CN102468506A - Method for preparing hydrogen by catalyzing and decomposing formic acid in functional ionic liquid - Google Patents
Method for preparing hydrogen by catalyzing and decomposing formic acid in functional ionic liquid Download PDFInfo
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- CN102468506A CN102468506A CN201010551599XA CN201010551599A CN102468506A CN 102468506 A CN102468506 A CN 102468506A CN 201010551599X A CN201010551599X A CN 201010551599XA CN 201010551599 A CN201010551599 A CN 201010551599A CN 102468506 A CN102468506 A CN 102468506A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for preparing hydrogen by catalyzing and decomposing formic acid in a functional ionic liquid. In the method, an amido functional ionic liquid is used; the formic acid is efficiently decomposed to prepare the hydrogen under a mild condition in catalyst systems such as ruthenium, palladium and the like; and reacted products only have target products: carbon dioxide and the hydrogen without unexpected carbon monoxide, so that the hydrogen can be directly applied to hydrogen-oxygen (air) fuel cells through simple gas separation, and the method has a wide application prospect.
Description
Technical field
The present invention relates to a kind of in functionalized ion liquid under the temperate condition catalysis formic acid decompose the method prepare hydrogen.
Background technology
The use of fossil fuel has caused serious pollution to atmospheric environment, particularly in the city, uses the tail gas of the motor vehicle emission of fossil fuel to become major pollution source in the present city.In today of growing interest global environment and human health, the automobile of developing and promote free of contamination fuel cell-driven has become current research focus and social trend.Hydrogen-oxygen (air) fuel cell is a kind of TRT of clean and effective, has high-energy-density, long circulation life and distinguishing feature such as pollution-free, and will occupy critical role future in fuel cell field.Yet the storage of hydrogen and transmission problem have seriously limited the practical application of hydrogen.
The preparation method of hydrogen has the steam reforming, Water gas shift/WGS of water electrolysis, methane or hydro carbons, the cracking of alcohol etc.; The water electrolysis method energy consumption is difficult on the vehicle fuel battery more greatly and uses; And all the other several methods all need high temperature; And the hydrogen of preparation inevitably contains carbon monoxide, and carbon monoxide is prone to make the work electrode of fuel cell to poison.Room temperature effectively releasing hydrogen gas have only metal or metallic compound, for example NaBH
4With the system (US6358488) of water, but there are significant disadvantages such as toxicity, price and fail safe in these systems.
Formic acid is a kind of important chemical product, and is nontoxic, can be used as food additives; Nonflammable, storage and transportation safety are convenient; Contain 4.4% hydrogen, catabolite has only hydrogen and carbon dioxide under appropraite condition, does not have accessory substances such as carbon monoxide, therefore can poisoning effect not arranged to the operation of fuel cells electrode.Based on this, formic acid causes Green Chemistry researcher's very big concern and discussion as the effective controlled preparation hydrogen of hydrogen source.M.Beller etc. (Angew.Chem.Int.Ed., 2008,47,3962-3965) with [RuCl
2(p-cymene)]
2And RuCl
2(PPh
3)
3Be catalyst, studied the catalytic decomposition hydrogen manufacturing of formic acid in the presence of organic base, studied of the influence of the consumption of different organic amines and organic amine simultaneously reaction room temperature or 40 ℃.The result shows, formic acid catalytic decomposition hydrogen manufacturing effectively, and product has only carbon dioxide and hydrogen, removes carbon dioxide and organic amine through separating, and hydrogen can directly apply to fuel cell.Meanwhile, and G.Laurenczy etc. (Angew.Chem.Int.Ed., 2008,47,3966-3968) with [Ru (H
2O)
6]
2+And RuCl
3Be catalyst, the catalytic decomposition hydrogen manufacturing when having studied HCOOH/HCOONa (9: the 1) aqueous solution in the presence of the part TPPTS respectively in room temperature to 120 ℃.More than 80 ℃, formic acid can decompose apace, and temperature high de-agglomeration more is fast more, and formic acid just can decompose about 95% in a few minutes in the time of 120 ℃.But in the above-mentioned reaction system, the former has used volatile organic amine, has increased the program of removing organic amine together during application, has also just increased complexity and the cost used; The latter has used the HCOONa aqueous solution and has replaced organic amine, though it does not have volatility, when low temperature or formic acid concn are low, all be prone to solidify, and the catalytic activity during this system low temperature is lower, has limited universality and popularity in its use.
Ionic liquid at room temperature (RTILs) is meant mainly by organic cation and inorganic or organic anion constitutes in room temperature or be bordering on the fused salt that is in a liquid state under the room temperature to have much incomparable special performances of molecular solvent such as extremely-low vapor pressure, high thermal and electrochemical stability, designability.Can design the ionic liquid of amino or functional amido as required, the characteristic of its extremely-low vapor pressure can remedy the volatile shortcoming of traditional organic amine, thereby replaces traditional organic amine.(J.Am.Chem.Soc. such as E.D.Bates; 2002; 124,926-927) synthesized can absorbing carbon dioxide novel amino functionalized ion liquid 1-(1-aminoalkyl)-3-butyl imidazole tetrafluoroborate, the absorbability of its absorbability and traditional absorbent organic amine is suitable.(CN101337939A such as Han Buxing; Angew.Chem.Int.Ed.; 2008; 47,1127-1129) with synthetic alkaline functional ionic liquid 1-(N, N-dimethyl aminoethyl)-2; 3-methylimidazole trifluoromethyl sulfonic acid is applied in the reaction of hydrogenation of carbon dioxide generation formic acid, has the productive rate of raising, separates simple, reusable advantage.
Summary of the invention
The object of the present invention is to provide a kind of in functionalized ion liquid the effective method of catalysis formic acid decomposing hydrogen-production.
The method of catalysis formic acid decomposing hydrogen-production in a kind of functionalized ion liquid is characterized in that this method adopts the functional amido ionic liquid, under the effect of complex metal, realizes catalytic decomposition hydrogen manufacturing;
Its cationic structural formula of functional amido ionic liquid is:
Above-mentioned R
1And R
3, R
4The C that representes respectively
1-C
8Alkyl, i.e. a kind of in methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl or the n-octyl, R
1, R
3And R
4Can be identical, also can be different; R
2Expression H (amino) or alkyl (amido), wherein alkyl refers to a kind of in methyl, ethyl or the isopropyl; N is 1 to 6 integer;
The ion liquid anion of functional amido is halogen anion, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N-or HCOO
-In a kind of;
Employed metal catalysts precursors is a kind of in ruthenic chloride, radium chloride, palladium bichloride, iridium chloride or the chlorauride;
The part of employed metallic catalyst is benzene, cymene, triphenylphosphine, 2; 2 '-bipyridine, three-(a sodium sulfonate group triphenyl) phosphine, ethylenediamine, N; N-dimethyl-ethylenediamine, tetramethylethylenediamine, 1; 10-Phen, 2-aminopyridine, L-proline or 1, a kind of in 4-two azo dicyclo [2.2.2] octanes.
Reaction condition of the present invention is: the temperature of formic acid decomposition reaction is 10-95 ℃, and pressure is normal pressure.
The mol ratio of metal catalysts precursors used in the present invention and part is 1-5.
Formic acid concn used in the present invention is 85-99wt%, and formic acid and ion liquid mol ratio are 0.5-10.
The mol ratio of formic acid of the present invention and complex metal is 100-2000.
The present invention adopts suitable functional amido ionic liquid; In catalyst systems such as ruthenium, palladium, realized the efficient decomposing hydrogen-production of formic acid under temperate condition; And the product of reaction has only target product carbon dioxide and hydrogen and the carbon monoxide do not expected; Thereby through simple gas separations, hydrogen can directly apply to hydrogen-oxygen (air) fuel cell, has broad application prospects.
The breadboard implementation process of the present invention is: in a single port double glazing reactor that contains magneton by the recirculated water heating, add catalyst, functionalized ion liquid and formic acid successively, be fixed on the magnetic stirring apparatus, connect the condenser pipe of logical recirculated water cooling.After the magnetic agitation, open the heat recirculated water that is heated to 40～80 ℃.(carbon dioxide: hydrogen=1: 1) measure through a normal temperature and pressure gas volume determinator (gas burette), the gas of generation is collected in the air bag gas volume that reaction produces, and by determination of infrared spectroscopy, the result shows CO
2The existence of gas and do not have CO.
The advantage that the present invention compares with the method for catalysis formic acid decomposing hydrogen-production in the past:
1. compare with organic amine formic acid decomposing solution, use the functional amido ionic liquid of extremely-low vapor pressure, formic acid decomposing hydrogen-production system is cleaned more;
2. compare with sodium formate formic acid decomposing solution, use the functional amido ionic liquid, make under the low temperature formic acid decomposing hydrogen-production system more efficient;
3. functional amido formate ion liquid has combined the characteristics of organic amine and sodium formate, and its application makes that formic acid decomposing hydrogen-production system cleans more under the low temperature, efficiently.
Embodiment
Embodiment 1
Take by weighing catalyst { RuCl
2(p-cymene) }
230.85 μ mol, ionic liquid Et2N-EMimBF
4[1-(N; N-diethylamide ethyl)-and the 3-methyl imidazolium tetrafluoroborate] 5mmol, formic acid (97%) 30.85mmol, 1.2mL; 80 ℃ of stirring and refluxing stoichiometric numbers hour; The cumulative volume of the gas of emitting in the record thermostatic process, wherein the cumulative volume of gas is 403mL in 1 hour, the cumulative volume of gas is 602mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 2
Use embodiment 1 said catalyst, ionic liquid H
2N-EMimBF
4(1-amino-ethyl-3-methyl imidazolium tetrafluoroborate) replaces the ionic liquid of embodiment 1,80 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 91mL in 1 hour, the cumulative volume of gas is 169mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 3
Use embodiment 1 said catalyst, ionic liquid Et
2N-EMimPF
6[1-(N, N-diethylamide ethyl)-3-methylimidazole hexafluorophosphate] replaces the ionic liquid of embodiment 1,80 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 225mL in 1 hour, the cumulative volume of gas is 305mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 4
Use embodiment 1 said catalyst, ionic liquid Et
2N-EMimOTf [1-(N, N-diethylamide ethyl)-3-methylimidazole fluoroform sulphonate] replaces the ionic liquid of embodiment 1,80 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 333mL in 1 hour, the cumulative volume of gas is 494mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 5
Use embodiment 1 said catalyst, ionic liquid Me
2N-EMimCl [1-(N, N-dimethyl aminoethyl)-3-methylimidazole villaumite] replaces the ionic liquid of embodiment 1,80 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 145mL in 1 hour, the cumulative volume of gas is 248mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 6
Use embodiment 1 said catalyst, ionic liquid Me
2N-EMimCl [1-(N, N-dimethyl aminoethyl)-3-methylimidazole villaumite] replaces the ionic liquid of embodiment 1,60 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 33mL in 1 hour, the cumulative volume of gas is 58mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 7
Use embodiment 1 said catalyst, ionic liquid i-Pr
2N-EMimCl [1-(N, N-diisopropylamine ethyl)-3-methylimidazole villaumite] replaces the ionic liquid of embodiment 1,60 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 108mL in 1 hour, the cumulative volume of gas is 206mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 8
Use embodiment 1 said catalyst, ionic liquid i-Pr
2N-EMimHCOO [1-(N, N-diisopropylamine ethyl)-3-methylimidazole formates] replaces the ionic liquid of embodiment 1,60 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 199mL in 1 hour, the cumulative volume of gas is 362mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 9
Use embodiment 1 said catalyst, ionic liquid i-Pr
2N-EMimHCOO [1-(N, N-diisopropylamine ethyl)-3-methylimidazole formates] replaces the ionic liquid of embodiment 1,40 ℃ of stirring and refluxing stoichiometric numbers hour, and wherein the cumulative volume of gas is 13mL in 1 hour, the cumulative volume of gas is 26mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 10
Use embodiment 1 said catalyst, ionic liquid i-Pr
2N-EMimHCOO [1-(N; N-diisopropylamine ethyl)-and 3-methylimidazole formates] replace the ionic liquid of embodiment 1, formic acid (97%) changes 10mmol into, 40 ℃ of stirring and refluxing stoichiometric numbers hour; Wherein the cumulative volume of gas is 60mL in 1 hour, and the cumulative volume of gas is 93mL (CO in 2 hours
2: H
2=1: 1).
Embodiment 11
Take by weighing catalyst { RuCl
2(p-cymene) } 230.85 μ mol, triethylamine 5mmol, formic acid (97%) 30.85mmol, 60 ℃ of stirring and refluxing stoichiometric numbers hour, wherein the cumulative volume of gas is 48mL in 1 hour, the cumulative volume of gas is 79mL (CO in 2 hours
2: H
2=1: 1).
Claims (5)
1. the method for catalysis formic acid decomposing hydrogen-production in the functionalized ion liquid is characterized in that this method adopts the functional amido ionic liquid, under the effect of complex metal, realizes catalytic decomposition hydrogen manufacturing;
Its cationic structural formula of functional amido ionic liquid is:
Above-mentioned R
1And R
3, R
4The C that representes respectively
1-C
8Alkyl, i.e. a kind of in methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl or the n-octyl, R
1, R
3And R
4Can be identical, also can be different; R
2Expression H (amino) or alkyl (amido), wherein alkyl refers to a kind of in methyl, ethyl or the isopropyl; N is 1 to 6 integer;
The ion liquid anion of functional amido is halogen anion, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-Perhaps HCOO
-In a kind of;
Employed metal catalysts precursors is a kind of in ruthenic chloride, radium chloride, palladium bichloride, iridium chloride or the chlorauride;
The part of employed metallic catalyst is benzene, cymene, triphenylphosphine, 2; 2 '-bipyridine, three-(a sodium sulfonate group triphenyl) phosphine, ethylenediamine, N; N-dimethyl-ethylenediamine, tetramethylethylenediamine, 1; 10-Phen, 2-aminopyridine, L-proline or 1, a kind of in 4-two azo dicyclo [2.2.2] octanes.
2. the method for claim 1, the temperature that it is characterized in that the formic acid decomposition reaction is 10-95 ℃, pressure is normal pressure.
3. the method for claim 1, the mol ratio that it is characterized in that metal catalysts precursors and part is 1-5.
4. the method for claim 1 is characterized in that formic acid concn is 85-99wt%, and formic acid and ion liquid mol ratio are 0.5-10.
5. the method for claim 1, the mol ratio that it is characterized in that formic acid and complex metal is 100-2000.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833914A (en) * | 2016-04-13 | 2016-08-10 | 大连理工大学 | Dinuclear complex catalyst, preparation method and application thereof in preparing hydrogen by catalyzing formic acid decomposition |
| CN106466639A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Low temperature anti-be poisoned homogeneous ruthenium iridium catalyst, its preparation method and application |
| CN106466640A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | The iridium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application |
| CN106466638A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | The ruthenium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application |
| JP2017043556A (en) * | 2015-08-26 | 2017-03-02 | 国立大学法人東北大学 | Compound, ionic liquid, platinum group element extraction agent, and platinum group element extraction method |
| CN108298499A (en) * | 2018-03-06 | 2018-07-20 | 大连理工大学 | A kind of method that water-soluble metal complexes catalysis formic acid decomposes hydrogen release |
-
2010
- 2010-11-16 CN CN201010551599XA patent/CN102468506A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Fuel Chemistry and Technology(燃料化学学报)》 20101031 LI Xue-li,et al. "Selective catalytic formic acid decomposition for hydrogen generation inionic liquids" 544-553 1-5 第38卷, 第5期 * |
| LI XUE-LI,ET AL.: ""Selective catalytic formic acid decomposition for hydrogen generation inionic liquids"", 《JOURNAL OF FUEL CHEMISTRY AND TECHNOLOGY(燃料化学学报)》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106466639A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Low temperature anti-be poisoned homogeneous ruthenium iridium catalyst, its preparation method and application |
| CN106466640A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | The iridium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application |
| CN106466638A (en) * | 2015-08-17 | 2017-03-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | The ruthenium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application |
| CN106466638B (en) * | 2015-08-17 | 2019-02-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | The ruthenium catalyst and its preparation method of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and application |
| CN106466640B (en) * | 2015-08-17 | 2019-09-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | The iridium catalyst and its preparation method of the anti-poison guard catalyst formic acid hydrogen manufacturing of efficient cryogenic and application |
| JP2017043556A (en) * | 2015-08-26 | 2017-03-02 | 国立大学法人東北大学 | Compound, ionic liquid, platinum group element extraction agent, and platinum group element extraction method |
| CN105833914A (en) * | 2016-04-13 | 2016-08-10 | 大连理工大学 | Dinuclear complex catalyst, preparation method and application thereof in preparing hydrogen by catalyzing formic acid decomposition |
| CN105833914B (en) * | 2016-04-13 | 2018-02-16 | 大连理工大学 | A kind of binuclear complex catalyst, preparation method and applications are in catalysis formic acid decomposing hydrogen-production |
| CN108298499A (en) * | 2018-03-06 | 2018-07-20 | 大连理工大学 | A kind of method that water-soluble metal complexes catalysis formic acid decomposes hydrogen release |
| CN108298499B (en) * | 2018-03-06 | 2021-04-20 | 大连理工大学 | Method for decomposing and releasing hydrogen by catalyzing formic acid with water-soluble metal complex |
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Application publication date: 20120523 |