CN114250146A - Device and method for producing acetic acid by reducing carbon dioxide with electrode - Google Patents

Device and method for producing acetic acid by reducing carbon dioxide with electrode Download PDF

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CN114250146A
CN114250146A CN202210060461.2A CN202210060461A CN114250146A CN 114250146 A CN114250146 A CN 114250146A CN 202210060461 A CN202210060461 A CN 202210060461A CN 114250146 A CN114250146 A CN 114250146A
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cathode
anode
chamber
carbon dioxide
cathode chamber
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杨阳
袁浩
史陈涛
钟宁
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Jiangsu Branch Of China Academy Of Science Technology Development
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    • C12M35/00—Means for application of stress for stimulating the growth of microorganisms or the generation of fermentation or metabolic products; Means for electroporation or cell fusion
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    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Abstract

The invention discloses a device and a method for producing acetic acid by reducing carbon dioxide with an electrode, and the device comprises an anode chamber and a cathode chamber which are separated by a cation exchange membrane, wherein an anode is arranged in the anode chamber, a cathode is arranged in the cathode chamber, the anode and the cathode are connected in series outside the anode chamber and the cathode chamber through a power supply to form a loop, and the distance between the cathode and the anode is 2-3 cm; an Ag/AgCl electrode for measuring relative potential is arranged in the cathode chamber; catholyte is added into the cathode chamber, anolyte is added into the anode chamber, acetogenic bacteria are inoculated into the cathode chamber, and a layer of biological membrane is formed in the cathode chamber through domestication; the bottom of cathode chamber is equipped with the micropore aeration entry that is used for letting in pure carbon dioxide gas, and the top is equipped with the carbon dioxide export, will with cation exchange membrane the reactor is separated into cathode chamber and anode chamber to PTEC solution is catholyte and anolyte, and the external potential is inserted and is produced acetic acid mixed bacteria, and pure carbon dioxide enters into the reactor through micropore aeration and produces acetic acid.

Description

Device and method for producing acetic acid by reducing carbon dioxide with electrode
Technical Field
The invention belongs to the technical field of resource utilization of carbon dioxide, and particularly relates to a device and a method for producing acetic acid by reducing carbon dioxide with an electrode.
Background
The rapid development of global economy and the large population growth have led to a rapid increase in the demand for energy. By 2035, oil, coal and natural gas will still be the major energy sources, accounting for over 75% of the total energy, which will result in more CO2 emissions. The global CO2 concentration reaches the new high 400ppm in history in 2015, and is improved by 50% compared with the 19 th century. At present, the emission of CO2 in the world still rapidly increases at a rate of 4% per year, and the emission of human CO2 reaches 40.2Gt by 2030 according to the prediction of the International energy agency. Therefore, the resource conversion of CO2 can reduce the content of greenhouse gases in the atmosphere, can also produce chemicals or biological fuels with high added values, realizes the recycling of CO2, and has great significance for relieving greenhouse effect and energy crisis.
Microbial Electrosynthesis System (MES) is an electrochemical reduction technology, and has attracted more and more attention in the fields of environment and energy. The system is a bioelectrochemical reactor which performs cathodic reduction or anodic oxidation using microorganisms adsorbed on electrodes as a catalyst. Research has shown that optimizing the autotrophic metabolism of microorganisms by laboratory evolution is an effective strategy to increase the bioconversion rate of CO 2. The microbial cell factory is coupled with an electrochemical technology, and the energy storage of electric energy to chemical energy can be realized by using a tiny voltage. The consumption of CO2 avoids the defects of traditional CO2 treatment methods such as trapping, storage and the like, and the occupied area is extremely small, so that the method does not compete with grain production for land. With the continuous deepening of mechanism research and the continuous expansion of application fields, the MES technology develops towards higher efficiency and greenness.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a device and a method for producing acetic acid by fixing carbon dioxide by using a microbial electrochemical system, so that the yield of carbon dioxide synthetic chemicals is increased.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a device for producing acetic acid by reducing carbon dioxide with electrodes comprises an anode chamber and a cathode chamber which are separated by a cation exchange membrane, wherein an anode is arranged in the anode chamber, a cathode is arranged in the cathode chamber, the anode and the cathode are connected in series outside the anode chamber and the cathode chamber through a power supply to form a loop, and the distance between the cathode and the anode is 2-3 cm; an Ag/AgCl electrode for measuring relative potential is arranged in the cathode chamber;
catholyte is added into the cathode chamber, anolyte is added into the anode chamber, acetogenic bacteria are inoculated into the cathode chamber, and a layer of biological membrane is formed in the cathode chamber through domestication;
the bottom of the cathode chamber is provided with a micropore aeration inlet for introducing pure carbon dioxide gas, and the top of the cathode chamber is provided with a carbon dioxide outlet.
Specifically, the cathode is made of carbon felt, and the processing steps are as follows:
s1: intercepting a plurality of carbon felts with proper sizes;
s2: soaking the carbon felt obtained in the step S1 in HCl aqueous solution at room temperature to remove metal impurities;
s3: soaking the carbon felt processed in the step S2 in NaOH aqueous solution at room temperature to remove organic matters adsorbed on the surface;
s4: and (5) washing the carbon felt treated in the step (S3) with deionized water, and drying to obtain the carbon felt.
Specifically, the cation exchange membrane is treated according to the following steps:
s1: intercepting a plurality of cation exchange membranes with proper sizes;
s2: placing the cation exchange membrane in H2O2Boiling in water solution, and washing with deionized water;
s3: subjecting the cation exchange membrane treated in step S2 to treatment in H2SO4Boiling in water solution, and washing with deionized water;
s4: and (4) washing the cation membrane treated in the step (S3) with deionized water, boiling with the deionized water, and storing in the deionized water for later use.
Specifically, the acetogenic bacteria are mixed bacteria, and comprise at least two of Proteobacteria (Proteobacteria), Firmicutes (Mycobacteria), Bacteroides (Bacteroides) and Spirochaetes (Spirochaetomycota).
Specifically, the catholyte is a PETC solution, and the formula is as follows: NH (NH)4Cl 0.5～2g/L，KCl 0.1～0.3g/L，MgSO4·7H2O 0.1～0.3g/L，NaCl 0.5～1g/L，KH2PO4 0.1～0.3g/L，CaCl20.01～0.03g/L，NaHCO30.5-2 g/L, pH 6.5-7.5, and solvent is water.
In use, water is oxidized in the anode chamber to form oxygen and protons, which pass from the anode chamber through the membrane catholyte chamber. The carbon dioxide enters a cathode gas chamber and then enters a gas diffusion channel of a cathode, the protons enter a catalytic layer of the cathode through the solution, and the microorganisms on the cathode accept electrons and the protons to reduce the carbon dioxide, thereby producing acetic acid. In a cell, a carbon felt is used as an anode, the prepared cathode and anode are used, a cation exchange membrane is used for dividing the reactor into a cathode chamber and an anode chamber, a PTEC solution is used as a catholyte and an anolyte, an external potential is applied, acetogenic mixed bacteria are inoculated, 100% of carbon dioxide enters the reactor through micropore aeration and reacts at the temperature of 25-35 ℃ to produce acetic acid.
Further, the present invention also provides a method for producing acetic acid by using the above apparatus, comprising the steps of:
(1) domestication of an autoxidal microorganism: adding the original inoculum into a PETC solution under the atmosphere of carbon dioxide gas, performing three-round turning grafting, wherein each round is turned for three times, the intermittent time is gradually shortened, the first round is 5 days, the second round is 3 days, and the third round is 1 day, and finally obtaining domesticated autotrophic microorganisms as acetogenic mixed bacteria;
(2) pouring catholyte submerging the Ag/AgCl electrode into the cathode chamber, and inserting the cathode; pouring anolyte with the same volume as the cathode chamber into the anode chamber, and inserting the anode;
(3) connecting a micropore aeration inlet of the device with a carbon dioxide pipeline, installing a filter head at the joint for filtering a membrane for sterilization, opening a pipeline valve to remove oxygen by aeration so as to enable a cathode chamber to be in an anaerobic environment;
(4) respectively connecting the cathode and the anode with a cathode and an anode of a power supply and an Ag/AgCl electrode by using titanium wires;
(5) after the catholyte is subjected to aeration and deoxygenation, the well-turned and connected high-activity acetogenic mixed bacteria are taken out, the mixed bacteria are injected into the catholyte from a cathode chamber sampling port, and then cathode CO is injected2The flow rate of (2) is adjusted to an appropriate flow rate.
Preferably, in the step (2), the cathode and the anode are respectively vertically suspended in the catholyte, so that the maximum projection planes of the cathode and the anode are parallel to the cation exchange membrane.
Preferably, in the step (4), the potential between the cathode and the anode is-0.85 to-1.2V relative to the Ag/AgCl electrode.
Preferably, in the step (5), the inoculation amount of the acetogenic mixed bacteria is 5% by volume.
Preferably, in the step (5), the reaction temperature is controlled to be 25-35 ℃.
Has the advantages that:
according to the device for producing acetic acid by electrochemically reducing carbon dioxide with microorganisms, the electrode spacing is reduced through the reactor design, and the solubility of carbon dioxide is effectively improved and the rate value of producing acetic acid is enhanced through the aeration micro-tube at the bottom. Through specific domestication of microorganisms, an autoxidal microorganism is utilized to form a biological membrane on a cathode, and the purpose of improving the efficiency of bioelectrochemistry for fixing carbon dioxide is achieved through the extracellular electron transfer performance of the microorganism.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic diagram of the structure of an apparatus for producing acetic acid by reducing carbon dioxide with an electrode according to the present invention.
Wherein each reference numeral represents:
1 an anode chamber; 2; 3, an anode; 4 a cation exchange membrane; 5 a cathode chamber; 6 a cathode; 7, biological membrane; 8, catholyte; 9 a microporous aeration inlet; 10 a carbon dioxide outlet; 11Ag/AgCl electrodes; 12 power supply.
Detailed Description
The invention will be better understood from the following examples.
As shown in figure 1, the device for producing acetic acid by reducing carbon dioxide with the electrode comprises an anode chamber 1 and a cathode chamber 5 which are separated by a cation exchange membrane 4, wherein an anode 3 is arranged in the anode chamber 1, a cathode 6 is arranged in the cathode chamber 5, the anode 3 and the cathode 6 are connected in series outside the anode chamber 1 and the cathode chamber 3 through a power supply 12 to form a loop, and the distance between the cathode and the anode is 2-3 cm; an Ag/AgCl electrode 11 for measuring relative potential is arranged in the cathode chamber 5.
Catholyte 8 is added into the cathode chamber 5, anolyte 2 is added into the anode chamber 1, acetogenic bacteria are inoculated into the cathode chamber 8, and a layer of biological membrane 7 is formed in the cathode chamber through domestication.
The bottom of the cathode chamber 5 is provided with a micropore aeration inlet 9 for introducing pure carbon dioxide gas, and the top is provided with a carbon dioxide outlet 10.
Wherein, the cathode 6 is made of carbon felt, and the processing steps are as follows:
s1: intercepting a plurality of carbon felts with the size suitable for experimental operation to be 5 multiplied by 20 cm;
s2: preparing 1mol/L HCl solution, namely, fixing the volume of 96ml concentrated hydrochloric acid to 1L deionized water, and soaking the carbon felt treated in the step S1 in the 1mol/L HCl solution for 24 hours at the temperature of 25 ℃ to remove metal impurities;
s3: preparing 1mol/L NaOH solution, namely dissolving 40g of NaOH solid in 1L of deionized water, and soaking the carbon felt treated in the step S2 in the 1mol/L NaOH solution for 24 hours at the temperature of 25 ℃ to remove organic matters adsorbed on the surface;
s4: and (4) washing the carbon felt treated in the step (S3) with deionized water, and drying at 60 ℃ to obtain the cathode with good hydrophobicity.
The cation exchange membrane 4 is treated as follows:
s1: intercepting a plurality of cation exchange membranes with the size suitable for experimental operation, wherein the size of the cation exchange membranes is 8.5 multiplied by 32 cm;
s2: preparing 3% (V/V) H2O2 solution, namely adding 25mL of 30% hydrogen peroxide to 250mL of deionized water, putting the cation exchange membrane in 3% (V/V) H2O2 solution, boiling for 2H, and washing with deionized water;
s3: preparing 0.5mol/L H2SO4 solution, namely adding 12.7mL of concentrated sulfuric acid to 250mL of deionized water, boiling the cationic membrane treated in the step S2 in 0.5mol/L H2SO4 solution for 2h, and washing with deionized water;
s4: and (4) cleaning the cation membrane treated in the step S3 by using deionized water, then boiling the cation membrane for two hours by using the deionized water, and storing the cation membrane in the deionized water for later use.
Domestication of an autoxidal microorganism: and adding the original inoculum into the PETC solution under the atmosphere of carbon dioxide gas, performing three rounds of turning grafting, wherein each round of turning grafting is performed for three times, the intermittent time is gradually shortened, the first round is performed for 5 days, the second round is performed for 3 days, and the third round is performed for 1 day, and finally obtaining the domesticated autotrophic microorganisms.
Example 1
The device for reducing carbon dioxide to produce acetic acid comprises the following steps:
(1) pouring catholyte which can submerge an Ag/AgCl electrode into the cathode chamber, inserting a cathode, plugging a plug into the cathode chamber, adjusting the cathode to be vertically suspended in the catholyte, enabling the maximum projection plane of the cathode to be parallel to the cation exchange membrane, pouring anolyte which has the same volume as the cathode chamber into the anode chamber, and inserting the anode into the cathode chamber to perform the same operation as the cathode chamber;
(2) CO of the device2The air inlet is connected with a carbon dioxide pipeline, a filter head with the diameter of 0.22 mu m is arranged at the connection part for filtering the membrane for sterilization, and CO is opened2The pipeline valve is adjusted to the maximum, the aeration is carried out for about 10min to remove oxygen, the subsequent adjustment is small, the cathode chamber is always in an anaerobic environment, and CO in the device2The gas path is connected with microporous aeration for increasing CO2The contact area of the gas with the microorganisms;
(3) connecting the cathode and the anode (carbon felt and iridium-plated titanium alloy mesh plate) with the cathode and the anode of a power supply respectively by using black and red wires, adding a 10-ohm resistor in the middle, and clamping clips of a data collector at two ends of the resistor;
(4) CO for catholyte2After aeration and deoxidization for 10min, the well-turned and inoculated high-activity acetogenic mixed bacteria are taken out, 5mL of mixed bacteria (Proteobacteria, Firmicutes, bacteriodes and Spirochaetes) are extracted by a disposable 5mL syringe, the inoculation amount is 5 percent of volume ratio, then the mixed bacteria are injected into catholyte from a sampling port of a cathode chamber, and cathode CO is injected into catholyte2The flow rate is adjusted to be proper, and the reaction temperature is controlled to be 25-35 ℃.
Wherein, the anolyte comprises the following components: 20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/LNaCl，2g/L KH2PO4，0.4g/L CaCl26g/L NaCl and 2g/L KCl, and the solvent is water.
The catholyte comprises the following components: 1.5g/L nitrilotriacetic acid, 3g/L MgSO4·7H2O，0.5g/L MnSO4·H2O，1g/L NaCl，0.1g/L FeSO4·7H2O，0.2g/L CoCl2·6H2O，0.1g/L CaCl2·2H2O，0.18mg/L ZnSO4·7H2O，0.01g/L CuSO4·2H2O，0.03g/L NiCl2·6H2O，0.02g/L KAl(SO4)2·12H2O，0.01g/L H3BO3，0.02g/L Na2MoO4·2H2O，0.02g/L Na2SeO4，0.02g/L Na2WO4，20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/L NaCl，2g/L KH2PO4，0.4g/L CaCl2，6g/L NaCl，2g/L KCl，1g/L NaHCO3The solvent is water.
(6) The potential between the cathode and the anode was applied at-1.2V (vs. Ag/AgCl electrode) using a potentiostat, and after 30 days of operation, the final acetic acid concentration was 0.55g L-1D-1。
Example 2
The device for reducing carbon dioxide to produce acetic acid comprises the following steps:
(1) pouring catholyte which can submerge an Ag/AgCl electrode into the cathode chamber, inserting a cathode, plugging a plug into the cathode chamber, adjusting the cathode to be vertically suspended in the catholyte, enabling the maximum projection plane of the cathode to be parallel to the cation exchange membrane, pouring anolyte which has the same volume as the cathode chamber into the anode chamber, and inserting the anode into the cathode chamber to perform the same operation as the cathode chamber;
(2) CO of the device2The air inlet is connected with a carbon dioxide pipeline, a filter head with the diameter of 0.22 mu m is arranged at the connection part for filtering the membrane for sterilization, and CO is opened2The pipeline valve is adjusted to the maximum, the aeration is carried out for about 10min to remove oxygen, the subsequent adjustment is small, the cathode chamber is always in an anaerobic environment, and CO in the device2The gas path is connected with microporous aeration for increasing CO2The contact area of the gas with the microorganisms;
(3) connecting the cathode and the anode (carbon felt and iridium-plated titanium alloy mesh plate) with the cathode and the anode of a power supply respectively by using black and red wires, adding a 10-ohm resistor in the middle, and clamping clips of a data collector at two ends of the resistor;
(4) CO for catholyte2After aeration and deoxidization for 10min, the well-turned and inoculated high-activity acetogenic mixed bacteria are taken out, 5mL of mixed bacteria (Proteobacteria, Firmicutes, bacteriodes and Spirochaetes) are extracted by a disposable 5mL syringe, the inoculation amount is 5 percent of volume ratio, then the mixed bacteria are injected into catholyte from a sampling port of a cathode chamber, and cathode CO is injected into catholyte2Is adjusted to a proper flow rate, and the reaction is carried outThe temperature is controlled to be 25-35 ℃.
Wherein, the anolyte comprises the following components: 20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/L NaCl，2g/L KH2PO4，0.4g/L CaCl26g/L NaCl and 2g/L KCl, and the solvent is water.
The catholyte comprises the following components: 1.5g/L nitrilotriacetic acid, 3g/L MgSO4·7H2O，0.5g/L MnSO4·H2O，1g/L NaCl，0.1g/L FeSO4·7H2O，0.2g/L CoCl2·6H2O，0.1g/L CaCl2·2H2O，0.18mg/L ZnSO4·7H2O，0.01g/L CuSO4·2H2O，0.03g/L NiCl2·6H2O，0.02g/L KAl(SO4)2·12H2O，0.01g/L H3BO3，0.02g/L Na2MoO4·2H2O，0.02g/L Na2SeO4，0.02g/L Na2WO4，20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/L NaCl，2g/L KH2PO4，0.4g/L CaCl2，6g/L NaCl，2g/L KCl，1g/L NaHCO3The solvent is water.
(6) The potential between the cathode and the anode was applied at-1.0V (relative to an Ag/AgCl electrode) using a potentiostat, and after 30 days of operation, the final acetic acid concentration was 0.45g L-1D-1。
Example 3
The device for reducing carbon dioxide to produce acetic acid comprises the following steps:
(1) pouring catholyte which can submerge an Ag/AgCl electrode into the cathode chamber, inserting a cathode, plugging a plug into the cathode chamber, adjusting the cathode to be vertically suspended in the catholyte, enabling the maximum projection plane of the cathode to be parallel to the cation exchange membrane, pouring anolyte which has the same volume as the cathode chamber into the anode chamber, and inserting the anode into the cathode chamber to perform the same operation as the cathode chamber;
(2) CO of the device2The air inlet is connected with a carbon dioxide pipeline, a filter head with the diameter of 0.22 mu m is arranged at the connection part for filtering the membrane for sterilization, and CO is opened2Pipe valve and adjusting valve to maximumOxygen is removed by gas for about 10min, the subsequent adjustment is small, the cathode chamber is always in an anaerobic environment, and CO in the device2The gas path is connected with microporous aeration for increasing CO2The contact area of the gas with the microorganisms;
(3) connecting the cathode and the anode (carbon felt and iridium-plated titanium alloy mesh plate) with the cathode and the anode of a power supply respectively by using black and red wires, adding a 10-ohm resistor in the middle, and clamping clips of a data collector at two ends of the resistor;
(4) CO for catholyte2After aeration and deoxidization for 10min, the well-turned and inoculated high-activity acetogenic mixed bacteria are taken out, 5mL of mixed bacteria (Proteobacteria, Firmicutes, bacteriodes and Spirochaetes) are extracted by a disposable 5mL syringe, the inoculation amount is 5 percent of volume ratio, then the mixed bacteria are injected into catholyte from a sampling port of a cathode chamber, and cathode CO is injected into catholyte2The flow rate is adjusted to be proper, and the reaction temperature is controlled to be 25-35 ℃.
Wherein, the anolyte comprises the following components: 20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/L NaCl，2g/L KH2PO4，0.4g/L CaCl26g/L NaCl and 2g/L KCl, and the solvent is water.
The catholyte comprises the following components: 1.5g/L nitrilotriacetic acid, 3g/L MgSO4·7H2O，0.5g/L MnSO4·H2O，1g/L NaCl，0.1g/L FeSO4·7H2O，0.2g/L CoCl2·6H2O，0.1g/L CaCl2·2H2O，0.18mg/L ZnSO4·7H2O，0.01g/L CuSO4·2H2O，0.03g/L NiCl2·6H2O，0.02g/L KAl(SO4)2·12H2O，0.01g/L H3BO3，0.02g/L Na2MoO4·2H2O，0.02g/L Na2SeO4，0.02g/L Na2WO4，20g/L NH4Cl，2g/L KCl，4g/L MgSO4·7H2O，16g/L NaCl，2g/L KH2PO4，0.4g/L CaCl2，6g/L NaCl，2g/L KCl，1g/L NaHCO3The solvent is water.
(6) A constant potential rectifier is used between the cathode and the anode to add-0.9V (relative voltage)At an Ag/AgCl electrode), the final acetic acid concentration was 0.25g L after 30 days of operation-1D-1。
The present invention provides a device and a method for producing acetic acid by electrode reduction of carbon dioxide, and a method and a means for implementing the method, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and embellishments can be made without departing from the principle of the present invention, and these modifications and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.

Claims (10)

1. The device for producing acetic acid by reducing carbon dioxide with the electrode is characterized by comprising an anode chamber (1) and a cathode chamber (5) which are separated by a cation exchange membrane (4), wherein an anode (3) is arranged in the anode chamber (1), a cathode (6) is arranged in the cathode chamber (5), and the anode (3) and the cathode (6) are connected in series outside the anode chamber (1) and the cathode chamber (3) through a power supply (12) to form a loop; an Ag/AgCl electrode (11) for measuring relative potential is arranged in the cathode chamber (5);
catholyte (8) is added into the cathode chamber (5), anolyte (2) is added into the anode chamber (1), acetogenic bacteria are inoculated into the cathode chamber (8), and a layer of biomembrane (7) is formed in the cathode chamber through domestication;
the bottom of the cathode chamber (5) is provided with a micropore aeration inlet (9) for introducing pure carbon dioxide gas, and the top is provided with a carbon dioxide outlet (10).
2. The apparatus for producing acetic acid by electrode reduction of carbon dioxide according to claim 1, wherein the cathode (6) is made of carbon felt, and the processing steps are as follows:
s1: intercepting a plurality of carbon felts with proper sizes;
s2: soaking the carbon felt obtained in the step S1 in HCl aqueous solution at room temperature to remove metal impurities;
s3: soaking the carbon felt processed in the step S2 in NaOH aqueous solution at room temperature to remove organic matters adsorbed on the surface;
s4: and (5) washing the carbon felt treated in the step (S3) with deionized water, and drying to obtain the carbon felt.
3. The apparatus for producing acetic acid by reducing carbon dioxide with an electrode according to claim 1, wherein the cation exchange membrane (4) is treated as follows:
s1: intercepting a plurality of cation exchange membranes with proper sizes;
s2: placing the cation exchange membrane in H2O2Boiling in water solution, and washing with deionized water;
s3: subjecting the cation exchange membrane treated in step S2 to treatment in H2SO4Boiling in water solution, and washing with deionized water;
s4: and (4) washing the cation membrane treated in the step (S3) with deionized water, boiling with the deionized water, and storing in the deionized water for later use.
4. The apparatus for producing acetic acid by reducing carbon dioxide with an electrode according to claim 1, wherein the acetogenic bacteria are mixed bacteria including at least two of Proteobacteria, Firmicutes, bacteriodes and Spirochaetes.
5. The apparatus for producing acetic acid by electrode reduction of carbon dioxide according to claim 1, wherein the catholyte (8) is a PETC solution, and the formulation thereof is as follows: NH (NH)4Cl 0.5～2g/L，KCl 0.1～0.3g/L，MgSO4·7H2O 0.1～0.3g/L，NaCl 0.5～1g/L，KH2PO4 0.1～0.3g/L，CaCl20.01～0.03g/L，NaHCO30.5-2 g/L, pH 6.5-7.5, and solvent is water.
6. A process for producing acetic acid using the apparatus of claim 1, comprising the steps of:
(1) domestication of an autoxidal microorganism: adding the original inoculum into a PETC solution under the atmosphere of carbon dioxide gas, performing three-round turning grafting, wherein each round is turned for three times, the intermittent time is gradually shortened, the first round is 5 days, the second round is 3 days, and the third round is 1 day, and finally obtaining domesticated autotrophic microorganisms as acetogenic mixed bacteria;
(2) pouring catholyte submerging the Ag/AgCl electrode into the cathode chamber, and inserting the cathode; pouring anolyte with the same volume as the cathode chamber into the anode chamber, and inserting the anode;
(3) connecting a micropore aeration inlet of the device with a carbon dioxide pipeline, installing a filter head at the joint for filtering a membrane for sterilization, opening a pipeline valve to remove oxygen by aeration so as to enable a cathode chamber to be in an anaerobic environment;
(4) respectively connecting the cathode and the anode with a cathode and an anode of a power supply and an Ag/AgCl electrode by using titanium wires;
(5) after the catholyte is subjected to aeration and deoxygenation, the well-turned and connected high-activity acetogenic mixed bacteria are taken out, the mixed bacteria are injected into the catholyte from a cathode chamber sampling port, and then cathode CO is injected2The flow rate of (2) is adjusted to an appropriate flow rate.
7. The method for producing acetic acid according to claim 6, wherein in the step (2), the cathode and the anode are respectively vertically suspended in the catholyte, so that the maximum projection planes of the cathode and the anode are parallel to the cation exchange membrane.
8. The method for producing acetic acid according to claim 6, wherein in the step (4), the potential between the cathode and the anode is in the range of-0.85 to-1.2V with respect to the Ag/AgCl electrode.
9. The method for producing acetic acid according to claim 6, wherein the amount of the inoculated acetogenic mixed bacteria in the step (5) is 5% by volume.
10. The method for producing acetic acid according to claim 6, wherein the reaction temperature in the step (5) is controlled to be 25 to 35 ℃.
CN202210060461.2A 2022-01-19 2022-01-19 Device and method for producing acetic acid by reducing carbon dioxide with electrode Pending CN114250146A (en)

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