CN117210830A - Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid - Google Patents
Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid Download PDFInfo
- Publication number
- CN117210830A CN117210830A CN202311247174.3A CN202311247174A CN117210830A CN 117210830 A CN117210830 A CN 117210830A CN 202311247174 A CN202311247174 A CN 202311247174A CN 117210830 A CN117210830 A CN 117210830A
- Authority
- CN
- China
- Prior art keywords
- cathode
- formic acid
- anode
- substrate
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 87
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 54
- 239000011261 inert gas Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005341 cation exchange Methods 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 50
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- -1 Hydrogen ions Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an electrochemical synthesis method and an electrolysis system of high-concentration pure formic acid, which specifically comprise the following steps: a) Electric powerPreparing a pole: the hydrophobic carbon paper with the microporous layer is used as a cathode substrate, a cathode catalyst can be sprayed upwards, and a gas diffusion cathode is formed after drying; irO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 For the anode; b) Electrochemical cell assembly: assembling the negative electrode and the positive electrode into a membrane electrode electrolytic cell, correspondingly using an anion exchange membrane and a cation exchange membrane, and separating the negative electrode from the positive electrode by using a solid electrolyte; c) Generating high-concentration pure formic acid: and introducing wet inert gas into the solid electrolyte of the membrane electrode electrolytic cell to lead out the generated formic acid, and electrifying the system to obtain high-concentration pure formic acid. The method provides a scheme for continuously, stably and effectively preparing the high-concentration pure formic acid, has the advantages of simple process, short time consumption and the like, and is suitable for large-scale expansion into industrial production.
Description
Technical Field
The invention relates to the technical field of electrochemical synthesis, in particular to an electrochemical synthesis method and an electrochemical electrolysis system of high-concentration pure formic acid.
Background
By electrocatalytic CO 2 Reduction technique of CO 2 The method is converted into high-added-value chemicals such as fuel and the like, and is an effective means for realizing a double-carbon strategy. The realization condition of the technology is normal temperature and normal pressure, and the technology has the advantages of mild reaction condition, high energy conversion efficiency, easy realization of large scale and the like, so that the technology is paid more attention to. Notably, electrocatalytic CO 2 Reduction to give formic acid as a liquid product, which has the advantages of high energy density, easy transport and storage of the product, and spontaneous separation from the gas, is electrocatalytic CO 2 One of the ideal products of the reduction.
However, currently for electrocatalytic CO 2 Reduction to high concentrations of pure formic acid still presents the following challenges. First, conventional electrocatalytic CO 2 The reduction process is mainly carried out in electrolyte (such as potassium bicarbonate and potassium hydroxide) solution, so that the generated formic acid is mixed with the electrolyte and mainly exists in the form of formate, and a subsequent separation process is needed, so that the cost is greatly increased. Second, electrocatalytic CO is performed in a conventional manner 2 The concentration of the formic acid produced by reduction is low, and the practical application requirement is difficult to meet. To solve the separation problem of liquid fuel and electrolyte by directly electrocatalytic CO 2 Reduction to produce high purity formic acid, xia, etc., a novel solid electrolyte membrane cell reactor was developed to achieve the production of 0.1M pure formic acid solution (nat. Energy,2019,4,776). Zheng et al also successfully achieved continuous production of pure aqueous formic acid using this type of reactor and canThe operation was continued for 180h with a final yield of 8 l of 0.1M pure formic acid solution (nat. Nanotechnol.,2021,16,1386).
Although the production of high purity formic acid can be achieved using solid electrolyte membrane electrode cells, the following problems remain: since the currently used solid electrolyte and ion exchange membrane are required to be kept in a wet state, a large amount of deionized water is required to be introduced into the solid electrolyte to keep the stability of the reactor, so that formic acid is diluted, and the concentration of pure formic acid continuously produced by the current solid electrolyte membrane electrode electrolytic cell is still low (< 1M), so that the practical application requirement is difficult to meet. Therefore, new strategies are still being developed to address this problem.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an electrochemical synthesis method and an electrochemical electrolysis system for high-concentration pure formic acid.
The invention provides an electrochemical synthesis method of high-concentration pure formic acid, which comprises the following steps:
introducing wet inert gas into the solid electrolyte part in the middle of the membrane electrode electrolytic cell to obtain CO 2 The gas is used as a raw material, sulfuric acid electrolyte is adopted, the membrane electrode electrolytic cell is electrified to obtain high-concentration pure formic acid, and the high-concentration pure formic acid is led out from the wet inert gas;
the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 。
Preferably, the catalyst of the cathode catalytic layer is tin-based, bismuth-based or indium-based, and the loading of the catalyst on the cathode substrate is 0.5-1 mg cm -2 。
Preferably, the IrO of the anode substrate surface 2 The load is 1-2 mgcm -2 。
Preferably, the CO introduced from the cathode of the membrane electrode electrolytic cell 2 The flow rate of the gas is 20-30 sccm.
Preferably, the concentration of sulfuric acid electrolyte adopted by the anode of the membrane electrode electrolytic cell is 0.05-0.5M, and the flow rate is 0.5-2 sccm.
Preferably, the humidified inert gas is humidified carbon dioxide gas or nitrogen gas.
Preferably, the wet inert gas is formed by heating dry inert gas to 50-100 ℃ in water, and the wettability is above 50%.
Preferably, the current for electrifying the membrane electrode electrolytic cell is 150-200 mA cm -2 。
The invention provides an electrochemical electrolysis system of high-concentration pure formic acid, which comprises a membrane electrode electrolytic cell and a heating device; the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the gas diffusion cathode has CO at it 2 A gas inlet; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The anode is provided with a sulfuric acid electrolyte inlet;
the solid electrolyte is positioned in the middle of the membrane electrode electrolytic cell and is communicated with a gas outlet of the heating device; the heating device is used for heating the dry inert gas in a water bath to form wet inert gas, and the wet inert gas is used for leading out the generated formic acid.
Preferably, the filling thickness of the solid electrolyte is 1-5 mm; the membrane electrode electrolytic cell is fixed by screws.
Compared with the prior art, the invention mainly improves the solid electrolyte membrane electrode electrolytic cell and the reaction condition thereof, wherein the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded withWith IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Simultaneously, wet inert gas is introduced into the solid electrolyte part to lead out high-concentration pure formic acid generated by the reaction. The method can realize continuous and stable production of the high-concentration pure formic acid solution, is simple to operate, has mild reaction conditions, and can effectively realize synthesis of the high-concentration pure formic acid (not lower than 1M). In addition, the high-concentration pure formic acid solution prepared by the method can directly drive the direct formic acid fuel cell to run, thereby meeting the actual application requirements.
Drawings
FIG. 1 is a schematic diagram showing the structure and function of a membrane electrode cell used in an embodiment of the present invention;
FIG. 2 is a schematic diagram of a membrane electrode assembly according to an embodiment of the present invention;
FIG. 3 is a graph showing the nuclear magnetic resonance spectrum of the high concentration pure formic acid solution prepared in example 1;
FIG. 4 shows the stability test results of the solid electrolyte system for the membrane electrode in example 1.
Detailed Description
The technical disclosure of the present invention will be clearly and fully described in connection with the following embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In one aspect, the invention provides an electrochemical synthesis method of high-concentration pure formic acid, comprising the following steps:
introducing wet inert gas into the solid electrolyte part in the middle of the membrane electrode electrolytic cell to obtain CO 2 The gas is used as a raw material, sulfuric acid electrolyte is adopted, the membrane electrode electrolytic cell is electrified to obtain high-concentration pure formic acid, and the high-concentration pure formic acid is led out from the wet inert gas;
the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode is provided with hydrophobic carbon with microporous layerThe paper is a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 。
In another aspect, the invention provides an electrochemical electrolysis system of high-concentration pure formic acid, comprising a membrane electrode electrolytic cell and a heating device; the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the gas diffusion cathode has CO at it 2 A gas inlet; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The anode is provided with a sulfuric acid electrolyte inlet;
the solid electrolyte is positioned in the middle of the membrane electrode electrolytic cell and is communicated with a gas outlet of the heating device; the heating device is used for heating the dry inert gas in a water bath to form wet inert gas, and the wet inert gas is used for leading out the generated formic acid.
FIG. 1 is a schematic diagram showing the structure and operation of a Membrane Electrode Assembly (MEA) according to an embodiment of the present invention, which mainly comprises a cathode (gas diffusion electrode+cathode catalyst), and an anode (titanium mesh+IrO) 2 ) Solid electrolyte and anion and cation exchange membranes. During the electrochemical reaction, CO is generated at the cathode 2 Reduction, oxygen precipitation reaction occurs at the anode, and formic acid radical (HCOO - ) Hydrogen ions (H) generated with the anode + ) The resultant formic acid is combined to form formic acid, and the resultant high-concentration pure formic acid solution is discharged from the reactor under a gas purge in which the solid electrolyte is wet.
FIG. 2 is a schematic diagram of a membrane electrode assembly for use in an embodiment of the invention, including a heating device for converting dry gas into humid gas; the heating device is communicated with a solid electrolyte part in the middle of the membrane electrode electrolytic cell, and the electrochemical electrolytic cell provided by the embodiment of the invention uses the solid electrolyte to realize the generation of pure formic acid. The two sides of the solid electrolyte in the length direction are respectively a cathode and an anode, and one side of the cathode relates to CO 2 Is provided with an anode liquid inlet and outlet at one side of the anode.
The embodiment of the invention firstly prepares the electrode: the hydrophobic carbon paper with the microporous layer is used as a cathode substrate, a cathode catalyst is sprayed upwards, and a gas diffusion electrode is formed after drying and is used for a cathode. And, using titanium mesh as the anode substrate, iridium dioxide (IrO) is supported upward, preferably by impregnation-calcination 2 ) For the anode.
In the embodiment of the invention, the cathode catalytic layer is formed by a cathode catalyst, and the catalyst can be tin-based, bismuth-based or indium-based materials, such as bismuth trioxide, tin dioxide, indium trioxide and the like, and has good activity, stability and the like. Preferably, the catalyst is supported on the cathode substrate at a level of 0.5 to 1mg cm -2 。
The anode of the invention takes titanium mesh as an anode substrate, and the surface of the anode is loaded with IrO 2 The electrochemical performance is better; irO of the anode substrate surface 2 The loading is preferably 1-2 mg cm -2 . The anode according to the embodiment of the invention can be prepared by using a dipping-calcining mode, and the preparation process specifically comprises the following steps: the titanium net is firstly treated with indium chloride (IrCl) with a certain concentration 3 ) Soaking in the solution, calcining at 500-600 deg.c in a tubular furnace for 5-10 min, repeating the said steps for several times to reach load of 1-2 mg cm -2 。
In addition to the membrane electrode prepared as described above, the electrochemical cell according to the embodiment of the present invention uses both an anion exchange membrane and a cation exchange membrane. In the specific electrochemical cell assembly, the cathode and the anode electrodes are assembled into the membrane electrode cell, the cathode side uses an anion exchange membrane, the anode side uses a cation exchange membrane, the cathode and the cation exchange membranes are separated by solid electrolyte, and all components are extruded together by screws.
In an embodiment of the present invention, the anion exchange membrane is preferably a Sustainion X37-50 Grade RT anion exchange membrane manufactured by Dioxide Materials company, U.S.A., having a film thickness of 50 microns; the cation exchange membrane preferably comprises one or more of Nafion 115, nafion 117 and Nafion1110, and has a membrane thickness of 127, 183 and 254 μm respectively.
In an embodiment of the present invention, the main component of the solid electrolyte is polystyrene divinylbenzene resin, the particle size is about 50 microns, and the filling thickness may be 1 to 5mm, preferably 2 to 3mm. The solid electrolyte is positioned in the middle of the membrane electrode electrolytic cell and is communicated with the gas outlet of the heating device. The heating device is used for heating dry inert gas in a water bath to form wet inert gas, and the wet inert gas is used for guiding out generated formic acid; the structure of the heating device is not particularly limited, and the dry inert gas can be heated to water with a certain temperature to improve the wettability to more than 50%, and the heating temperature is generally 50-100 ℃. For example, the dry inert gas is heated to 80 ℃ in water to achieve 60% wetting.
After the electrochemical electrolysis system is assembled, the embodiment of the invention introduces wet inert gas into the middle solid electrolyte part of the membrane electrode electrolytic cell to lead out the generated pure formic acid; the cathode is continuously introduced with CO with a certain flow rate 2 The gas, anode is filled with sulfuric acid solution, and then 150-200mA.cm can be filled into the system -2 Thereby obtaining a high concentration of pure formic acid of 1M or more.
In an embodiment of the invention, the cathode of the membrane electrode electrolytic cell adopts CO 2 The flow rate of the gas is preferably 20-30 sccm; the concentration of the electrolyte used for the anode is preferably 0.05 to 0.5M, more preferably 0.1 to 0.5M, and the flow rate thereof may be 0.5 to 2sccm, such as 2 mL. Min -1 . The current of the membrane electrode electrolytic cell is 150-200 mA cm -2 。
Preferably, the wet inert gas introduced into the solid electrolyte in the middle part of the membrane electrode electrolytic cell for synthesizing the high-concentration pure formic acid is CO 2 Or N 2 The wettability is above 50%. The wettability herein means the mass of water vapor contained in a unit volume of air, and 50% wettability is calculated to contain about 1.2g/L of water.
The invention is thatThe embodiment relates to an electrochemical synthesis method and an electrolysis system of high-concentration pure formic acid, and the method comprises the following steps: a) Electrode preparation: the hydrophobic carbon paper with the microporous layer is used as a cathode substrate, a cathode catalyst is sprayed upwards, and a gas diffusion electrode is formed after drying and is used for a cathode; irO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 For the anode; b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes to separate, and all components are extruded together by screws; c) Generating high-concentration pure formic acid: and b) introducing wet inert gas into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, wherein the inert gas can be heated into water with a certain temperature to improve the wettability of the inert gas, and then electrifying the system to obtain the high-concentration pure formic acid. The method provides a scheme for effectively preparing the high-concentration pure formic acid, solves the problems that the concentration of the formic acid is low and the high-concentration pure formic acid is difficult to obtain due to separation of the formic acid and an electrolyte in the traditional electrochemical method, has the advantages of simple process, short time consumption, continuous and stable reaction and the like, and is suitable for large-scale expansion into industrial production.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
Example 1
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 A hydrophobic carbon paper with a microporous layer is used as a cathode substrate, wherein the thickness of the hydrophobic carbon paper is about 190 micrometers, the thickness of the microporous layer is about 45 micrometers, and Bi is used as a cathode substrate 2 O 3 The cathode catalyst is firstly dispersed in isopropanol, then the cathode catalyst is sprayed on a substrate, and a gas diffusion electrode is formed after drying and is used for the cathode, and the final cathode catalyst loading is 1mg cm -2 . Using titanium meshFor the anode substrate, the mesh number of titanium is 100 meshes, the pores are about 0.15mm, and IrO is loaded upwards by a dipping-calcining method 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and anode electrodes in the step a) into a membrane electrode electrolytic cell, wherein a Sustainion X37-50 Grade RT anion exchange membrane is used on the cathode side, a Nafion1110 cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes and is used for separation, the main component of the solid electrolyte is polystyrene divinylbenzene resin, the particle size is about 50 microns, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws (electrode substrate parameters in the following examples, and the electrolyte and the ion exchange membrane of the electrolytic cell are the same);
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water at 80 ℃ to ensure that the wettability reaches 60%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 To obtain 2M high-concentration pure formic acid.
FIG. 3 shows the nuclear magnetic resonance spectrum data of the high concentration pure formic acid solution produced in example 1 of the present invention, wherein the concentration of the pure formic acid produced was found to be 2M.
Fig. 4 is a graph of a 300-hour stability test of the solid electrolyte battery of example 1 of the present invention, which shows that the cell pressure of the solid electrolyte battery is not significantly attenuated, stabilized at about 4V, and the faraday efficiency of formic acid is not significantly attenuated, stabilized at about 70%, and the overall battery energy efficiency is about 27.4% in the 300-hour stability test.
Example 2
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 Hydrophobic carbon paper with microporous layer is used as cathode substrate, bi is used as cathode substrate 2 O 3 The cathode catalyst is first dispersed in isopropanol and then the cathode is sprayed onto the substrateThe polar catalyst is dried to form a gas diffusion electrode for the cathode, and the final catalyst loading of the cathode is 1mg cm -2 . IrO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes to separate, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water at 60 ℃ to ensure that the wettability reaches 50%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 To obtain 3M high-concentration pure formic acid.
Example 3
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 Hydrophobic carbon paper with microporous layer is used as cathode substrate, bi is used as cathode substrate 2 O 3 The cathode catalyst is firstly dispersed in isopropanol, then the cathode catalyst is sprayed on a substrate, and a gas diffusion electrode is formed after drying and is used for the cathode, and the final cathode catalyst loading is 1mg cm -2 . IrO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes to separate, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water with the temperature of 100 ℃ to ensure that the wettability reaches 70%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 1.5M of high-concentration pure formic acid is obtained.
Example 4
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 Hydrophobic carbon paper with microporous layer is used as cathode substrate, bi is used as cathode substrate 2 O 3 The cathode catalyst is firstly dispersed in isopropanol, then the cathode catalyst is sprayed on a substrate, and a gas diffusion electrode is formed after drying and is used for the cathode, and the final cathode catalyst loading is 1mg cm -2 . IrO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes to separate, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water at 80 ℃ to ensure that the wettability reaches 60%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 100mA cm -2 1M of high-concentration pure formic acid is obtained.
Example 5
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 Hydrophobic carbon paper with microporous layer is used as cathode substrate, snO 2 The cathode catalyst is first dispersed in isopropyl alcohol,then spraying a cathode catalyst on the substrate, drying to form a gas diffusion electrode for the cathode, wherein the final cathode catalyst loading is 1mg cm -2 . IrO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membranes to separate, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water at 80 ℃ to ensure that the wettability reaches 60%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 To obtain 2M high-concentration pure formic acid.
Example 6
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 Hydrophobic carbon paper with microporous layer as cathode substrate, in 2 O 3 The cathode catalyst is firstly dispersed in isopropanol, then the cathode catalyst is sprayed on a substrate, and a gas diffusion electrode is formed after drying and is used for the cathode, and the final cathode catalyst loading is 1mg cm -2 . IrO is supported upward by impregnation-calcination method using titanium mesh as anode substrate 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein an anion exchange membrane is used on the cathode side, a cation exchange membrane is used on the anode side, solid electrolyte is used in the middle of the cathode and the cation membrane to separate the cathode and the anode, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-concentration pure formic acid: introducing wet nitrogen into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) to lead out the generated formic acid, heating the gas into water at 80 ℃ to ensure that the wettability reaches 60%, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 1.5M of high-concentration pure formic acid is obtained.
Comparative example 1
a) Electrode preparation: the utilization area is 2 multiplied by 2cm 2 A hydrophobic carbon paper with a microporous layer is used as a cathode substrate, wherein the thickness of the hydrophobic carbon paper is about 190 micrometers, the thickness of the microporous layer is about 45 micrometers, and Bi is used as a cathode substrate 2 O 3 The cathode catalyst is firstly dispersed in isopropanol, then the cathode catalyst is sprayed on a substrate, and a gas diffusion electrode is formed after drying and is used for the cathode, and the final cathode catalyst loading is 1mg cm -2 . Titanium mesh with 100 meshes and pores of about 0.15mm is used as an anode substrate, and IrO is loaded upwards by a dipping-calcining method 2 Final IrO 2 The loading was 1mg cm -2 For the anode;
b) Assembling an electrochemical electrolytic cell: assembling the cathode and the anode in the step a) into a membrane electrode electrolytic cell, wherein a Sustainion X37-50 Grade RT anion exchange membrane is used on the cathode side, a Nafion1110 cation exchange membrane is used on the anode side, a solid electrolyte is used between the cathode and the cation membrane and is used for separation, the main component of the solid electrolyte is polystyrene divinylbenzene resin, the particle size is about 50 microns, the filling thickness of the solid electrolyte is about 2mm, and all components are extruded together by screws;
c) Generating high-purity formic acid: introducing a flow rate of 0.5mL min into the middle solid electrolyte part of the membrane electrode electrolytic cell in the step b) -1 To lead out the generated formic acid, and continuously introducing CO with the flow rate of 30sccm into the cathode 2 Anode inlet flow rate of 2mL min -1 Is then passed through the system with 200mA cm -2 0.2M pure formic acid was obtained.
From the above examples, the present invention is mainly to improve the solid electrolyte membrane electrode electrolytic cell and its reaction conditions, wherein the gas diffusion cathode uses hydrophobic carbon paper with microporous layer as the cathode substrate, and the surface of the cathode substrate has a cathode catalytic layer; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Simultaneously, wet inert gas is introduced into the solid electrolyte part to lead out high-concentration pure formic acid generated by the reaction. The invention can realize continuous and stable production of high-concentration pure formic acid solution, the concentration of pure formic acid is not lower than 1M, and the continuous production can last 300 hours; and the method is simple to operate, mild in reaction condition and beneficial to large-scale popularization and application. In addition, the high-concentration pure formic acid solution prepared by the method can directly drive the direct formic acid fuel cell to run, thereby meeting the actual application requirements.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An electrochemical synthesis method of high-concentration pure formic acid is characterized by comprising the following steps:
introducing wet inert gas into the solid electrolyte part in the middle of the membrane electrode electrolytic cell to obtain CO 2 The gas is used as a raw material, sulfuric acid electrolyte is adopted, the membrane electrode electrolytic cell is electrified to obtain high-concentration pure formic acid, and the high-concentration pure formic acid is led out from the wet inert gas;
the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layerThe method comprises the steps of carrying out a first treatment on the surface of the The anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 。
2. The electrochemical synthesis method according to claim 1, wherein the catalyst of the cathode catalytic layer is a tin-based, bismuth-based or indium-based material, and the catalyst is supported on the cathode substrate at a loading of 0.5-1 mg-cm -2 。
3. The electrochemical synthesis process according to claim 1, wherein the anode substrate surface is IrO 2 The load is 1-2 mg cm -2 。
4. The electrochemical synthesis process according to claim 1, wherein the CO introduced at the cathode of the membrane electrode assembly cell 2 The flow rate of the gas is 20-30 sccm.
5. The electrochemical synthesis method according to claim 1, wherein the concentration of sulfuric acid electrolyte adopted by the anode of the membrane electrode electrolytic cell is 0.05-0.5M, and the flow rate is 0.5-2 sccm.
6. The electrochemical synthesis process according to any one of claims 1 to 5, wherein the humidified inert gas is humidified carbon dioxide gas or nitrogen gas.
7. The electrochemical synthesis method according to claim 6, wherein the wet inert gas is formed by heating dry inert gas to 50 to 100 ℃ in water, and the wettability is 50% or more.
8. The electrochemical synthesis method according to claim 6, wherein the current applied to the membrane electrode assembly cell is 150 to 200mA cm -2 。
9. An electrochemical electrolysis system of high-concentration pure formic acid is characterized by comprising a membrane electrodeAn electrolytic cell and a heating device; the membrane electrode assembly cell includes: a gas diffusion cathode, an anion exchange membrane, a solid electrolyte, a cation exchange membrane and an anode which are sequentially compounded; the gas diffusion cathode takes hydrophobic carbon paper with a microporous layer as a cathode substrate, and the surface of the cathode substrate is provided with a cathode catalytic layer; the gas diffusion cathode has CO at it 2 A gas inlet; the anode takes a titanium net as an anode substrate, and the surface of the anode substrate is loaded with IrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The anode is provided with a sulfuric acid electrolyte inlet;
the solid electrolyte is positioned in the middle of the membrane electrode electrolytic cell and is communicated with a gas outlet of the heating device; the heating device is used for heating the dry inert gas in a water bath to form wet inert gas, and the wet inert gas is used for leading out the generated formic acid.
10. The electrochemical electrolysis system according to claim 9, wherein the solid electrolyte has a fill thickness of 1 to 5mm; the membrane electrode electrolytic cell is fixed by screws.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311247174.3A CN117210830A (en) | 2023-09-25 | 2023-09-25 | Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311247174.3A CN117210830A (en) | 2023-09-25 | 2023-09-25 | Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117210830A true CN117210830A (en) | 2023-12-12 |
Family
ID=89050880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311247174.3A Pending CN117210830A (en) | 2023-09-25 | 2023-09-25 | Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117210830A (en) |
-
2023
- 2023-09-25 CN CN202311247174.3A patent/CN117210830A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI414636B (en) | Membrane reactor | |
| TWI448325B (en) | Method for electrochemically transforming carbon dioxide | |
| US9574276B2 (en) | Production of low temperature electrolytic hydrogen | |
| US11035045B2 (en) | Apparatus for producing organic hydride and method for producing organic hydride using same | |
| CN110117794B (en) | Electro-reduction of CO2Three-chamber type electrolytic cell device for preparing formate and electrolytic method thereof | |
| CN103178283B (en) | Hydrogen-bromine energy storage battery structure | |
| CN101748423B (en) | Efficient electrochemical reactor of electro-catalysis in-situ hydrogen peroxide | |
| TWI448327B (en) | Membrane reactor | |
| Tatapudi et al. | Simultaneous Synthesis of Ozone and Hydrogen Peroxide in a Proton‐Exchange‐Membrane Electrochemical Reactor | |
| WO2021160759A1 (en) | Electrochemical cell for the synthesis of hydrogen peroxide | |
| US7056423B2 (en) | Apparatus for producing hydrogen, electrochemical device, method for producing hydrogen and method for generating electrochemical energy | |
| CN108441885A (en) | A kind of composite material and its application in urea aoxidizes assistance Acid-Base electrolytic cell device for preparing hydrogen | |
| WO2024017053A1 (en) | Ship carbon dioxide tail gas treatment system | |
| CN113174600A (en) | Porous nickel screen electrolytic water catalytic material and preparation method thereof | |
| CN117210830A (en) | Electrochemical synthesis method and electrochemical electrolysis system of high-concentration pure formic acid | |
| CN213570766U (en) | Water decomposition hydrogen production device based on lead net | |
| CN212077164U (en) | Electric energy supply type electrochemical reactor | |
| CN112251765B (en) | Water-splitting hydrogen production device based on lead net and preparation method and use method thereof | |
| CN219099334U (en) | Movable hydrogen peroxide preparation facilities | |
| JP3921300B2 (en) | Hydrogen generator | |
| KR102610119B1 (en) | Water management unit in hydrogen generating system using water electrolysis | |
| CN113611873B (en) | SO (SO) 2 Preparation and laying method of anode support body of depolarized electrolytic cell | |
| US9273405B1 (en) | Electrolysis device for chlorine production | |
| CN111206264A (en) | Electric energy supply type electrochemical reactor and use method thereof | |
| CN117684191A (en) | Device and method for preparing multi-carbon compound by high-temperature electrolytic tank series membrane electrode reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |