methods described in US 7 534 303 B2.

2. Fisher-Mottlau Pore Volume Assessment The following starting materials were employed.

Basolite Z1200 (Example 1 ) and Basolite A520 (Aluminum Fumarate, Comparative Example)

Toluene

Undecane

Procedure: The corresponding organic solvent was added drop wise to the stirred powdered material. As soon as the solid particles started to coagulate (pore volume is now filled with solvent) the addition was stopped.

Basolite Z1200 powder uptake (hydrophobic MOF)

Toluene: 1 .43g/g MOF

Undecane: 1.65g/g MOF

Comparative example Basolite A520 (hydrophilic MOF)

Toluene: 1 .80 g/g MOF

Undecane: 1.60 g/g MOF

The Fisher Mottlau tests show an increased take up of toluene and undecane by using A520. However surprisingly, this metal-organic framework material is not suitable for the present process and use as demonstrated below.

3. Water/Oil Model System tests

The following starting materials were employed.

Basolite Z1200 (Example 1 ) and Basolite A520 (Comparative Example)

Toluene + 500 ppm Lumogen F (red colorant)

Undecane + 500 ppm Lumogen F (red colorant)

Distilled water

Brine (Distilled water + 3.5 wt% sodium chloride) Test without stirring:

Procedure: According to Table 1 and 2 water or brine (45 ml) and subsequently toluene or un- decane (5 ml) were added to a glass with a lid. The MOF powder than was added to the glass without stirring or any other form of agitation. The resulting mixture was characterized with regard to distribution of MOF and colorant in the phases.

4.1 Comparative Experiments (Basolite A520)

Table 1 : Comparative Experiments:

Results directly after addition:

U 1 .1 A: Small amounts of A520 at the phase border and dispersed in the water phase. Large amounts of precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

U2.1 A: Small amounts of A520 at the phase border and dispersed in the water phase. Large amounts of precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

T1.1 A: Strong precipitation of Solid. Colorant stays in toluene phase. No A520 in the organic phase visible.

T2.1 A: Strong precipitation of Solid. Colorant stays in toluene phase. No A520 in the organic phase visible.

Results after 72 hours:

U 1 : Complete precipitation. Organic phase clear, slightly colored. Water phase clear, no color. U2: Nearly complete precipitation. Small amounts of A520 at the phase border. Organic phase clear, slightly colored. Water phase clear, no color.

T1 : Complete precipitation. Organic phase clear, intensive colored (red colorant). Water phase clear, no color.

T2: Complete precipitation. Organic phase clear, intensive colored (red colorant). Water phase clear, no color. Conclusion: No uptake of organic phase by MOF A520

Filtration tests

Procedure:

After 72 h without agitation the content of a glass was poured on a Buchner filter equipped with a paper filter to separate the solid from the liquid phase.

Results of filtration tests:

U2.1 A: A520 staying in the filter is deeply colored. The filtrate consists of a two phase system: the undecane phase is slightly colored, the water phase is clear.

T2.1 A: A520 staying in the filter is lightly colored. The filtrate consists of a two phase system: the toluene phase is deeply colored, the water phase is clear.

Conclusion: For Basolite A520 no separation of the organic phase from the water phase could be observed.

4.2 Additional Comparative Experiments (IR-MOF8, A100, Cu-lsophthalic acid ("Cu-ISO") MOF)

Procedure: According to Table 2 water or brine (45 ml) and subsequently toluene or undecane (5 ml) were added to a glass with a lid. The MOF powder than was added to the glass without stirring or any other form of agitation. The resulting mixture was characterized with regard to distribution of MOF and colorant (as described above) in the phases.

Table 2: Comparative Experiments:

¹> IR-MOF 8 = Zinc naphthalene-2,6-dicarboxylate

2> A100 = Aluminum therephthalate Results directly after addition:

U_IR8: Large amounts of IR8 at the phase border. No precipitate. Colorant stays in toluene phase.

U_A100: Large amounts of A100 at the phase border and dispersed in the water phase. Small amounts of precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

U_Cu-lso: Large amounts of Cu-lso at the phase border. No precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

T_IR8: Strong precipitation of Solid. Colorant stays in toluene phase.

T_A100: Large amounts of A100 at the phase border and dispersed in the water phase.

Small amounts of precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

T_Cu-lso: Large amounts of Cu-lso at the phase border. No precipitate. Colorant Lumogen is adsorbed in the MOF particle. Clear organic phase.

Results after 72 h:

U_IR8: Nearly complete precipitation. Small amounts of IR8 at the phase border. Organic phase clear, slightly colored. Water phase clear, no color.

U_A100: Nearly complete precipitation. Small amounts of A100 at the phase border. Organic phase clear. Water phase clear, no color.

U_Cu-lso: Almost no precipitation. Large amounts of Cu-lso at the phase border. Organic phase clear. Water phase clear, no color.

T_IR8: Nearly complete precipitation. Small amounts of IR8 at the phase border. Organic phase clear, slightly colored. Water phase clear, no color.

T_A100: Nearly complete precipitation. Small amounts of A100 at the phase border. Organic phase clear. Water phase clear, no color.

T_Cu-lso: Almost no precipitation. Large amounts of Cu-lso at the phase border. Organic phase clear. Water phase clear, no color.

Conclusion: No uptake of organic phase by MOFs. 5. Inventive examples with Basolite Z1200

Results directly after addition:

U 1 .1 Z-2.1Z: Z1200 floats on the water phase. The undecane phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation. The upper half of Z1200 is not colored, full capacity not reached.

T1.1 Z-2.1Z: Z1200 floats on the brine phase. The toluene phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation.

Results after 72 h:

U 1 .1 Z-2.1Z: Z1200 floats on the water phase. No change.

T1.1 Z: Minor amount precipitated, color intensity at Z1200 slightly decreased

T2.1 Z: Color intensity at Z1200 slightly decreased

Experiments with milled Z1200 (smaller particle size)

100 g of Z1200 powder from example 1 were subjected to a milling procedure employing a ball mill (Thermomix TM31 Vorwerk 500W) and milling with 2500-3000 RPM for 10 min.

Surface area remained unchanged with 1800 m²/g.

Table 4: Experiments according to the above procedure

Brine

5 ml. Un5 ml_ 3.5 wt%

Z1200 M decane Toluene Water NaCI

U 1 MZ 2.25 g 3.71 g 45 ml_

U2MZ 2.25 g 3.71 g 45 ml_

T1 MZ 3.03 g 4.33 g 45 mi-

T2MZ 3.03 g 4.33 g 45 ml. Results directly after addition:

U 1 MZ-2MZ: Z1200 floats on the water phase. The undecane phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation. The upper half of Z1200 is not colored, full capacity not reached

T1 MZ-2MZ: Z1200 floats on the brine phase. The toluene phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation.

Results after 72 h:

U 1 MZ-2MZ: No change

T1 MZ-2MZ: No change

Filtration tests

Procedure:

After 72 h without agitation the content of a glass was poured on a glass frit to separate the solid from the liquid phase. To check the reusability of Z1200 for experiments U 1 -2 the filter cake was dried under vacuum over night at 120 °C. The dried powder was subjected to the same treatment like described above.

Results of filtration tests:

U 1 .1 Z-F1 - U2.1 Z-F1 : The undecane phase stayed in the solid Z1200. No two phase system in the filtrate was detected.

T1 .1 Z-F1 - T2.1 Z-F1 : The undecane phase stayed in the solid Z1200. No two phase system in the filtrate was detected.

Results of second filtration test:

U 1 .1 Z-F2 - U2.1 Z-F2: The undecane phase stayed in the solid Z1200. The filtrate consists of the water phase.

The filter cake was dried under vacuum over night at 120 °C. An XRD pattern analysis demonstrates the constancy of the structural integrity after two consecutive adsorption/desorption experiments. The influence of the Langmuir surface area is depicted in the following table 5. Table 5: Langmuir surface area fresh - and spent adsorbent

Experiments with agitation

Procedure: Water or brine (45 ml) and subsequently toluene or undecane (5 ml) were added to a glass with a lid and a magnetic stir bar. The MOF powder was added to the glass under stirring with 250 RPM.

Table 6: Experiments with Agitation:

Results directly after addition:

U 1 SZ: Z1200 floats on the water phase. The undecane phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation. The upper half of Z1200 is not colored. The stirrer is slightly colored.

U2SZ: Z1200 floats on the water phase. The undecane phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation. The upper half of Z1200 is not colored, full capacity not reached. Small parts of Z1200 attached to the linker.

T1 -2SZ: Z1200 floats on the brine phase. The toluene phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation. Small parts of Z1200 attached to the linker.

Results after 72 h of stirring:

U 1 -T2SZ: No change. Experiments with Shaking

Procedure: 45 ml of brine and at second 3.71 g undecane (with 500 ppm Lumogen) were added to a glass with a lid. 2.25 g Z1200 powder than was added to the glass. The glass was put on a vibrating plate (200 RPM/ min) for 60 min to simulate waves on the sea.

Z1200 after shaking test: U 1 SZ

U 1 SZ: Z1200 floats on the water phase. The undecane phase is completely soaked up by Z1200 powder. The water phase is clear, no precipitation.

Experiments with Z1200 in a bag

Procedure: 45 ml of water or brine and 5 ml of undecane were added to a glass with a lid. The MOF powder was put into a bag made of three-layered cellulose wipe (commercially obtained from Kolibri) and subsequently put into the glass.

Table 8 Experiments with MOF in a bag

Results directly after addition of the filled bag with Z1200:

T1 BZ-T2BZ: The toluene phase is soaked up by the Z1200 in the bag. The bags are floating on the top.

Results after 72h addition of the filled bag with Z1200: T1 BZ- T2BZ: No change.

The cellulose bags could be easily removed and only one phase (water phase) remained.

Experiments with Z1200, crude oil, and salt water

Materials:

Z1200 (example 1 )

Crude oil (Wintershall Holding GmbH, 226 mPa^»s @20 °C) Salt water (obtained by dissolving 56429.0 mg of CaCI₂ ^»2H₂0, 22420.2 mg of MgCI₂ ^»6H₂0, 132000.0 mg of NaCI, 270.0 mg of Na₂S0₄, and 380.0 mg of NaB0₂ ^»4H₂0 to 1 L of deionized water, adjusting pH to 5,5 - 6,0 with HCI afterwards)

Procedure:

98 ml of salt water was poured into a glass bottle, and then 2 ml of crude oil and 1.0 g of Z1200 powder were added. The glass bottle was put on a vibrating plate (200 RPM/ min) for 60 min to simulate waves on the sea. The mixture after shaking was filtered, and the solid phase was recovered. The recovered solid phase, crude oil adsorbed on Z1200, was washed with 1.5 L of n- hexane under manually stirring with a spatula. The brown powder was obtained after drying the solid phase at 65 °C under vacuum. The obtained brown powder was again tested for adsorption of crude oil: 99 ml of salt water, 1 ml of crude oil, and 0.5 g of the brown powder were used, following the same procedure with the first trial

Characterization:

Carbon contents of the following samples were measured by elemental analysis:

- pristine Z1200

- crude oil adsorbed on Z1200, after washed with 1.5 L n-hexane

- filtered liquid phase of the mixture of crude oil, salt water, and Z1200 after shaking at the first trial

- the salt water

The results are shown in Table 9. About 98.3 % of adsorbed crude oil was recovered by 1.5L hexane (Input crude oil: 2 ml. = 1 .8 g, and adsorbed crude oil on Z1200 after the washing: 0.03 g ((44,3g - 41 ,3g) / 100g * 1 g))

Table 9. Carbon contents

6. Comparative Experiments Oil (Basolite A520)

Materials:

A520

Procedure:

98 ml of salt water was poured into a glass bottle, and then 2 ml of crude oil and 1 g of A520 powder were added. The glass bottle was put on a vibrating plate (200 RPM/ min) for 60 min to simulate waves on the sea. The mixture after shaking was filtered.

Crude oil remained on the filter paper, but A520 went through the filter paper without adsorbing crude oil.

Claims

Patent Claims

1 . A method for at least partly uptaking a spilled liquid comprising at least one liquid hydrocarbon, the method comprising the step of

(a) contacting the spilled liquid comprising at least one liquid hydrocarbon with a binder agent comprising at least one porous metal-organic framework material, wherein the at least one metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion, wherein the at least one organic compound is based on imidazole, which is unsubstituted or substituted with one or more substituents independently selected from the group consisting of Ci-6 alkyl, phenyl and benzyl.

2. The method of claim 1 , wherein the binder agent consists of at least one porous metal- organic framework material.

3. The method of claim 1 or 2, wherein the at least one metal ion is selected from the group of metals consisting of copper, iron, aluminum, zinc, magnesium, zirconium, titanium, vanadium, molybdenum, tungsten, indium, calcium, strontium, cobalt, nickel, platinum, rhodium, ruthenium, palladium, scandium, yttrium, a lanthanide, manganese and rhenium.

4. The method of any one of claims 1 to 3, wherein the at least one metal ion is Zn²⁺.

5. The method of any one of claims 1 to 4, wherein the at least one organic compound is 2- methylimidazole, 2-ethylimidazole, 2-benzylimidazole or a deprotonated form thereof.

6. The method of any one of claims 1 to 5, wherein the liquid is in form of a pool of liquid.

7. The method of any one of claims 1 to 6, wherein the at least one liquid hydrocarbon is gasoline, diesel or an oil.

8. The method of any one of claims 1 to 7, wherein the at least one liquid hydrocarbon is spilled oil.

9. The method of any one of claims 1 to 8, wherein the liquid is at least one liquid hydrocarbon mixed with water.

10. The method of any one of claims 1 to 9, wherein the liquid is at least one liquid hydrocarbon mixed with sea water.

1 1 . The method of any one of claims 1 to 10, wherein the at least one metal-organic framework material is in form of shaped bodies.

12. The method of any one of claims 1 to 1 1 , wherein the contacting is carried out by pouring the at least one binder agent onto the liquid.

13. The method of any one of claims 1 to 12, wherein the at least one metal-organic framework is contained in containment booms or dissolvable packs.

14. The method of any one of claims 1 to 13, wherein the at least one metal-organic framework material is recycled after step (a).

15. Use of a binder agent comprising at least one porous metal-organic framework material for at least partly uptaking a liquid comprising at least one liquid hydrocarbon, wherein the at least one metal-organic framework material comprises at least one organic compound coordinated to at least one metal ion and wherein the at least one organic compound is based on imidazole, which is unsubstituted or substituted with one or more substituents independently selected from the group consisting of Ci-6 alkyl, phenyl and benzyl.