CN110273164A - The method of electrochemical reduction CO2 oxalic acid in aromatic ester ion liquid system - Google Patents
The method of electrochemical reduction CO2 oxalic acid in aromatic ester ion liquid system Download PDFInfo
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- CN110273164A CN110273164A CN201910571800.1A CN201910571800A CN110273164A CN 110273164 A CN110273164 A CN 110273164A CN 201910571800 A CN201910571800 A CN 201910571800A CN 110273164 A CN110273164 A CN 110273164A
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- oxalic acid
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Abstract
The present invention provides one kind in aromatic ester ion liquid system electrochemical reduction CO2The method of oxalic acid processed, the aromatic ester ionic liquid synthesized respectively with tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide, tetraethyl phosphonium hydroxide, three hexyl phosphonium hydroxide of myristyl using methyl p-hydroxybenzoate is as electrolyte and catalyst, and Pb is working electrode, Pt is to electrode, Ag/Ag+For reference electrode, electrochemical reduction CO is carried out in H-type electrolytic cell2Oxalic acid processed.This method has many advantages, such as that current density is big, oxalic acid generating rate is fast.
Description
Technical field
The present invention relates to CO2Application technology as the second resource field, and in particular to one kind is in aromatic ester ion liquid system
Electrochemical reduction CO2The method of oxalic acid processed.
Background technique
In recent years, carbon dioxide (CO2) main greenhouse gases are used as, discharge amount and concentration are big with fossil fuel
Amount is burnt and is continuously increased, and produces tremendous influence to weather and environment, CO2Emission reduction has caused extensive concern in the world.Separately
Outside, CO2It is also considered as natural, abundant, reproducible cheap carbon source.Therefore, to CO2It is trapped and is converted, especially will
CO2Reduction be converted into the fuel such as CO, formic acid, methanol and other high added values chemicals be international research hot spot.CO at present2
The method of reduction mainly includes thermal reduction, photo catalytic reduction, electrochemical reduction etc..Traditional thermal reduction generally requires high temperature height
The more harsh condition such as pressure, catalyst, photo-reduction catalytic efficiency and the efficiency of solar energy utilization are lower, and to catalyst
Performance requirement is higher.And electrochemical reduction can guarantee CO2Under mild conditions have it is higher activation, transformation efficiency and compared with
High selectivity of product, and have many advantages, such as equipment it is small, it is easy to operate, be easy to industry amplification.Therefore, pass through electrochemical reduction
Method realize CO2Conversion possess broader development space and application prospect.
Oxalic acid is a kind of important Organic Chemicals, widely used.In recent years, as oxalic acid is in medical industry and rare earth
The extension in the fields such as processing industry, the demand sustainable growth of oxalic acid.Traditional oxalic acid production technology mainly has sodium formate method, CO even
Join vapor phase method and ethylene glycol oxidation etc..Sodium formate method technical maturity is suitble to large-scale production, but the strong acid that production process uses
Highly basic can bring more serious environmental problem, and product yield is low；It is clear that CO is coupled vapor phase method atom utilization height, technical process
It is clean, but the Pd catalyst used is expensive, high production cost；Ethylene glycol oxidation simple process, operating condition are flexible, but make
It is too high for the ethylene glycol price of raw material.These conventional methods mostly have that high production cost, yield are low, seriously polluted.
Therefore, the Green production method for developing oxalic acid is of great significance.
Pass through electrochemical reduction CO2Oxalic acid processed is a kind of excellent process, can produce grass under mild conditions
Acid.For electrochemical reduction CO2Most important two o'clock: on the one hand oxalic acid processed is needed to CO2The higher electrolyte of absorptive capacity,
Dissolution CO can be fully absorbed2, reactant concentration is improved, to enhance the mass transfer effect of electrolytic process；On the other hand, height is needed
Effect activation CO2, it converts CO as quickly as possible by it2 .- Intermediate, and then dimerization coupling is converted into oxalic acid.Electrochemical reduction
CO2The reaction process of oxalic acid processed is about CO2First obtaining 1 electron reduction is CO2 .-Free radical anion intermediate, so latter two
CO2 .-Free radical anion two is polymerized to oxalate C2O4 2-.When in electrolyte containing the substance for being provided with proton H, CO2 .-Intermediate
It is easy to and H+In conjunction with generation formic acid, therefore reaction process needs sprotic electrolytic environments.
The novel medium that ionic liquid is made of zwitterion completely as one kind has not volatile, nonflammable, conductive
The advantages that property is strong, can be widely applied to the fields such as catalysis, electrochemistry.Ionic liquid is as electrochemical reduction CO2Field it is excellent
Electrolyte has high-efficiency dissolution-activation CO2, the aqueous solutions such as control accurate product, electrochemical window mouth width, electric conductivity is strong and pure have
The unique advantage that solvent does not have.Patent WO/2018/016844 is to electrode, Ag/Ag by working electrode, Zn of Pb+For ginseng
Than electrode, it is electrolyte using organic solvent DMSO, the quaternary ammonium salt ([TBAPF of 0.1 mol/L is added6]) it is used as assisted electrolysis matter
Carry out electrochemical reduction CO2Research, finally obtains product zinc oxalate.But the process reduction potential is higher, and current density is small, thus
Cause the generating rate of oxalic acid (salt) slower.Uttam R. Pokharel etc. (Science,2010,327:313-315.)
Reporting by working electrode, Pt of glass carbon is to electrode, Ag/AgCl for reference electrode, by 0.1 mol/L's
[TBAPF6] Cu(II is added in-DMF electrolyte) complex as catalyst, can effectively reduce CO2Reduction overpotential simultaneously improves
CO2It is converted into the selectivity of oxalic acid, but the system equally exists the small problem of current density.Currently, in electrochemical reduction CO2System
In the relevant report of oxalic acid, current density is generally less than 8 mA/cm2, the generating rate of oxalic acid is largely lower than 0.15 mmol/
(cm2H).
Summary of the invention
The invention proposes one kind in aromatic ester ion liquid system electrochemical reduction CO2The method of oxalic acid processed, gram
Existing electrochemical reduction CO is taken2Oxalic acid technology current density processed is small, oxalic acid generating rate is slow, assisted electrolysis matter need to be added simultaneously
And the problem of catalyst, it is put forward for the first time the electrochemical reduction CO in aromatic ester ionic liquid compound system2The method of oxalic acid processed,
Ionic liquid can play activating catalytic CO simultaneously2With conductive effect, this method can effectively increase current density, improve oxalic acid generation
Rate.
Realize the technical scheme is that
One kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, with aromatic ester ionic liquid
As electrolyte and catalyst, electrochemical reduction CO is carried out in H-type electrolytic cell2Oxalic acid processed.
The H-type electrolytic cell Anodic liquid is the H of 0.1 mol/L of concentration2SO4Or 0.1 mol/L Na2SO4Solution,
Pb is working electrode, Pt is to electrode, Ag/Ag+For reference electrode.
The current potential of the electrochemical reduction is -2.5 V of V ~ -2.9,2 h of electrolysis time.
Aromatic ester ionic liquid is that aromatic ester compound is dissolved in proton-inert organic solvent, and being configured to concentration is
The compound system of 0.1 ~ 1 mol/L is as catholyte.
The aromatic ester ionic liquid is reacted to obtain by methyl p-hydroxybenzoate with quaternary ammonium base or quaternary phosphonium alkali.
The molar ratio of the methyl p-hydroxybenzoate and quaternary ammonium base or quaternary phosphonium alkali is 1: 1, and reaction temperature is 25-30
DEG C, the reaction time is 10-12 h.
The quaternary ammonium base is tetraethyl ammonium hydroxide or tetrabutylammonium hydroxide, and quaternary phosphonium alkali is tetraethyl phosphonium hydroxide or ten
Three hexyl phosphonium hydroxide of tetraalkyl.
The proton-inert organic solvent is acetonitrile (ACN), N,N-dimethylformamide (DMF) or dimethyl sulfoxide
One or both of (DMSO).
The beneficial effects of the present invention are: the present invention proposes that design synthesizes a kind of virtue of proton inertia (without proton activity H)
For fragrant esters ionic liquid as electrolyte, it has relatively by force activation CO2Ability simultaneously has catalysis CO2 .-Free radical anion dimerization
The effect of coupling, can be in the case where mass transfer enhancement, increasing current density by CO2It is reduced to oxalic acid.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 be ionic liquid 4-(methoxycarbonyl group of the present invention) phenol tetraethyl ammonium ([TEA] [4-MF-PhO]) core
Magnetic hydrogen spectrogram.
Fig. 2 is the FTIR spectrum figure of ionic liquid of the present invention [TEA] [4-MF-PhO].
Fig. 3 is the density map of ionic liquid of the present invention [TEA] [4-MF-PhO].
Fig. 4 is the viscogram of ionic liquid of the present invention [TEA] [4-MF-PhO].
Fig. 5 is that the LSV of [TEA] [4-MF-PhO]-ACN electrolyte electrolytic process of various concentration of the present invention is bent
Line.
Fig. 6 is the it curve graph that [TEA] [4-MF-PhO]-ACN electrolyte of the present invention is electrolysed under different potentials.
Fig. 7 is testing result figure of the oxalic acid standard items of the present invention in high performance liquid chromatography.
Fig. 8 is testing result figure of the electrolysate of the present invention in high performance liquid chromatography.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
One kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, condition are as follows:
(1) 4-(methoxycarbonyl group) phenol tetraethyl ammonium ([TEA] [4-MF-PhO]) synthesis
The ionic liquid is to be synthesized by methyl p-hydroxybenzoate and tetraethyl ammonium hydroxide by 1: 1 molar ratio reaction.
The synthesis temperature is 25 DEG C, is stirred under condition of normal pressure, and the reaction time is 10 h.After reaction revolving except ethyl alcohol and
Water, 65 DEG C of the temperature, 0.5 h of time；75 DEG C, 2 h of time.Finally move into 75 DEG C of 24 h of drying of vacuum oven.
[TEA] [4-MF-PhO] ionic liquid synthetic route is as follows:
(2) electrochemical reduction CO in [TEA] [4-MF-PhO] ion liquid system2Oxalic acid processed
It takes 0.8442 g [TEA] [4-MF-PhO] to be dissolved in acetonitrile and is configured to 30 mL, concentration is that the solution of 0.1 mol/L makees cathode
Electrolyte prepares 0.1 mol/L H2SO4Weak solution makees anolyte, is separated among two Room of H-type electrolytic cell using Nafion membrane.To
30 min CO are passed through in catholyte2, saturation is reached, is then carried out using the three-electrode system of electrochemical workstation
Electrolysis is electrolysed 2 h in -2.5 V of V ~ -2.9 of constant potential respectively.High performance liquid chromatography detection is carried out to the electrolyte after electrolysis,
In 10 mA/cm2Current density under, the generating rate of oxalic acid is 0.2 mmol/(cm2H).
Embodiment 2
One kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, condition are as follows:
(1) 4-(methoxycarbonyl group) phenol tetrabutylammonium ([TBA] [4-MF-PhO]) preparation
Methyl p-hydroxybenzoate and tetrabutylammonium hydroxide are synthesized by the molar ratio reaction of 1:1.The synthesis temperature is 30
DEG C, it is stirred under condition of normal pressure, the reaction time is 11 h.It rotates after reaction and removes second alcohol and water, 65 DEG C of the temperature,
0.5 h of time；75 DEG C, 2 h of time.Finally move into 75 DEG C of 24 h of drying of vacuum oven.
(2) electrochemical reduction CO in [TBA] [4-MF-PhO] ion liquid system2Oxalic acid processed
It takes 1.1809 g [TBA] [4-MF-PhO] to be dissolved in acetonitrile and is configured to 30 mL, concentration is that the solution of 0.1 mol/L makees cathode
Electrolyte prepares 0.1 mol/L H2SO4Weak solution makees anolyte, is separated among two Room of H-type electrolytic cell using Nafion membrane.To
30 min CO are passed through in catholyte2, saturation is reached, is then carried out using the three-electrode system of electrochemical workstation
Electrolysis is electrolysed 2 h in -2.5 V of V ~ -2.9 of constant potential respectively.High performance liquid chromatography detection is carried out to the electrolyte after electrolysis,
In 9.5 mA/cm2Current density under, the generating rate of oxalic acid is 0.18 mmol/(cm2H).
Embodiment 3
One kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, condition are as follows:
(1) 4-(methoxycarbonyl group) phenol tetraethyl phosphorus ([TEP] [4-MF-PhO]) preparation
Methyl p-hydroxybenzoate and tetraethyl phosphonium hydroxide are synthesized by 1: 1 molar ratio reaction.The synthesis temperature is
It 30 DEG C, stirs under condition of normal pressure, the reaction time is 12 h.Revolving removes second alcohol and water, the temperature 65 after reaction
DEG C, 0.5 h of time；75 DEG C, 2 h of time.Finally move into 75 DEG C of 24 h of drying of vacuum oven.
(2) electrochemical reduction CO in [TEP] [4-MF-PhO] ion liquid system2Oxalic acid processed
It takes 4.476 g [TEP] [4-MF-PhO] to be dissolved in dimethyl sulfoxide and is configured to 30 mL, concentration is the solution of 0.5 mol/L
Make catholyte, prepares 0.1 mol/L H2SO4Weak solution makees anolyte, among two Room of H-type electrolytic cell using Nafion membrane every
It opens.30 min CO are passed through into catholyte2, saturation is reached, the three-electrode system of electrochemical workstation is then used
It is electrolysed, is electrolysed 2 h in -2.5 V of V ~ -2.9 of constant potential respectively.High performance liquid chromatography is carried out to the electrolyte after electrolysis
Detection, in 8 mA/cm2Current density under, the generating rate of oxalic acid is 0.18 mmol/(cm2H).
Embodiment 4
One kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, condition are as follows:
(1) 4-(methoxycarbonyl group) three hexyl phosphorus ([P of phenol myristyl66614] [4-MF-PhO]) preparation
Methyl p-hydroxybenzoate and three hexyl phosphonium hydroxide of myristyl are synthesized by 1: 1 molar ratio reaction.The conjunction
It is 30 DEG C at temperature, is stirred under condition of normal pressure, the reaction time is 12 h.Revolving removes second alcohol and water after reaction, described
65 DEG C of temperature, 0.5 h of time；75 DEG C, 2 h of time.Finally move into 75 DEG C of 24 h of drying of vacuum oven.
(2) [P66614] electrochemical reduction CO in [4-MF-PhO] ion liquid system2Oxalic acid processed
Prepare [the P of 1 mol/L66614] [4-MF-PhO]-DMF solution makees catholyte, prepare 0.1 mol/L Na2SO4
Solution makees anolyte, is separated among two Room of H-type electrolytic cell using Nafion membrane.30 min CO are passed through into catholyte2,
Reach saturation, be then electrolysed using the three-electrode system of electrochemical workstation, respectively -2.5 V of constant potential ~ -
2.9 V are electrolysed 2 h.High performance liquid chromatography detection is carried out to the electrolyte after electrolysis, in 8 mA/cm2Current density under, oxalic acid
Generating rate be 0.15 mmol/(cm2H).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. one kind electrochemical reduction CO in aromatic ester ion liquid system2The method of oxalic acid processed, it is characterised in that: with fragrance
Esters ionic liquid carries out electrochemical reduction CO as electrolyte and catalyst in H-type electrolytic cell2Oxalic acid processed.
2. the electrochemical reduction CO according to claim 1 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the H-type electrolytic cell Anodic liquid is the H of 0.1 mol/L of concentration2SO4Or 0.1 mol/L Na2SO4Solution,
Pb is working electrode, Pt is to electrode, Ag/Ag+For reference electrode.
3. the electrochemical reduction CO according to claim 2 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the current potential of the electrochemical reduction is -2.5 V of V ~ -2.9,2 h of electrolysis time.
4. the described in any item electrochemical reduction CO in aromatic ester ion liquid system of claim 1-32The side of oxalic acid processed
Method, it is characterised in that: aromatic ester ionic liquid is that aromatic ester compound is dissolved in proton-inert organic solvent, is configured to dense
Degree is the compound system of 0.1 ~ 1 mol/L as catholyte.
5. the electrochemical reduction CO according to claim 4 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the aromatic ester ionic liquid is reacted to obtain by methyl p-hydroxybenzoate with quaternary ammonium base or quaternary phosphonium alkali.
6. the electrochemical reduction CO according to claim 5 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the molar ratio of the methyl p-hydroxybenzoate and quaternary ammonium base or quaternary phosphonium alkali is 1: 1, and reaction temperature is 25-
30 DEG C, the reaction time is 10-12 h.
7. the electrochemical reduction CO according to claim 5 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the quaternary ammonium base be tetraethyl ammonium hydroxide or tetrabutylammonium hydroxide, quaternary phosphonium alkali be tetraethyl phosphonium hydroxide or
Three hexyl phosphonium hydroxide of myristyl.
8. the electrochemical reduction CO according to claim 4 in aromatic ester ion liquid system2The method of oxalic acid processed,
Be characterized in that: the proton-inert organic solvent is one of acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide or two
Kind.
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Cited By (1)
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| CN114540847A (en) * | 2022-02-15 | 2022-05-27 | 中国科学院过程工程研究所 | Ionic liquid reinforced CO containing nitrile group and phenolic hydroxyl group2Method for preparing oxalate by electroreduction |
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| US20140158547A1 (en) * | 2012-07-26 | 2014-06-12 | Liquid Light, Inc. | Multiphase Electrochemical Reduction of CO2 |
| CN103752134A (en) * | 2014-01-08 | 2014-04-30 | 浙江大学 | Efficient and energy-saving method for trapping carbon by ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114540847A (en) * | 2022-02-15 | 2022-05-27 | 中国科学院过程工程研究所 | Ionic liquid reinforced CO containing nitrile group and phenolic hydroxyl group2Method for preparing oxalate by electroreduction |
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