CN219886195U - Device for preparing formic acid and hydrogen - Google Patents
Device for preparing formic acid and hydrogen Download PDFInfo
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- CN219886195U CN219886195U CN202320315040.XU CN202320315040U CN219886195U CN 219886195 U CN219886195 U CN 219886195U CN 202320315040 U CN202320315040 U CN 202320315040U CN 219886195 U CN219886195 U CN 219886195U
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 336
- 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 168
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 168
- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000000926 separation method Methods 0.000 claims abstract description 227
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 127
- 239000007789 gas Substances 0.000 claims abstract description 109
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 claims abstract description 68
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000004891 communication Methods 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 29
- 238000007599 discharging Methods 0.000 claims description 27
- 239000002808 molecular sieve Substances 0.000 claims description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 26
- 239000010411 electrocatalyst Substances 0.000 claims description 23
- 238000009792 diffusion process Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000009833 condensation Methods 0.000 claims description 16
- 230000005494 condensation Effects 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000012546 transfer Methods 0.000 claims description 11
- 239000000498 cooling water Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229940021013 electrolyte solution Drugs 0.000 description 95
- 239000003792 electrolyte Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004280 Sodium formate Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 4
- 235000019254 sodium formate Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The utility model provides a device for preparing formic acid and hydrogen, which comprises an anode electrocatalysis module, wherein electrolyte solution in an electrolyte solution chamber arranged in the anode electrocatalysis module generates O through the electrocatalysis effect of an anode catalyst in the anode electrocatalysis module 2 The method comprises the steps of carrying out a first treatment on the surface of the A cathode electrocatalytic module configured to be cathodically catalyzedElectrocatalytic action of the agent causes the electrolyte solution, CO 2 Producing formic acid; CO 2 A separation chamber module in communication with the cathode electrocatalysis module interior configured to receive the formic acid produced, unreacted CO 2 And an electrolyte solution; a heating module in communication with the outlet D and configured to heat formic acid and electrolyte solution; a formic acid hydrogen production module configured to produce H over a formic acid hydrogen production catalyst 2 And CO 2 The method comprises the steps of carrying out a first treatment on the surface of the A mixed gas separation chamber module configured to separate an electrolyte solution, H 2 And CO 2 ；H 2 A separation chamber module configured to separate H 2 And CO 2 。
Description
Technical Field
The utility model belongs to the technical field of electrocatalysis, and particularly relates to a device for preparing formic acid and hydrogen.
Background
Combustion of fossil fuels to create atmospheric CO 2 Other concentrations increase, thereby causing global warming, CO 2 The electro-reduction technology can utilize renewable power of clean energy sources to convert CO 2 The method is a sustainable development path for high-added-value chemicals and fuels and for realizing artificial carbon circulation.
However, how to realize the economical and efficient preparation of H 2 Is important for the development of hydrogen energy economy. At present, the common small-scale hydrogen production method mainly comprises two modes of methanol/natural gas reforming hydrogen production and water electrolysis hydrogen production. The reaction process of reforming hydrogen production is complex, the system is huge, the requirement on equipment is high, and the mobility is poor.
Formic acid is considered a promising hydrogen carrier because of its volume and weight H 2 The capacities were 53gl respectively -1 And 4.4wt% and corresponds to 1.77kWhl -1 Is a high energy density of (a). Formic acid can be synthesized by sustainable routes, e.g. CO 2 Is carried out in the presence of a catalyst. Or partial oxidation of wet biomass. Dehydrogenation of formic acid to H 2 And CO 2 Is thermodynamically advantageous in the gas phase (Δgo= -6.9kcalmol -1 )。
At present, the domestic and foreign formic acid process mainly comprises three types: traditional production process, biological production process and CO 2 A hydrogenation production process. The traditional production process can be divided into a sodium formate method and a methyl formate hydrolysis method, wherein the sodium formate method firstly adopts CO to react with NaOH to obtain sodium formate, and then the sodium formate reacts with sulfuric acid to finally obtain formic acid. The methyl formate hydrolysis method uses methanol and CO to generate carboxylation reaction and then generates formic acid by hydrolysis, and is the current main method And (5) a flow process.
The electrocatalytic direct hydrogen production generally has two devices, one is an alkaline electrolytic tank, namely, a certain amount of alkali or salt is added into the electrolytic tank to enhance conductivity, and H is obtained at the anode and the cathode respectively 2 And oxygen, and water is electrolyzed by the electrolysis device to prepare H 2 Still has the problems of high energy consumption and poor economy. The PEM electrolyzer has the advantages of simple operation, separated anode and cathode, certain partial pressure of gas, no alkali solution, etc. and is widely used in industry. The theoretical electrolysis voltage of the hydrogen production by water electrolysis is 1.23V, and in the actual hydrogen production process by electrolysis, the electrolysis voltage is as high as 1.4-1.5V due to certain loss;
the industrial process for the preparation of formic acid uses two industrial raw materials, methanol and CO, at a cost corresponding to the cost of CO 2 Slightly higher than the water.
Disclosure of Invention
Aiming at the defects existing in the prior art, the utility model aims to provide a device for preparing formic acid and hydrogen, which integrates various processes, has light weight and strong operability and can produce CO 2 Recycling gas and electrolyte to prepare H 2 And exhaust gas is prevented from being generated.
To achieve the purpose, the utility model adopts the following technical scheme:
The utility model provides a device for preparing formic acid and hydrogen, which comprises:
an anode electrocatalyst module having an electrolyte solution chamber for containing an electrolyte solution and a gas-liquid separation chamber disposed therein, the electrolyte solution in the electrolyte solution chamber generating O by electrocatalysis of an anode catalyst in the anode electrocatalyst module 2 ；
A first gas diaphragm is arranged in the gas-liquid separation chamber, and separates the gas-liquid separation chamber into a first separation chamber and is used for accommodating O 2 The first gas membrane is configured to separate O 2 The electrolyte solution enters the first separation chamber;
the first separation chamber is provided with a supply stationAn outlet A for discharging the electrolyte solution, the second separation chamber being provided with a supply O 2 A discharged outlet L, the electrolyte solution chamber being provided with an inlet B communicating with the outlet a;
a cathode electrocatalysis module provided with an inlet C for receiving electrolyte solution entering through the anode electrocatalysis module, wherein the inlet C is communicated with CO 2 A source, the cathode electrocatalyst module configured to cause the electrolyte solution, CO, via electrocatalytic action of a cathode catalyst 2 Producing formic acid;
CO 2 A separation chamber module in communication with the cathode electrocatalysis module interior configured to receive the formic acid produced, unreacted CO 2 And an electrolyte solution;
the CO 2 The separation chamber module is configured to separate out CO 2 The CO 2 The separation chamber module is provided with an outlet O and an outlet D which are communicated with the inlet C, and the outlet D is configured to discharge separated formic acid and electrolyte solution;
a heating module in communication with the outlet D and configured to heat formic acid and electrolyte solution;
a formic acid hydrogen production module, the interior of which is communicated with the heating module, the formic acid hydrogen production module is configured to prepare H through a formic acid hydrogen production catalyst 2 And CO 2 ；
The formic acid hydrogen production module is provided with a device for discharging the electrolyte solution and H 2 And CO 2 Outlet I of (a);
a mixed gas separation chamber module configured to separate an electrolyte solution, H 2 And CO 2 The mixed gas separating chamber module is provided with an inlet U communicated with the outlet I, an outlet H communicated with the inlet B and a supply H 2 And CO 2 An outlet P for discharging;
H 2 a separation chamber module configured to separate H 2 And CO 2 The H is 2 The separation chamber module is provided with an inlet Q communicated with the outlet P and is used for discharging H 2 Is communicated with the inlet C and is used for discharging CO 2 Is provided for the outlet T of (c).
Preferably, the anode electrocatalysis module comprises:
the electrolyte solution chamber and the gas-liquid separation chamber are arranged on the electrolyte solution chamber plate;
the first insulating layer plate is configured to prevent anode current from passing through, a first through hole and a fourth through hole which are communicated with the electrolyte solution chamber are formed in the first insulating layer plate, and the fourth through hole is communicated with the gas-liquid separation chamber;
the anode plate is provided with uniformly distributed first grooves, one end of each first groove is provided with a second port communicated with the first port, and the other end of each first groove is provided with a third port communicated with the fourth port;
the electrolyte solution is able to enter the anode plate, which electrocatalytic to water within the electrolyte solution to produce O 2 。
Preferably, the anode electrocatalyst module further comprises an anode gas diffusion layer sheet disposed between the anode plate and the anode catalyst plate, the anode gas diffusion layer sheet configured to homogenize an electrolyte solution and H 2 Mass transfer and transport between.
Preferably, the cathode electrocatalyst module comprises a cathode catalyst plate and a cathode plate disposed in sequence, the cathode catalyst plate being disposed on a side adjacent to the anode catalyst plate;
a second groove is formed in the cathode plate, a ninth through hole is formed in one end of the second groove, and a tenth through hole is formed in the other end of the second groove;
a fifth through hole communicated with the electrolyte solution chamber is formed in the first insulating layer plate, a sixth through hole communicated with the fifth through hole is formed in the anode plate, and a seventh through hole communicated with the sixth through hole is formed in the anode gas diffusion layer plate;
an eighth through hole communicated with the seventh through hole is formed on the cathode catalyst plate, and the eighth through holeThe eighth port is communicated with the ninth port, and the tenth port is communicated with the CO 2 The interior of the separation chamber module.
Preferably, the cathode electrocatalysis module further comprises a cathode gas diffusion layer plate disposed between the cathode plate and the cathode catalyst plate, and the cathode gas diffusion layer plate is provided with a fifteenth port communicated with the eighth port and the ninth port.
Preferably, the cathode electrocatalyst module further comprises a separator sheet disposed between the anode electrocatalyst module and the cathode electrocatalyst module, the separator sheet configured to convert anode-produced O 2 And H generated by cathode 2 、CO 2 And the isolation diaphragm plate is provided with a twelfth through hole, and the tenth through hole is communicated with the seventh through hole and the eighth through hole.
Preferably, the CO 2 The separation chamber module comprises CO 2 A separation frame plate and a second gas membrane arranged therein, the second gas membrane being connected to the CO 2 A third separation chamber and a fourth separation chamber are respectively formed between the separation frame plates, and the fourth separation chamber is communicated with the inside of the cathode electrocatalytic module;
the second gas barrier is configured to block CO 2 Passing formic acid and electrolyte solution into the third separation chamber within the fourth separation chamber;
the outlet D is arranged in the third separation chamber, and the outlet O is arranged in the fourth separation chamber.
Preferably, the heating module comprises a heating chamber assembly and an insulating layer, wherein the insulating layer is positioned on the heating chamber assembly and the CO 2 Between the separation chamber modules, the thermal insulation layer is configured to block heat of the heating chamber assembly from the CO 2 A separation chamber module transfer;
an inlet E communicated with the outlet D is formed in the heating chamber assembly, a heating flow passage for introducing a heating medium into the heating chamber assembly is formed in the heating chamber assembly, and an outlet F and an inlet S are formed in one end of the heating flow passage;
And a thirteenth through hole for passing through formic acid and electrolyte solution and communicated with the formic acid hydrogen production module is formed in the heating chamber assembly.
Preferably, the apparatus for preparing formic acid and hydrogen further comprises a condensation module, and the formic acid hydrogen production module comprises:
the formic acid hydrogen production chamber piece and the formic acid hydrogen production catalyst plate are arranged inside the formic acid hydrogen production chamber piece and are positioned between the formic acid hydrogen production chamber piece and the heating chamber component;
the inside of the formic acid hydrogen producing chamber part is communicated with the thirteenth port, and the formic acid hydrogen producing chamber part is configured to produce H from formic acid and electrolyte solution in the formic acid hydrogen producing chamber part under the catalysis of a formic acid hydrogen producing catalyst 2 And CO 2 The formic acid hydrogen producing chamber part is provided with a device for discharging electrolyte solution H 2 And CO 2 And an outlet I in communication with the condensing module.
Preferably, the condensation module includes:
the condensation chamber piece is internally provided with a product conveying pipe, one end of the product conveying pipe is an inlet J communicated with the outlet I, and the other end of the product conveying pipe is an outlet V communicated with the mixed gas separation chamber module;
an inlet G communicated with external cooling water and an outlet R used for discharging the cooling water are arranged on the condensation chamber piece;
And a heat insulating plate disposed between the condensation chamber member and the formic acid hydrogen producing chamber member, the heat insulating plate being configured to block the condensation chamber member from transferring cool air to the formic acid hydrogen producing chamber member.
Preferably, the mixed gas separation chamber module includes:
a mixed gas separating chamber shell provided with an outlet H, an inlet U communicated with the outlet V and an outlet P;
a third gas diaphragm is arranged in the mixed gas separating chamber shell;
the third gas diaphragm is arranged inside the mixed gas separation chamber shell, and is respectively formed into a fifth separation chamber and a sixth separation chamber with the mixed gas separation chamber shell, one end of the outlet H is communicated with the fifth separation chamber, the other end of the outlet H is communicated with the inlet B, and the inlet U and the outlet P are both communicated with the sixth separation chamber;
and a droplet catcher disposed in the sixth separation chamber and above the third gas membrane.
Preferably, the H 2 The separation chamber module includes:
H 2 a separation chamber housing provided on one side of the mixed gas separation chamber housing;
the first molecular sieve membrane and the second molecular sieve membrane which are arranged in parallel are both arranged on the H 2 An interior of the separation chamber housing;
The first molecular sieve membrane, the second molecular sieve membrane and the H 2 A seventh separation chamber, an eighth separation chamber and a ninth separation chamber are sequentially formed between the separation chamber shells;
the first molecular sieve membrane is configured to separate H 2 Passing it into the seventh separation chamber, the second molecular sieve membrane being configured to separate CO 2 Passing it into the eighth separation chamber;
the H is 2 The separating chamber shell is provided with a device for discharging H 2 An outlet K communicating with the outlet P, and an outlet T communicating with the outlet C, the outlet K being provided in the seventh separation chamber, the outlet Q being provided in the eighth separation chamber, and the outlet T being provided in the ninth separation chamber.
Compared with the prior art, the utility model has the following beneficial effects:
the formic acid is used as a liquid fuel and a hydrogen source, has the advantages of portability, high hydrogen content, environmental friendliness and the like, and most importantly, the theoretical electrolytic voltage is low, so that the voltage required by the electrolytic hydrogen production of the formic acid is greatly lower than that required by the electrolytic hydrogen production of water, the consumption of electric energy is greatly reduced, and the feasibility is provided for small-scale on-site hydrogen production.
The electrocatalytic preparation of formic acid only requires the use of CO 2 And water, the other electrolyte solution is not used in the whole catalytic process Consumption, electricity saving and raw material cost reduction.
CO is treated in the utility model 2 The device integrates the electrocatalytic preparation of formic acid and the catalytic hydrogen production of formic acid, and realizes the integration of the preparation of formic acid and the hydrogen production of formic acid.
Drawings
FIG. 1 is an exploded view of an apparatus for producing formic acid and hydrogen in the present utility model;
FIG. 2 is a schematic view showing the structure of the apparatus for producing formic acid and hydrogen according to the first angle of the present utility model;
fig. 3 is a schematic view showing the structure of the apparatus for producing formic acid and hydrogen according to the second aspect of the present utility model.
Wherein, 1, an anode electrocatalysis module; 11. an electrolyte chamber plate; 111. a first gas membrane; 110. an electrolyte solution chamber; 120. a gas-liquid separation chamber; 120a, a first separation chamber; 120b, a second separation chamber;
12. a first insulating layer plate; 13. an anode plate; 130. an anode conductive sheet; 131. a first trench; 14. an anode catalyst plate; 1a, a first through hole; 2a, a fourth port; 3a, a second port; 4a, a third port; 15. an anode gas diffusion layer plate;
2. a cathode electrocatalysis module; 21. a cathode catalyst plate; 22. a cathode plate; 221. a cathode conductive sheet; 220. a second trench; 23. a cathode gas diffusion layer plate; 5a, a fifth port; 6a, a sixth through port; 7a, a seventh through port; 8a, an eighth through port; 9a, a ninth through port; 10a, a tenth through port; 11a, eleventh opening; 12a, a twelfth port; 13a, thirteenth through-openings; 14a, a fourteenth port;
3、CO 2 A separation chamber module; 31. CO 2 Separating the frame plates; 32. a second gas membrane; 32a, a third separation chamber; 32b, a fourth separation chamber;
4. a heating module; 41. a heating chamber assembly; 411. a heating chamber housing; 412. heating pipes; 42. a thermal insulation layer;
5. a formic acid hydrogen production module; 51. a formic acid hydrogen producing chamber member; 511. a formic acid hydrogen-producing shell; 512. a first separator; 511a, a first chamber; 511b, a second chamber; 52. a formic acid hydrogen production catalyst plate;
6. a condensing module; 61. a condensing chamber member; 62. a thermal insulation plate; 63. a product transfer tube;
7. a mixed gas separation chamber module; 71. a mixed gas separation chamber housing; 71a, a fifth separation chamber; 71b, a sixth separation chamber; 72. a third gas separator; 73. a droplet catcher;
8、H 2 a separation chamber module; 81. h 2 A separation chamber housing; 81a, seventh separation chamber; 81b, eighth separation chamber; 81c, a ninth separation chamber; 82. a first molecular sieve membrane; 83. a second molecular sieve membrane;
9. a second insulating laminate; 24. and (5) isolating the membrane plate.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present utility model more apparent, the technical solutions of the embodiments of the present utility model will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present utility model, and it is apparent that the described embodiments are some embodiments of the present utility model, but not all embodiments of the present utility model. The components of the embodiments of the present utility model generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the utility model, as presented in the figures, is not intended to limit the scope of the utility model, as claimed, but is merely representative of selected embodiments of the utility model. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present utility model, it should be noted that, directions or positional relationships indicated by terms such as "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or are directions or positional relationships conventionally put in use of the inventive product, are merely for convenience of describing the present utility model and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific direction, be configured and operated in a specific direction, and thus should not be construed as limiting the present utility model. Furthermore, the terms "first," "second," "third," and the like are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance. In the description of the present utility model, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present utility model, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed", "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected or integrally connected; either mechanically or electrically. The specific meaning of the above terms in the present utility model will be understood in specific cases by those of ordinary skill in the art.
In the present utility model, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
Embodiments of the present utility model are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the utility model.
As shown in fig. 1 to 3, an apparatus for producing formic acid and hydrogen is provided in this embodiment, and the hydrogen production apparatus includes an anode electrocatalysis module 1, a cathode electrocatalysis module 2, and CO 2 Separation chamber module 3, formic acid hydrogen production module 5, condensation module 6, mixed gas separation chamber module 7 and H 2 A separation chamber module 8, wherein the anode electrocatalyst module 1 is internally provided with an electrolyte solution chamber 110 and a gas-liquid separation chamber 120, and the electrolyte solution in the electrolyte solution chamber 110 generates O through the electrocatalyst action of an anode catalyst in the anode electrocatalyst module 1 2 The electrolyte solution chamber 110 is configured to contain O 2 And an electrolyte solution, the gas separation chamber 120 being configured such that the gas separation chamber 120 is configured to contain the electrolyte solution and O that are refluxed after reaction 2 The method comprises the steps of carrying out a first treatment on the surface of the The gas-liquid separation chamber 120 is provided with an outlet A for discharging the electrolyte solution and a supply O 2 The discharged outlet L, the electrolyte solution chamber 110 is provided with an inlet B communicating with the a port. Specifically, O 2 And the electrolyte solution after reaction returns to the gas-liquid separation chamber 120, and the gas-liquid separation chamber 120 flows out the electrolyte solution after reaction from the outlet A to the inlets B and O 2 Discharged through outlet L and collected.
The cathode electrocatalytic module 2 is provided with an inlet C, the cathode electrocatalytic module 2 is used for receiving electrolyte solution entering through the anode electrocatalytic module 1, and the inlet C is communicated with CO 2 The source, cathode electrocatalyst module 2 is configured to cause the electrolyte solution, CO, to be catalyzed by the electrocatalyst of the cathode catalyst 2 Formic acid is produced.
CO 2 The separation chamber module 3 is in internal communication with the cathode electrocatalytic module 2 and is configured to receive the formic acid produced, unreacted CO 2 And an electrolyte solution. CO 2 The separation chamber module 3 is configured to separate out CO 2 ，CO 2 The separation chamber module 3 is provided with an outlet O and an outlet D communicating with the inlet C, the outlet D being configured to discharge the separated formic acid and electrolyte solution. Specifically by CO 2 CO separated by the separation chamber module 3 2 Through outlet O rowExiting to inlet C, the separated formic acid and electrolyte solution are discharged to heating module 4 via outlet D for heating.
The heating module 4 is in communication with the outlet D and is configured to heat the formic acid and the electrolyte solution. The inside of the formic acid hydrogen production module 5 is communicated with the heating module 4, and the formic acid hydrogen production module 5 is configured to prepare H through a formic acid hydrogen production catalyst 2 And CO 2 . The formic acid hydrogen production module 5 is provided with a device for discharging electrolyte solution H 2 And CO 2 Is provided.
The condensing module 6 is configured to remove the electrolyte solution, H 2 And CO 2 The condensing module 6 is provided with an inlet J communicated with the outlet I and is used for discharging electrolyte solution and H 2 And CO 2 Is provided for the outlet V of (c).
The mixed gas separation chamber module 7 is configured to separate an electrolyte solution, H 2 And CO 2 The mixed gas separating chamber module 7 is provided with an inlet U communicated with the outlet V, an outlet H communicated with the inlet B and a supply H 2 And CO 2 An outlet P for discharging. Specifically, electrolyte solution, H 2 And CO 2 Discharged from the outlet V to the inlet U, the electrolyte solution separated by the mixed gas separating chamber module 7 is discharged from the outlet H to the inlet B, and the separated H 2 And CO 2 Discharged through the outlet P.
H 2 The separation chamber module 8 is configured to separate H 2 And CO 2 ，H 2 The separation chamber module 8 is provided with an inlet Q communicated with the outlet P and is used for discharging H 2 Is communicated with the inlet C and is used for discharging CO 2 Is provided for the outlet T of (c).
In the present embodiment, O is produced by electrolyzing water of an electrolyte solution using the anode electrocatalysis module 1 2 ，O 2 The electrolyte solution flows back to the gas-liquid separation chamber 120 together with the electrolyte solution, and the electrolyte solution after reaction flows out from the gas-liquid separation chamber 120 to the inlets B and O through the outlet A 2 Discharged through the outlet L and collected for use.
The cathode electrocatalytic module 2 is provided with an inlet C, electrolyte solution enters the cathode electrocatalytic module 2 through the anode electrocatalytic module 1, and CO 2 Is infused intoOpening C is led into the cathode electrocatalytic module 2, electrolyte solution and CO 2 Formic acid is produced in the cathode electrocatalyst module 2 by the electrocatalytic action of a cathode catalyst.
CO 2 The separation chamber module 3 is communicated with the inside of the cathode electrocatalytic module 2, and the prepared formic acid and unreacted CO 2 And electrolyte solution into CO 2 Separation chamber, CO 2 The separated formic acid and electrolyte solution enter the cathode electrocatalytic module 2 again through an inlet C for recycling, and the prepared formic acid and electrolyte solution are heated in the heating module 4 through an outlet D.
The inside of the formic acid hydrogen production module 5 is communicated with the heating module 4, and the heated hydrogen flows into the formic acid hydrogen production module 5 to produce H under the action of a formic acid hydrogen production catalyst 2 And CO 2 Electrolyte solution, H 2 And CO 2 Are all discharged to an inlet J of a condensing module 6 communicated with the outlet I, and the condensing module 6 is used for cooling H 2 And CO 2 。
The mixed gas separation chamber module 7 is used for separating electrolyte solution, H 2 And CO 2 The separated electrolyte solution is discharged to an inlet B through an outlet H, and the separated H 2 And CO 2 Enter H through the outlet P and the inlet Q 2 In the separation chamber module 8, H after separation 2 Discharged through an outlet K to be collected for use, and separated CO 2 Is discharged through the outlet T to the inlet C to be recycled again by the cathode electrocatalysis module 2.
In the embodiment, the formic acid is used as the liquid fuel and the hydrogen source, has the advantages of portability, high hydrogen content, environmental friendliness and the like, and most importantly, the theoretical electrolytic voltage is low, so that the voltage required by the electrolytic hydrogen production of the formic acid is greatly lower than that required by the electrolytic hydrogen production of water, the consumption of electric energy is greatly reduced, and the feasibility is provided for small-scale on-site hydrogen production.
The electrocatalytic preparation of formic acid only requires the use of CO 2 And water, other electrolyte solutions are not consumed in the whole catalytic process, and the raw material cost is reduced while electricity is saved.
CO is treated in the application 2 Electrocatalytic preparation of formic acid and catalytic hydrogen production from formic acidThe device integrates the electrocatalytic preparation of formic acid and the catalytic hydrogen production of formic acid, thus realizing the integration of the preparation of formic acid and the hydrogen production of formic acid.
Preferably, the anode electrocatalyst module 1 includes an electrolyte chamber plate 11, a first insulating layer plate 12, an anode plate 13, and an anode catalyst plate 14, which are sequentially disposed, and an electrolyte solution chamber 110 and a gas-liquid separation chamber 120 are disposed on the electrolyte chamber plate 11. The first insulating layer 12 is configured to prevent the passage of anode current, and the first insulating layer 12 is provided with a first port 1a and a fourth port 2a communicating with the electrolyte solution chamber 110, the fourth port 2a communicating with the gas-liquid separation chamber 120.
The anode plate 13 is provided with uniformly distributed first grooves 131, one end of the first groove 131 is provided with a second port 3a communicated with the first port 1a, and the other end is provided with a third port 4a communicated with the fourth port 2 a. Electrolyte solution enters the anode plate 13, and the anode catalyst plate 14 electrically catalyzes water in the electrolyte solution to generate O 2 。
Preferably, the anode electrocatalyst module 1 further comprises an anode gas diffusion layer plate 15 disposed between the anode plate 13 and the anode catalyst plate 14, the anode gas diffusion layer plate 15 being configured to homogenize the electrolyte solution and the H 2 Mass transfer and transport between.
Preferably, the electrolyte chamber plate 11 is provided with an electrolyte chamber 110 and a gas-liquid separation chamber 120 inside, the gas-liquid separation chamber 120 is provided with a first gas membrane 111 inside, and the first gas membrane 111 separates the gas-liquid separation chamber 120 into a first separation chamber 120a and is used for accommodating O 2 The first gas membrane 111 is configured to separate O 2 The electrolyte solution after that enters the first separation chamber 120a. Namely, a first separation chamber 120a is defined between the first gas membrane 111 and the electrolyte chamber plate 11, a second separation chamber 120b is defined between the first gas membrane 111 and the outer wall of the electrolyte chamber plate 11, an outlet A is arranged in the first separation chamber 120a, an outlet L is arranged in the second separation chamber 120b, and the electrolyte chamber 110 is communicated with the first through hole 1 a.
In this embodiment, the first separation chamber 120a is rectangular, the second separation chamber 120b is L-shaped, and the shapes of the first separation chamber 120a and the second separation chamber 120b can be adjusted according to practical situations.
Preferably, the anode plate 13 is provided with uniformly distributed first grooves 131, and the first grooves 131 are distributed in a shape of a Chinese character 'hui'. As shown in fig. 1, the first grooves 131 are distributed along the upper and lower folds.
Preferably, the cathode electrocatalyst module 2 comprises a cathode catalyst plate 21 and a cathode plate 22 arranged in sequence, the cathode catalyst plate 21 being arranged on the side close to the anode catalyst plate 14.
The cathode plate 22 is provided with a second groove 220, one end of the second groove 220 is provided with a ninth through hole 9a, and the other end is provided with a tenth through hole 10a.
The first insulating layer plate 12 is provided with a fifth port 5a communicated with the electrolyte solution chamber 110, the anode plate 13 is provided with a sixth port 6a communicated with the fifth port 5a, the anode catalyst plate 14 is provided with a fourteenth port 14a communicated with both the sixth port 6a and the seventh port 7a, and the anode gas diffusion layer plate 15 is provided with a seventh port 7a communicated with the sixth port 6 a.
The cathode catalyst plate 21 is provided with an eighth port 8a communicated with the seventh port 7a, the eighth port 8a is communicated with a ninth port 9a, and the tenth port 10a is communicated with CO 2 The interior of the chamber module 3.
Preferably, the cathode electrocatalyst module 2 further comprises a cathode gas diffusion layer plate 23 disposed between the cathode plate 22 and the cathode catalyst plate 21, and the cathode gas diffusion layer plate 23 is provided with a fifteenth port 15a communicating with both the eighth port 8a and the ninth port 9 a.
Preferably, the cathodic electrocatalytic module 2 and CO 2 A second insulating layer 9 is arranged between the separation chamber modules 3, the second insulating layer 9 being configured to prevent the passage of current, and to prevent the transfer of current to the CO during operation of the cathode electrocatalytic module 2 2 Within the separation chamber module 3. Specifically, one side of the second insulating laminate 9 is in contact with the cathode plate 22, and the other side is in contact with CO 2 The separation chamber modules 3 are in contact. Correspondingly, the second insulating layer 9 is provided with an eleventh opening 11a, and the eleventh opening 11a and CO 2 The separation chamber module 3 and the tenth port 10a are both communicated.
Preferably, the cathode electrocatalytic module 2 further comprises a separator plate 24 arranged between the anode electrocatalytic module 1 and the cathode electrocatalytic module 2, the separator plate 24 being configured to bring about the production of O by the anode 2 And H generated by cathode 2 、CO 2 The separator plate 24 is provided with a twelfth opening 12a, and the tenth opening 12a is communicated with the seventh opening 7a and the eighth opening 8 a.
Preferably, CO 2 The separation chamber module 3 comprises CO 2 A separation frame plate 31 and a second gas diaphragm 32 provided therein, the second gas diaphragm 32 and CO 2 The separation frame plates 31 form a third separation chamber 32a and a fourth separation chamber 32b therebetween, respectively, and the fourth separation chamber 32b communicates with the inside of the cathode electrocatalysis module 2.
The second gas membrane 32 is configured to block CO 2 In the fourth separation chamber 32b, and formic acid and an electrolyte solution are passed into the third separation chamber 32a.
An outlet D is provided in the third separation chamber 32a, an outlet O is provided in the fourth separation chamber 32b, the eleventh opening 11a communicates with the fourth separation chamber 32b, and the second gas diaphragm 32 separates CO 2 Separated in the fourth separation chamber 32b, formic acid and electrolyte solution enter the third separation chamber 32a through the second gas membrane 32 and are discharged through the outlet D.
In the present embodiment, the method is used in CO 2 The separation frame plate 31 is internally provided with a second gas membrane 32 for blocking the passage of gas, not liquid, i.e. CO 2 Blocked in the fourth separation chamber 32b, formic acid and electrolyte solution enter the third separation chamber 32a to react with unreacted CO 2 Is recycled after separation.
Preferably, the heating module 4 comprises a heating chamber assembly 41 and an insulating layer 42, the insulating layer 42 being located between the heating chamber assembly 41 and the CO 2 Between the separation modules 3, the insulating layer 42 is configured to block heat of the heating chamber assembly 41 from being directed toward CO 2 The separation chamber module 3 communicates.
An inlet E communicated with the outlet D is arranged on the heating chamber assembly 41, a heating runner is arranged in the heating chamber assembly 41, an outlet F and an inlet S are arranged at one end of the heating runner, a heating medium is introduced into the heating runner through the inlet S and flows out through the outlet F, a tenth three-way port 13a communicated with the formic acid hydrogen production module 5 is arranged in the heating chamber assembly 41, and formic acid and electrolyte solution enter the formic acid hydrogen production module 5 through the thirteenth port 13 a.
Specifically, the heating chamber assembly 41 includes a heating chamber housing 411 and heating pipes 412 disposed inside the heating chamber housing 411 and reciprocally arranged in a zigzag shape, wherein a heating flow passage is disposed inside the heating chamber housing 411, and one end of the heating pipe 412 is communicated with an inlet F and one end is communicated with an outlet S. Formic acid and electrolyte solution discharged through the outlet D are communicated with the inlet E of the heating chamber assembly 41 through an external pump, enter the heating chamber shell 411, are heated by a heating medium in the heating pipe 412, and enter the formic acid hydrogen production module 5 through the thirteenth through hole 13 a.
Preferably, the formic acid hydrogen production module 5 includes a formic acid hydrogen production chamber part 51 and a formic acid hydrogen production catalyst plate 52, wherein the formic acid hydrogen production catalyst plate 52 is disposed inside the formic acid hydrogen production chamber part 51 and between the formic acid hydrogen production chamber part 51 and the heating chamber assembly 41.
The inside of the formic acid hydrogen producing chamber part 51 communicates with the thirteenth port 13a, and formic acid and electrolyte solution enter the inside of the formic acid hydrogen producing chamber part 51, and the formic acid hydrogen producing chamber part 51 is configured such that the formic acid and electrolyte solution therein produce H under the catalysis of the formic acid hydrogen producing catalyst 2 And CO 2 The formic acid hydrogen producing chamber member 51 is provided with a discharge port for discharging the electrolyte solution H 2 And CO 2 And an outlet I in communication with the condensation module 6.
In this embodiment, formic acid is prepared by the cathode electrocatalysis module 2, and the generated formic acid is transported into the formic acid hydrogen producing chamber part 51, and the required H is generated under the action of the formic acid hydrogen producing catalyst in the formic acid hydrogen producing chamber part 51 2 And CO 2 ，CO 2 Can be collected for recycling of the anode electrocatalysis module 1.
Specifically, the above-mentioned formic acid hydrogen producing chamber part 51 includes a formic acid hydrogen producing housing 511, and a first partition plate 512 disposed inside the formic acid hydrogen producing housing 511, the first partition plate 512 dividing the formic acid hydrogen producing chamber part 51 into a first chamber 511a and a second chamber 511b communicating with each other, the first chamber 511a communicating with the thirteenth port 13a, and formic acid being producedThe hydrogen catalyst plate 52 is disposed in the second chamber 511b, and the formic acid and the electrolyte solution flow into the second chamber 511b through the first chamber 511a, and the reaction of the formic acid is catalyzed by the hydrogen-generating catalyst plate 52 to generate H 2 And CO 2 The outlet I is provided in the second chamber 511b.
Preferably, the condensing module 6 includes a condensing chamber member 61 and a heat insulating plate 62, the condensing chamber member 61 is internally provided with a product transfer pipe 63, one end of the product transfer pipe 63 is an inlet J communicating with the outlet I, and the other end is an outlet V communicating with the mixed gas separating chamber module 7. The condensing chamber member 61 is provided with an inlet G communicating with external cooling water and an outlet R for discharging the cooling water.
A heat insulating plate 62 is provided between the condensation chamber member 61 and the formic acid hydrogen producing chamber member 51, the heat insulating plate 62 being configured to block the condensation chamber member 61 from delivering cold air to the formic acid hydrogen producing chamber member 51.
In this embodiment, the electrolyte solution, H 2 And CO 2 Cooling the product in the product conveying pipe 63 to cool the water vapor in the mixture to obtain electrolyte solution and H as final product 2 And CO 2 。
Preferably, the mixed gas separation chamber module 7 includes a mixed gas separation chamber housing 71, and a third gas membrane 72 and a droplet catcher 73 disposed therein, wherein an outlet H, an inlet U communicating with the outlet V, and an outlet P are disposed on the mixed gas separation chamber housing 71.
The third gas diaphragm 72 is provided inside the mixed gas separation chamber housing 71. The third gas diaphragm 72 is provided inside the mixed gas separation chamber housing 71, and is formed into a fifth separation chamber 71a and a sixth separation chamber 71B with the mixed gas separation chamber housing 71, respectively, and an outlet H communicates with the fifth separation chamber 71a at one end and with an inlet B at the other end, and both of the inlet U and the outlet P communicate with the sixth separation chamber 71B.
A droplet catcher 73 is provided in the sixth separation chamber 71b and above the third gas diaphragm 72.
Specifically, the inlet U is located below the outlet P, and the droplet catcher 73 is disposed in the sixth separation chamber 71b above the third gas diaphragm 72, and the droplet catcher 73 is for preventing liquid in the sixth separation chamber 71b from splashing.
The third gas membrane 72 is configured to block the passage of gas and not the passage of liquid, specifically, the electrolyte solution is discharged through the outlet H after entering the fifth separation chamber 71a through the third gas membrane 72, and is again fed to the inlet B by the feeding of the pump to be recycled. H in the sixth separation chamber 71b 2 And CO 2 Is discharged to H through outlet P 2 Within the separation chamber module 8.
Preferably H 2 The separation chamber module 8 includes H 2 A separation chamber housing 81 disposed in parallel with H 2 A first molecular sieve membrane 82 and a second molecular sieve membrane 83 inside the separation chamber housing 81, wherein H 2 The separation chamber housing 81 is provided on one side of the mixed gas separation chamber housing 71.
First molecular sieve membrane 82, second molecular sieve membrane 83 and H 2 The seventh separation chamber 81a, the eighth separation chamber 81b, and the ninth separation chamber 81c are formed in this order between the separation chamber housings 81.
The first molecular sieve membrane 82 is configured to separate H 2 Passing it into a seventh separation chamber 81a, a second molecular sieve membrane 83 configured to separate CO 2 Making it enter the eighth separation chamber 81b.
H 2 The separation chamber housing 81 is provided with a discharge port for discharging H 2 An outlet K communicating with the outlet P, and an outlet T communicating with the outlet C, the outlet K being provided in the seventh separation chamber 81a, the outlet Q being provided in the eighth separation chamber 81b, and the outlet T being provided in the ninth separation chamber 81C.
The first molecular sieve membrane 82 and the second molecular sieve membrane 83 are arranged in parallel along the vertical direction, and H is taken as follows 2 The separation chamber housing 81 is divided into a seventh separation chamber 81a, an eighth separation chamber 81b, and a ninth separation chamber 81c in this order from left to right.
The first molecular sieve membrane 82 is capable of providing H 2 Through the second molecular sieve membrane 83, into the seventh separation chamber 81a and out through the outlet K for CO 2 Through the eighth separation chamber 81b and out through the outlet T which communicates with the inlet C, CO via an external pump 2 Cathode electrocatalytic module 2Recycling again to prepare formic acid and H 2 。
The operation of the apparatus for producing formic acid and hydrogen in this example is as follows:
the electrolyte solution in this example is aqueous KHCO3, which is fed into the whole hydrogen plant by an external pump through inlet port B of electrolyte solution chamber 110 of electrolyte chamber plate 11. A positive voltage is externally applied to the anode conductive sheet 130 of the anode plate 13, and a negative voltage is applied to the cathode conductive sheet 221 of the cathode plate 22. The heating medium is externally supplied to the inlet S heating medium of the heating chamber, and flows out from the outlet F heating medium through the heating pipe 412. Cooling water is added from the outside from an inlet G of the condensing chamber, and then the cooling water is discharged from an outlet R.
Anode cycle: the electrolyte solution is in pure liquid phase from the electrolyte solution chamber 110 of the electrolyte chamber plate 11, the internal liquid is KHCO3, enters the anode plate 13 through the first through hole 1a of the second insulating layer plate 9 and the second through hole 3a, and is uniformly distributed on the whole anode plate 13 through the first grooves 131 on the anode plate 13 and the anode gas diffusion layer plate 15. Oxygen is generated by catalysis of the anode catalyst plate 14, the oxygen and electrolyte are discharged from the third port 4a, enter the separation chamber of the electrolyte chamber plate 11 through the fourth port 2a, are filtered by the first gas membrane 111, electrolyte solution is discharged from the outlet A, are conveyed by the pump and enter the hydrogen production device through the inlet B for the next cycle, and the oxygen is discharged from the outlet L and is collected and utilized.
Cathode cycle: the electrolyte solution passes through the fifth port 5a of the second insulating layer 9, the sixth port 6a of the anode plate 13, the fourteenth port 14a of the anode gas diffusion layer, the seventh port 7a of the anode catalyst, the tenth port 12a of the separator plate 24, the eighth port 8a of the cathode catalyst plate 21, the fifteenth port 15a of the cathode gas diffusion layer 23, the ninth port 9a of the cathode plate 22, and enters the cathode plate 22 from the electrolyte solution chamber 110.
CO 2 Gas enters the cathode plate 22 through the inlet C of the cathode plate 22. Electrolyte solution and CO 2 Is passed through the second grooves 2 on the cathode plate 2220 are uniformly distributed throughout the cathode plate 22 with cathode gas diffusion layers 23. Electrolyte solution and CO are passed through cathode catalyst plate 21 2 Is catalyzed to produce formic acid. Formic acid and electrolyte solution, unreacted complete CO 2 The gas is discharged from the tenth port 10a of the cathode plate 22 and enters CO through the eleventh port 2 A fourth separation chamber 32b of the separation chamber module 3 for separating formic acid and an electrolyte solution from CO through the second gas membrane 32 2 Separating, separating the separated CO 2 Discharged through the outlet O, collected and then enters the cathode plate 22 through the inlet C for cyclic reaction, namely unreacted CO 2 And then enters the inlet C again after passing through the outlet O port, and is recycled.
The separated formic acid and electrolyte solution are discharged from the outlet D and connected with the inlet E of the heating chamber assembly 41 through an external pump, discharged from the thirteenth port 13a after passing through the heating flow passage in the heating chamber housing 411, enter the formic acid catalytic hydrogen production module, namely enter the first chamber 511a of the formic acid hydrogen production chamber member 51, catalyze the formic acid in the mixed solution through the formic acid hydrogen production catalyst in the formic acid catalytic hydrogen production chamber member, and produce H 2 And CO 2 . Electrolyte solution and reaction product H 2 、CO 2 Discharged from the outlet I together, enters the product conveying pipe 63 of the condensing chamber member 61 from the inlet J by an external pump to cool, liquefy the water vapor into liquid water, and then the electrolyte, H 2 、CO 2 Is discharged through the outlet V and enters the first chamber 511a of the mixed gas separation chamber member through the inlet U via the external connection, and the electrolyte solution is discharged through the outlet H and transported through the pump and then enters the hydrogen plant for recycling through the inlet B for the next cycle by filtration through the third gas membrane 72.
H 2 And CO 2 After passing through the droplet catcher 73, the mixed gas is discharged from the outlet P, and enters into H from the inlet Q after being externally connected 2 An eighth separation chamber 81b of the separation chamber member, through the first molecular sieve membrane 82, is filled with H 2 Pass and filter off CO 2 Enters a seventh separation chamber 81a, and filtered H 2 Discharged from the outlet K and collected, and the other part of the gas is separated by a second molecular sieve membrane 83 to make CO 2 By entering the ninth separation chamber 81c, filtered CO 2 Discharged from the outlet T, collected and then enters the cathode plate 22 through the outlet C for cyclic reaction.
The heating module 4 and CO 2 The separation chamber module 3, the formic acid hydrogen production module 5 and the condensation module 6 are a formic acid thermocatalytic hydrogen production cycle, and the cathode electrocatalytic module 2-anode electrocatalytic module 1 is an electrocatalytic CO 2 The formic acid preparation cycle can control the reaction rate through the increase and decrease of the number of the modules, so as to reach the balance of the system.
The whole system is a cycle, through CO 2 Is used for achieving H at low voltage of-0.02V 2 Is produced, CO 2 And electrolyte is not consumed in the whole process, and only water is practically consumed in the whole process. Compared with direct electrolysis of water, the method greatly reduces the consumption of electric energy and avoids the corrosion of alkali liquor or acid liquor to equipment.
It is to be understood that the above examples of the present utility model are provided for clarity of illustration only and are not limiting of the embodiments of the present utility model. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the utility model are desired to be protected by the following claims.
Claims (12)
1. An apparatus for producing formic acid and hydrogen, comprising:
an anode electrocatalyst module (1) having an electrolyte solution chamber (110) and a gas-liquid separation chamber (120) disposed therein for containing an electrolyte solution, the electrolyte solution in the electrolyte solution chamber (110) generating O by the electrocatalyst action of an anode catalyst in the anode electrocatalyst module (1) 2 ；
A first gas membrane (111) is arranged in the gas-liquid separation chamber (120), and the first gas membrane (111) separates the gas-liquid separation chamber (120)Is a first separation chamber (120 a) and is used for containing O 2 The first gas membrane (111) is configured to separate O 2 The electrolyte solution after passing into the first separation chamber (120 a);
the first separation chamber (120 a) is provided with an outlet A for discharging the electrolyte solution, and the second separation chamber (120 b) is provided with an outlet O for discharging the electrolyte solution 2 An outlet L for discharging, the electrolyte solution chamber (110) being provided with an inlet B communicating with the outlet a;
a cathode electrocatalysis module (2) provided with an inlet C, the cathode electrocatalysis module (2) is used for receiving electrolyte solution entering through the anode electrocatalysis module (1), and the inlet C is communicated with CO 2 A source, the cathode electrocatalyst module (2) being configured to cause the electrolyte solution, CO, to be subjected to an electrocatalytic action of a cathode catalyst 2 Producing formic acid;
CO 2 a separation chamber module (3) in internal communication with the cathodic electrocatalytic module (2) configured to receive the formic acid produced, unreacted CO 2 And an electrolyte solution;
the CO 2 The separation chamber module (3) is configured to separate out CO 2 The CO 2 The separation chamber module (3) is provided with an outlet O and an outlet D which are communicated with the inlet C, and the outlet D is configured to discharge separated formic acid and electrolyte solution;
a heating module (4) in communication with the outlet D and configured to heat formic acid and electrolyte solution;
a formic acid hydrogen production module (5) the inside of which is communicated with the heating module (4), the formic acid hydrogen production module (5) being configured to produce H by a formic acid hydrogen production catalyst 2 And CO 2 ；
The formic acid hydrogen production module (5) is provided with a device for discharging the electrolyte solution H 2 And CO 2 Outlet I of (a);
a mixed gas separation chamber module (7) configured to separate an electrolyte solution, H 2 And CO 2 The mixed gas separating chamber module (7) is provided with an inlet U communicated with the outlet I, an outlet H communicated with the inlet B and a supply H 2 And CO 2 An outlet P for discharging;
H 2 a separation chamber module (8) configured to separate H 2 And CO 2 The H is 2 The separation chamber module (8) is provided with an inlet Q communicated with the outlet P and is used for discharging H 2 Is communicated with the inlet C and is used for discharging CO 2 Is provided for the outlet T of (c).
2. The apparatus for preparing formic acid and hydrogen according to claim 1, characterized in that said anodic electrocatalytic module (1) comprises:
The electrolyte solution chamber (110) and the gas-liquid separation chamber (120) are arranged on the electrolyte solution chamber plate (11);
the first insulating layer plate (12) is configured to prevent anode current from passing, a first through hole (1 a) and a fourth through hole (2 a) which are communicated with the electrolyte solution chamber (110) are formed in the first insulating layer plate (12), and the fourth through hole (2 a) is communicated with the gas-liquid separation chamber (120);
the anode plate (13) is provided with first grooves (131) which are uniformly distributed, one end of each first groove (131) is provided with a second port (3 a) communicated with the first port (1 a), and the other end of each first groove is provided with a third port (4 a) communicated with the fourth port (2 a);
the electrolyte solution is able to enter the anode plate (13), the anode catalyst plate (14) electrocatalytic to water within the electrolyte solution to produce O 2 。
3. The apparatus for producing formic acid and hydrogen according to claim 2, wherein the anode electrocatalyst module (1) further comprises an anode gas diffusion layer plate (15) disposed between the anode plate (13) and the anode catalyst plate (14), the anode gas diffusion layer plate (15) being configured to homogenize an electrolyte solution and H 2 Mass transfer and transport between.
4. A plant for the preparation of formic acid and hydrogen according to claim 3, characterized in that said cathodic electrocatalytic module (2) comprises a cathodic catalyst plate (21) and a cathodic plate (22) arranged in succession, said cathodic catalyst plate (21) being arranged on the side close to said anodic catalyst plate (14);
a second groove (220) is formed in the cathode plate (22), a ninth through hole (9 a) is formed in one end of the second groove (220), and a tenth through hole (10 a) is formed in the other end of the second groove;
a fifth through hole (5 a) communicated with the electrolyte solution chamber (110) is formed in the first insulating layer plate (12), a sixth through hole (6 a) communicated with the fifth through hole (5 a) is formed in the anode plate (13), and a seventh through hole (7 a) communicated with the sixth through hole (6 a) is formed in the anode gas diffusion layer plate (15);
an eighth through hole (8 a) communicated with the seventh through hole (7 a) is formed in the cathode catalyst plate (21), the eighth through hole (8 a) is communicated with the ninth through hole (9 a), and the tenth through hole (10 a) is communicated with the CO 2 The inside of the separation chamber module (3).
5. The apparatus for producing formic acid and hydrogen as defined in claim 4, wherein said cathode electrocatalytic module (2) further comprises a cathode gas diffusion layer plate (23) disposed between said cathode plate (22) and said cathode catalyst plate (21), said cathode gas diffusion layer plate (23) being provided with a fifteenth port (15 a) communicating with both said eighth port (8 a) and said ninth port (9 a).
6. The apparatus for producing formic acid and hydrogen as defined by claim 5, wherein said cathode electrocatalytic module (2) further comprises a separator plate (24) disposed between the anode electrocatalytic module (1) and the cathode electrocatalytic module (2), said separator plate (24) being configured to produce O from the anode 2 And H generated by cathode 2 、CO 2 Separately, a twelfth through hole (12 a) is formed in the isolation diaphragm plate (24), and the twelfth through hole (12 a) is communicated with the seventh through hole (7 a) and the eighth through hole (8 a).
7. The apparatus for producing formic acid and hydrogen as defined in claim 6 wherein said CO 2 The separation chamber module (3) comprises CO 2 A separation frame plate (31) and a second gas membrane (32) arranged therein, the second gas membrane (32) being in contact with the CO 2 A third separation chamber (32 a) and a fourth separation chamber (32 b) are respectively formed between the separation frame plates (31), and the fourth separation chamber (32 b) is communicated with the inside of the cathode electrocatalytic module (2);
the second gas membrane (32) is configured to block CO 2 Passing formic acid and electrolyte solution into the third separation chamber (32 a) within the fourth separation chamber (32 b);
the outlet D is provided in the third separation chamber (32 a), and the outlet O is provided in the fourth separation chamber (32 b).
8. The apparatus for producing formic acid and hydrogen as claimed in any one of claims 1 to 7, characterized in that the heating module (4) comprises a heating chamber assembly (41) and a heat insulating layer (42), the heat insulating layer (42) being located in the heating chamber assembly (41) and the CO 2 Between the separation chamber modules (3), the thermal insulation layer (42) is configured to block heat of the heating chamber assembly (41) from the CO 2 A separation chamber module (3) for transfer;
an inlet E communicated with the outlet D is formed in the heating chamber assembly (41), a heating flow passage for introducing a heating medium into the heating chamber assembly (41) is formed in the heating chamber assembly, and an outlet F and an inlet S are formed in one end of the heating flow passage;
a thirteenth through hole (13 a) for passing through formic acid and electrolyte solution and communicated with the formic acid hydrogen production module (5) is arranged in the heating chamber assembly (41).
9. The apparatus for producing formic acid and hydrogen as defined in claim 8, further comprising a condensing module (6), said formic acid hydrogen producing module (5) comprising:
a formic acid hydrogen producing chamber member (51) and a formic acid hydrogen producing catalyst plate (52), the formic acid hydrogen producing catalyst plate (52) being disposed inside the formic acid hydrogen producing chamber member (51) and between the formic acid hydrogen producing chamber member (51) and the heating chamber assembly (41);
The inside of the formic acid hydrogen producing chamber member (51) is communicated with the thirteenth port (13 a), and the formic acid hydrogen producing chamber member (51) is configured such that the formic acid and electrolyte solution therein produce H under the catalysis of the formic acid hydrogen producing catalyst 2 And CO 2 The formic acid hydrogen producing chamber member (51) is provided with a device for discharging electrolyte solution and H 2 And CO 2 And an outlet I communicating with the condensation module (6).
10. The apparatus for producing formic acid and hydrogen according to claim 9, wherein the condensing module (6) comprises:
a condensation chamber (61) in which a product transfer pipe (63) is disposed, one end of the product transfer pipe (63) being an inlet J communicating with the outlet I, and the other end being an outlet V communicating with the mixed gas separation chamber module (7);
an inlet G communicated with external cooling water and an outlet R used for discharging the cooling water are arranged on the condensation chamber piece (61);
a heat insulating plate (62) disposed between the condensation chamber member (61) and the formic acid hydrogen producing chamber member (51), the heat insulating plate (62) being configured to block the condensation chamber member (61) from transmitting cold air to the formic acid hydrogen producing chamber member (51).
11. The apparatus for producing formic acid and hydrogen according to claim 10, wherein the mixed gas separation chamber module (7) comprises:
A mixed gas separating chamber housing (71) provided with an outlet H, an inlet U communicated with the outlet V, and an outlet P;
a third gas diaphragm (72) is provided inside the mixed gas separation chamber housing (71);
the third gas diaphragm (72) is arranged inside the mixed gas separation chamber housing (71), and is respectively formed into a fifth separation chamber (71 a) and a sixth separation chamber (71B) with the mixed gas separation chamber housing (71), one end of the outlet H is communicated with the fifth separation chamber (71 a), the other end of the outlet H is communicated with the inlet B, and the inlet U and the outlet P are communicated with the sixth separation chamber (71B);
and a droplet catcher (73) which is provided in the sixth separation chamber (71 b) and is positioned above the third gas diaphragm (72).
12. The apparatus for producing formic acid and hydrogen as defined in claim 11 wherein said H 2 The separation chamber module (8) comprises:
H 2 a separation chamber housing (81) provided on one side of the mixed gas separation chamber housing (71);
a first molecular sieve membrane (82) and a second molecular sieve membrane (83) which are arranged in parallel are arranged on the H 2 An interior of the separation chamber housing (81);
the first molecular sieve membrane (82), the second molecular sieve membrane (83) and the H 2 A seventh separation chamber (81 a), an eighth separation chamber (81 b) and a ninth separation chamber (81 c) are sequentially formed between the separation chamber housings (81);
the first molecular sieve membrane (82) is configured to separate H 2 Passing it into the seventh separation chamber (81 a), the second molecular sieve membrane (83) being configured to separate CO 2 Passing it into the eighth separation chamber (81 b);
the H is 2 The separation chamber housing (81) is provided with a device for discharging H 2 An outlet K communicating with the outlet P, and an outlet T communicating with the outlet C, the outlet K being provided in the seventh separation chamber (81 a), the outlet Q being provided in the eighth separation chamber (81 b), and the outlet T being provided in the ninth separation chamber (81C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320315040.XU CN219886195U (en) | 2023-02-24 | 2023-02-24 | Device for preparing formic acid and hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202320315040.XU CN219886195U (en) | 2023-02-24 | 2023-02-24 | Device for preparing formic acid and hydrogen |
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| CN219886195U true CN219886195U (en) | 2023-10-24 |
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| CN202320315040.XU Active CN219886195U (en) | 2023-02-24 | 2023-02-24 | Device for preparing formic acid and hydrogen |
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