CN100381610C - Electrochemical preparing method with [OH] ion liquid anion - Google Patents

Electrochemical preparing method with [OH] ion liquid anion Download PDF

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Publication number
CN100381610C
CN100381610C CNB2005100723247A CN200510072324A CN100381610C CN 100381610 C CN100381610 C CN 100381610C CN B2005100723247 A CNB2005100723247 A CN B2005100723247A CN 200510072324 A CN200510072324 A CN 200510072324A CN 100381610 C CN100381610 C CN 100381610C
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ion
electrolysis
ion liquid
ionic liquid
anode
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CN1710148A (en
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张建敏
张锁江
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to an ionic liquid precursor, which is ionic liquid using halogen anions as anions. The anions (such as bromine ions) of the ionic liquid precursor loss electrons and precipitate halogen simple substances (such as bromine) at an anode, and simultaneously, hydrogen gas is released and hydroxyl ions are generated at a cathode. Due to the use of diaphragm electrolysis, namely a female diaphragm and a male diaphragm, corresponding ions can only selectively pass through the diaphragms to reach corresponding electrode chambers; therefore, the generated products such as the bromine and the hydroxyl ions can not carry out reactions to pollute the finally prepared ionic liquid whose anions are the hydroxyl ions. The preparation technology only consumes electric energy and has the advantages of low cost and no pollution discharge to environment, and therefore, the green preparation of the ionic liquid is truly realized.

Description

Negatively charged ion is [OH] -Ion liquid electrochemical preparation method
Technical field:
The present invention relates to negatively charged ion and be [OH] -Ion liquid electrochemical preparation method.
Background technology:
Ionic liquid is a kind of emerging solvent and reaction medium.Because unique physicochemical property such as it are non-volatile, structure can design, ionic liquid has a extensive future fields such as extracting and separating, catalyzed reaction, is expected to replace volatile environmentally harmful conventional organic solvents in 21 century.
Ion liquid preparation all is the preparation methods that adopt ion-exchange at present, for example, and [bmim] [BF 4] promptly be [bmim] [Cl] and NaBF 4Realize ion-exchange in the aqueous solution earlier, the method by organic solvent such as dichloromethane extraction prepares again.Often because can not realize that ionic exchanges fully, the ionic liquid that causes preparing contains foreign ion to the ionic liquid that this method prepares.This point is proposed emphatically in the amino acid ion liquid preparation of reporting recently, as improvement, it is that anionic glyoxaline ion liquid is exchanged for hydroxide ion to bromide anion by anion-exchange column that this author has taked bromide anion, prepares purified amino acid ion liquid with amino acid by neutralization reaction then.
But, ion exchange resin will consume a large amount of water, sodium hydroxide, hydrochloric acid and be used for regeneration of resin when exchange operations, and the very rare product solution of the concentration that obtains will evaporate removes water solvent, this has increased this preparation technology's cost undoubtedly, and the waste water of discharging also can pollute environment.
As everyone knows, chlorine industry has adopted electrochemical preparation technology, and NaCl has been prepared purified sodium hydroxide, hydrogen and chlorine by the electrolytic method of film.Adopt electrochemical method to prepare ionic liquid, could fundamentally reduce the cost of technology, realize zero disposal of pollutants environment.
Summary of the invention
The present invention adopts the method for electrochemical electrolysis, has realized that negatively charged ion is [OH] -Ion liquid electrochemical preparation.
Ionic liquid presoma among the present invention be a kind of be anion ion liquid with the halogen negatively charged ion, the negatively charged ion of this ionic liquid presoma (as bromide anion) loses electronics at anode and separates out halogen simple substance (as bromine), separates out hydrogen and generates hydroxide ion at negative electrode simultaneously.Owing to adopted the film electrolysis, i.e. cavity block and anode membrane, corresponding ion can only optionally pass film and arrive corresponding electrode vessel, and therefore product that generates such as bromine and the hydroxide ion negatively charged ion that pollutes final preparation that can not react is [OH] -Ionic liquid.
[OH]-ion is the electrochemical preparation method of anion ion liquid, it is characterized in that halide-ions is the method for anion ion liquid by electrochemical electrolysis, separate out halogen simple substance at anode, separate out hydrogen and generate hydroxide ion at negative electrode, owing to adopted the film electrolysis, be cavity block and anode membrane, corresponding ion can only optionally pass film and arrive corresponding electrode vessel, finally prepare negatively charged ion for [OH]-ionic liquid.Being used for electrolytic ion liquid negatively charged ion is Br-or Cl-or I-or F-, and positively charged ion is phosphines, glyoxaline compound, aminated compounds.Electrolysis can be adopted single electrolyzer or parallel connection of many electrolyzers or operated in series, electrolytic temperature is between 253.15K-373.15K, negative electrode that electrolysis is used and anode comprise titanium electrode or platinum electrode or nickel electrode or Graphite Electrodes or stainless steel electrode, and electrolysis comprises constant-current electrolysis and constant-potential electrolysis dual mode.
Because only consumed electric energy among this preparation technology, cost is low,, therefore really realized ion liquid green preparation to the zero environmental discharging.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
With [P (C 4H 9) 4] [Br] insert the feed chamber between the cavity block and anode membrane in the electrolyzer, cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[P (C 4H 9) 4] +Enter cathode compartment by anode membrane, [Br] -Enter the anolyte compartment by cavity block, bromide anion loses electronics and separates out bromine simple substance on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [P (C 4H 9) 4] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 2
With [P (C 4H 9) 4] [Cl] insert the feed chamber between the cavity block and anode membrane in the electrolyzer, cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[P (C 4H 9) 4] +Enter cathode compartment by anode membrane, [Cl] -Enter the anolyte compartment by cavity block, chlorion loses electronics and separates out elemental chlorine on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [P (C 4H 9) 4] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 3
[EMIM] [Br] inserted the feed chamber between the cavity block and anode membrane in the electrolyzer, and cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[EMIM] +Enter cathode compartment by anode membrane, [Br] -Enter the anolyte compartment by cavity block, bromide anion loses electronics and separates out bromine simple substance on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [EMIM] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 4
[BMIM] [Br] inserted the feed chamber between the cavity block and anode membrane in the electrolyzer, and cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[BMIM] +Enter cathode compartment by anode membrane, [Br] -Enter the anolyte compartment by cavity block, bromide anion loses electronics and separates out bromine simple substance on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [BMIM] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 5
[HMIM] [Br] inserted the feed chamber between the cavity block and anode membrane in the electrolyzer, and cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[HMIM] +Enter cathode compartment by anode membrane, [Br] -Enter the anolyte compartment by cavity block, bromide anion loses electronics and separates out bromine simple substance on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [HMIM] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 6
[HMIM] [Cl] inserted the feed chamber between the cavity block and anode membrane in the electrolyzer, and cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[HMIM] +Enter cathode compartment by anode membrane, [Cl] -Enter the anolyte compartment by cavity block, chlorion loses electronics and separates out elemental chlorine on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [HMIM] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 7
With [N (C 4H 9) 4] [Cl] insert the feed chamber between the cavity block and anode membrane in the electrolyzer, cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[N (C 4H 9) 4] +Enter cathode compartment by anode membrane, [Cl] -Enter the anolyte compartment by cavity block, chlorion loses electronics and separates out elemental chlorine on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [N (C 4H 9) 4] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 8
With [P (C 15H 31) 4] [Cl] insert the feed chamber between the cavity block and anode membrane in the electrolyzer, cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[P (C 15H 31) 4] +Enter cathode compartment by anode membrane, [Cl] -Enter the anolyte compartment by cavity block, chlorion loses electronics and separates out elemental chlorine on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [P (C 15H 31) 4] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.
Embodiment 9
With [P (C 12H 25) 1(C 4H 9) 3] [Cl] insert the feed chamber between the cavity block and anode membrane in the electrolyzer, cathode compartment and anolyte compartment all add deionized water, and logical direct current carries out electrolysis.[P (C 12H 25) 1(C 4H 9) 3] +Enter cathode compartment by anode membrane, [Cl] -Enter the anolyte compartment by cavity block, chlorion loses electronics and separates out elemental chlorine on the anode, and hydrogen is separated out on the negative electrode, and generates hydroxide ion, thereby obtains [P (C 12H 25) 1(C 4H 9) 3] [OH].Productive rate can reach 100%, and current efficiency is greater than 95%.

Claims (6)

1.[OH] -Ion is the electrochemical preparation method of anion ion liquid, it is characterized in that halide-ions is the method for anion ion liquid by electrochemical electrolysis, separate out halogen simple substance at anode, separate out hydrogen and generate hydroxide ion at negative electrode, owing to adopted the film electrolysis, be cavity block and anode membrane, corresponding ion can only optionally pass film and arrive corresponding electrode vessel, finally prepares negatively charged ion and is [OH] -Ionic liquid.
2. ion liquid electrochemical preparation method according to claim 1, it is characterized in that being used for electrolytic ion liquid negatively charged ion is Br -Or Cl -Or I -Or F -, positively charged ion is phosphines, glyoxaline compound, aminated compounds.
3. ion liquid electrochemical preparation method according to claim 1 is characterized in that electrolysis can adopt single electrolyzer or parallel connection of many electrolyzers or operated in series.
4. ion liquid electrochemical preparation method according to claim 1 is characterized in that electrolytic temperature is between 253.15K-373.15K.
5. ion liquid electrochemical preparation method according to claim 1 is characterized in that negative electrode and anode comprise titanium electrode or platinum electrode or nickel electrode or Graphite Electrodes or stainless steel electrode.
6. ion liquid electrochemical preparation method according to claim 1 is characterized in that electrolysis comprises constant-current electrolysis and constant-potential electrolysis dual mode.
CNB2005100723247A 2005-05-30 2005-05-30 Electrochemical preparing method with [OH] ion liquid anion Expired - Fee Related CN100381610C (en)

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CN100381610C true CN100381610C (en) 2008-04-16

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1181077C (en) * 2000-05-30 2004-12-22 默克专利股份有限公司 Ion liquid
CN1569801A (en) * 2004-04-29 2005-01-26 华东师范大学 Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1181077C (en) * 2000-05-30 2004-12-22 默克专利股份有限公司 Ion liquid
CN1569801A (en) * 2004-04-29 2005-01-26 华东师范大学 Ionic liquid bis-ammonium acetate and catalytic synthesis process therefor

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