CN207699678U - A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes - Google Patents

A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes Download PDF

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Publication number
CN207699678U
CN207699678U CN201721406758.0U CN201721406758U CN207699678U CN 207699678 U CN207699678 U CN 207699678U CN 201721406758 U CN201721406758 U CN 201721406758U CN 207699678 U CN207699678 U CN 207699678U
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plate
flow
reaction solution
gas
runner
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隋升
孙志刚
柳杨
冯亮杰
曹孟常
邢涛
向康
杨宏泉
郭强
蒋超
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Shanghai Jiaotong University
Sinopec Engineering Group Co Ltd
Sinopec Ningbo Engineering Co Ltd
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Shanghai Jiaotong University
Sinopec Engineering Group Co Ltd
Sinopec Ningbo Engineering Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The utility model is related to a kind of hydrogen manufacturing electrolyzers of oxidation solution containing carbon pastes, including Hydrogen Unit (10), it is characterised in that the Hydrogen Unit (10) includes the anode plate (5) being tightly connected successively, flow-field plate (4), half membrane electrode (3), hydrophobic carbon paper sum aggregate gas plate (1) along the flow direction of reaction solution;Wherein, the flow-field plate (4) is equipped with reaction solution runner (41), the entrance connection reaction solution source of the reaction solution runner (41), the outlet of the reaction solution runner (41) connects out-of-bounds, and the reaction solution runner (41) penetrates through the flow-field plate (4);The gas collection plate (1) is equipped with gas flow (11), gas flow (11) the connection gas collecting tube (6);The gas collection plate (1), half membrane electrode (3), flow-field plate (4) and anode plate (5) are sequentially connected electrically;The gas collection plate (1) connects power cathode by negative electrode collector plate (71), and the anode plate (5) connects positive pole by positive electrode current collecting plate (72).

Description

A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes
Technical field
The utility model is related to arrive coal hydrogen preparation field, a kind of direct hydrogen production electrolyzer of oxidation solution containing carbon pastes is referred specifically to.
Background technology
World's coal storage is abundant, and coal is considered as the obtainable most cheap energy on the earth, for a long time in the energy It is occupied an important position in consumption, but thus also brings and the air pollution greatly damaged and titanium dioxide are caused to environment and ecology Carbon emission problem.Equally, coal accounting example in the consumption of China's primary energy is up to 75%, and that there is utilization ratios is low, Waste the problems such as serious.Consideration based on environmental protection and future source of energy safety is studied novel coal utilization mode and is carried High coal utilization efficiency has great positive effect.
CN201310096085.3 is disclosed《A kind of process producing purified hydrogen and carbon dioxide from coal》, use Oxidant chemical oxidation coal dust slurries generate carbon dioxide, and the reduction-state oxidant then generated is again by electrochemical oxidation Restore regeneration, and generates hydrogen.In the process of the present invention, the chemical oxidation and oxidant electrochemical oxidation of coal dust slurries Regeneration carries out in closed reaction kettle and electrochemical reaction cell respectively:Coal dust is in aqueous sulfuric acid by ferric ion oxygen Change, ferric ion, which then restores, becomes ferrous ion, and ferrous ion converts (regeneration) at three in electrochemical reaction cell again Valence iron ion, to realize that oxidant recycles.This technique avoids coal particles can wear noble metal electrode, causes to produce hydrogen It is of high cost;It is solid phase-solid phase reaction between electrode and pulverized coal particle, reaction rate is extremely low, and current density is usually no more than 10mA/ cm2, can not industrialized production.But electrolyzer used in this application is by anode chamber, the matter of cathode chamber and folder between the chambers Proton exchange is constituted, and when work, anode chamber and cathode chamber will have electrolyte, with the progress of reaction, reactant in electrolyte Concentration declines, and reaction rate declines therewith;Anode and cathode increases the resistance of ionic conduction, reduces electric energy apart from larger Utilization ratio and hydrogen-producing speed.
Invention content
Technical problem to be solved in the utility model is provided and a kind of efficiently and is avoided that for the present situation of the prior art Anode catalyst abrasion, the hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes for being easy to industrialized production.
Technical solution is used by the utility model solves above-mentioned technical problem:This contains carbon pastes oxidation solution hydrogen manufacturing electricity consumption Solve device, including Hydrogen Unit, it is characterised in that the Hydrogen Unit includes the anode being tightly connected successively along the flow direction of reaction solution Plate, flow-field plate, membrane electrode, hydrophobic carbon paper sum aggregate gas plate;
Wherein, the flow-field plate is equipped with reaction solution runner, and the entrance connection reaction solution feed liquor of the reaction solution runner is total Pipeline, the outlet connection go out liquid house steward road of the reaction solution runner, and the reaction solution total pipeline penetrates through the flow-field plate;
The gas collection plate is equipped with gas flow, and the gas flow is connected to gas collection total pipeline;
The gas collection plate, half membrane electrode, flow-field plate and anode plate are sequentially connected electrically;
The gas collection plate connects power cathode by negative electrode collector plate, and the anode plate connects power supply by positive electrode current collecting plate Anode.
The reaction solution runner snakelike arrangement in the flow-field plate;Or the reaction solution runner has a plurality of parallel cloth It sets;
The width of the reaction solution runner is 3~6mm, depth is 3~8mm.
The gas flow is elongated runner, and the surface serpentine along the gas collection plate is arranged, the width of the gas flow Degree is 1~3mm, and depth is 1~2mm.
The Hydrogen Unit has multiple, and each Hydrogen Unit is sequentially connected in series arrangement;
Positive electrode current collecting plate connection is positioned at the anode plate of the Hydrogen Unit of upstream, and negative electrode collector plate connection is positioned at downstream The gas collection plate of Hydrogen Unit;The negative electrode collector plate connects power cathode, and the positive electrode current collecting plate connects positive pole;And And the outside of the positive electrode current collecting plate connects the first insulating end plate, the outside of the negative electrode collector plate connects the second insulating end plate.
The gas collection plate is graphite cake, and flow-field plate is titanium plate.
The entrance of the reaction solution runner is located at the lower part of the flow-field plate, and the outlet of the reaction solution runner is positioned at described The top of flow-field plate;The gas collecting tube is located at the top of the gas flow.
The lower part of the gas flow is also associated with drain pipe.
The preparation method of half membrane electrode is as follows:
Pt/C catalyst, proton conductor resinoid bond and polytetrafluoroethylene (PTFE) dispersion emulsion are pressed into 75-85:10-20:3-10 Weight ratio is added in dispersant, is uniformly mixed, is configured to slurry;
The dispersant is the mixture of water, ethyl alcohol and isopropanol;
The slurry is coated in and forms electrode layer that thickness is 5-15 microns on dielectric film to get to half film Electrode;
Alternatively, the slurry is coated on polytetrafluoroethylene film, membrane stratiform electrode is formed, is then transferred to electrolyte again On film, electrode layer that thickness is 5-15 microns is formed to get to half membrane electrode.
The dielectric film preferably is selected from perfluorosulfonic acid proton exchange film or polybenzimidazole membrane.
Compared with prior art, electrolyzer provided by the utility model can be carried out directly to containing carbon pastes oxidation solution Electrolytic hydrogen production, the only cyclic oxidation agent solution in electrolyzer, the abrasion so as to avoid coal particle to catalyst electrode, reactor Service life is long, and production efficiency is high, is 5-12 times of the prior art, and operating cost reduces, environmental-friendly, cleanliness without any pollution.
Electrolyzer provided by the utility model is especially suitable for processing coal slurry, biomass slurry and/or sludge slurry.
Description of the drawings
Fig. 1 is the stereoscopic schematic diagram of the utility model embodiment assembling structure;
Fig. 2 is the decomposition diagram of Fig. 1;
Fig. 3 is the stereoscopic schematic diagram of gas collection plate in the utility model embodiment;
Fig. 4 is the stereoscopic schematic diagram of flow-field plate in the utility model embodiment.
Fig. 5 is the longitudinal sectional view along gas collecting tube axis in Fig. 1;
Fig. 6 is the longitudinal sectional view along inlet tube axis in Fig. 1.
Specific implementation mode
The utility model is described in further detail below in conjunction with attached drawing embodiment.
As shown in Figures 1 to 6, this contains carbon pastes oxidation solution hydrogen manufacturing and includes with electrolyzer:
Hydrogen Unit 10, has multiple, shows that three Hydrogen Units are sequentially connected in series in figure;Each Hydrogen Unit is along reaction solution Flow direction includes anode plate 5, flow-field plate 4, half membrane electrode 3, hydrophobic carbon paper (not shown) and the gas collection being tightly connected successively Plate 1;And gas collection plate 1, half membrane electrode 3, flow-field plate 4 and anode plate 5 are sequentially connected electrically.Gas collection plate 1 uses stone in the present embodiment Prepared by black plate, flow-field plate 4 is prepared using titanium plate.
Wherein, flow-field plate 4 is equipped with reaction solution runner 41, and the snakelike coiling in flow-field plate 4 of reaction solution runner 41 is arranged, instead It is entrance to answer the lower port in liquid stream road 41, and reaction solution source is connected by inlet connection 42;The upper port of reaction solution runner 41 For outlet, out-of-bounds downstream is connected by discharge connection 43;And reaction solution runner 41 penetrates through flow-field plate 4, i.e. reaction solution runner 41 Flow-field plate 4 is set to form engraved structure.In the present embodiment the width of reaction solution runner 41 be 5mm, depth 5mm.
Reaction solution runner 41 in the present embodiment has a plurality of, is arranged in parallel successively, and lower port 44 is connected to the total runner of feed liquor, The total runner of feed liquor connects inlet connection 42, and port 45 is connected to out the total runner of liquid thereon, goes out the total runner connection outlet take over of liquid 43.
Gas collection plate 1 is equipped with gas flow 11, and gas flow 11 is connected to gas collecting tube 6;Gas flow 11 is elongated runner, Setting is bent along the surface of gas collection plate 1, the width of gas flow 11 is 2mm, depth 1.5mm.The upper port of gas flow 11 12 connection gas collecting tubes 6, for collecting and drawing the hydrogen in gas flow 11;Gas flow 11 in the present embodiment have it is a plurality of, It is arranged in parallel successively;The lower port 13 of gas flow 11 is connected with drain pipe 8, for issuable in exhaust gas flowpath 11 Raffinate.
Negative plate 71 for connecting power cathode and the positive plate 72 for connecting positive pole are separately connected both ends Gas collection plate 1 and anode plate 5 on Hydrogen Unit;And the outside of negative plate 71 and positive plate 72 is separately connected insulating end plate.This reality It includes end plate 74 and the insulation board 73 positioned at 74 inside of end plate to apply the insulating end plate in example.
Anode plate 5 is titanium mesh, and physically or electrically chemical method depositing noble metal or precious metal alloys are used on surface; Noble metal is golden (Au), platinum (Pt), iridium (Ir), rhodium (at least one of Rh), Palladium (Pd) and ruthenium (Ru).
In the present embodiment, the preparation method of half membrane electrode 3 is as follows:
Pt/C catalyst, proton conductor resinoid bond and polytetrafluoroethylene (PTFE) dispersion emulsion are pressed 80:15:5 weight ratios add Enter into dispersant, is uniformly mixed, is configured to slurry;Proton conductor resinoid bond selects Nafion dispersion liquids.
The dispersant is the mixture of water, ethyl alcohol and isopropanol;The proportioning of three be water 1~5, ethyl alcohol 10~30, Remaining is isopropanol.
Slurry is sprayed on a side surface of dielectric film, forms electrode layer that thickness is 10 microns to get to described Half membrane electrode.Electrode layer is towards hydrophobic carbon paper.
Slurry can also be directly printed onto using silk screen print method on dielectric film;Or slurry can also be coated in poly- On tetrafluoroethylene, membrane stratiform electrode is formed, is then transferred on dielectric film again, forms the electrode that thickness is 5-15 microns Layer is to get to half membrane electrode.
Dielectric film in the present embodiment selects perfluorosulfonic acid proton exchange film.
Explanation uses the process for making hydrogen of the coal slurry electrolyzer by taking coal slurry oxidation solution as an example, specific as follows:
Coal slurry oxidation solution is pumped into inlet connection, is distributed via inlet connection, into the reaction solution of each Hydrogen Unit In runner, under pressure along reaction solution flow passage.Due to flow-field plate hollow out, the one side of reaction solution runner is located next to The dielectric film of half membrane electrode is close in anode plate, another side.Fe in coal slurry oxidation solution2+It is aoxidized back on anode plate Fe3+, the H in oxidation solution+Electrolyzer cathode chamber is then entered by half membrane electrode, hydrogen is reduced on cathode.The hydrogen of generation Gas penetrates hydrophobic carbon paper, diffuses into gas flow, then electrolyzer is discharged by gas collecting tube.
Since solid particle being not present in coal slurry oxidation solution, so blockage problem is not present in anode liquid runner, also need not Worry that the noble metal catalyst on anode plate is worn, reaction solution runner is made wide and shallow a, side as far as possible according to actual needs Face can increase the contact area of liquid and electrode to improve hydrogen-producing speed, on the other hand reduce anode at a distance from cathode from And reduce energy loss.

Claims (9)

1. a kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes, including Hydrogen Unit (10), it is characterised in that the Hydrogen Unit (10) include anode plate (5), flow-field plate (4), half membrane electrode (3), the hydrophobic carbon paper being tightly connected successively along the flow direction of reaction solution With gas collection plate (1);
Wherein, the flow-field plate (4) is equipped with reaction solution runner (41), and the entrance of the reaction solution runner (41) connects reaction solution The outlet in source, the reaction solution runner (41) connects out-of-bounds, and the reaction solution runner (41) penetrates through the flow-field plate (4);
The gas collection plate (1) is equipped with gas flow (11), gas flow (11) the connection gas collecting tube (6);
The gas collection plate (1), half membrane electrode (3), flow-field plate (4) and anode plate (5) are sequentially connected electrically;
The gas collection plate (1) connects power cathode by negative electrode collector plate (71), and the anode plate (5) passes through positive electrode current collecting plate (72) positive pole is connected.
2. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 1, it is characterised in that the reaction solution runner (41) the snakelike arrangement in the flow-field plate (4);Or the reaction solution runner (41) has a plurality of and is arranged in parallel;
The width of the reaction solution runner (41) is 3~6mm, depth is 3~8mm.
3. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 2, it is characterised in that the gas flow (11) it is elongated runner, the surface serpentine along the gas collection plate (1) is arranged, and the width of the gas flow (11) is 1~ 3mm, depth are 1~2mm.
4. the hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes according to claims 1 to 3 any claim, it is characterised in that The Hydrogen Unit has multiple, and each Hydrogen Unit is sequentially connected in series arrangement;
Positive electrode current collecting plate (72) connects the anode plate (5) in the Hydrogen Unit of upstream, and negative electrode collector plate (71) connects downstream hydrogen manufacturing list Gas collection plate (1) in member;And the outside of the positive electrode current collecting plate (72) connects the first insulating end plate, the negative electrode collector plate (71) outside connects the second insulating end plate.
5. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 4, it is characterised in that the gas collection plate (1) is Graphite cake, the flow-field plate (4) are titanium plate.
6. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 5, it is characterised in that the reaction solution runner (41) entrance is located at the lower part of the flow-field plate (4), and the outlet of the reaction solution runner (41) is located at the flow-field plate (4) Top;The gas collecting tube (6) is located at the top of the gas flow (11).
7. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 4, it is characterised in that the gas flow (11) lower part is also associated with drain pipe (8).
8. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 1, it is characterised in that half membrane electrode (3) Preparation method it is as follows:
Pt/C catalyst, proton conductor resinoid bond and polytetrafluoroethylene (PTFE) dispersion emulsion are pressed into 75-85:10-20:3-10 weights Amount ratio is added in dispersant, is uniformly mixed, and slurry is prepared;
The dispersant is the mixture of water, ethyl alcohol and isopropanol;
The slurry is coated in and forms electrode layer that thickness is 5-15 microns on dielectric film to get to the membrane electrode (3);
Alternatively, the slurry is coated on polytetrafluoroethylene film, film layer electrode is formed, is then transferred on dielectric film again, Electrode layer that thickness is 5-15 microns is formed to get to the membrane electrode (3).
9. the hydrogen manufacturing of oxidation solution containing carbon pastes electrolyzer according to claim 8, it is characterised in that the dielectric film choosing From perfluorosulfonic acid proton exchange film or polybenzimidazole membrane.
CN201721406758.0U 2017-10-27 2017-10-27 A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes Active CN207699678U (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107893238A (en) * 2017-10-27 2018-04-10 中石化宁波工程有限公司 A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107893238A (en) * 2017-10-27 2018-04-10 中石化宁波工程有限公司 A kind of hydrogen manufacturing electrolyzer of oxidation solution containing carbon pastes

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