CN1044626C - Split circulation hydrolytic hydrogen-making technology and equipment thereof - Google Patents

Split circulation hydrolytic hydrogen-making technology and equipment thereof Download PDF

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Publication number
CN1044626C
CN1044626C CN95116125A CN95116125A CN1044626C CN 1044626 C CN1044626 C CN 1044626C CN 95116125 A CN95116125 A CN 95116125A CN 95116125 A CN95116125 A CN 95116125A CN 1044626 C CN1044626 C CN 1044626C
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oxygen
hydrogen
electrolyzer
liquid
separator
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CN1129261A (en
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许俊明
邓宏顺
郭建富
魏志昆
要振祥
王建峰
赵迎春
许卫
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Tianjin Mainland Hydrogen Equipment Co Ltd
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The present invention discloses a split circulation hydrolytic hydrogen making process and equipment thereof. The present invention is characterized in that in an electrolytic process, electrolytic solution containing hydrogen and electrolytic solution containing oxygen are separated, the electrolytic solution containing hydrogen is processed by independent filtration and cooling and is pumped back to a hydrogen side chamber of an electrolytic tank, electrolytic solution containing oxygen is processed by independent filtration and cooling and is pumped back to an oxygen side chamber of the electrolytic tank, the independent hydrogen side circulation and the independent oxygen side circulation of the electrolytic solution containing hydrogen and the electrolytic solution containing oxygen are formed. The present invention has the advantages that the produced gas purity is high, the hydrogen gas purity is not less than 99.9%, and the oxygen gas purity is not less than 99.5%, the energy consumption of direct current is low, the circulation speed is high, and the service life is long.

Description

Discrete circulating water electrolytic process for making hydrogen and equipment
What the present invention relates to is discrete circulating water electrolytic process for making hydrogen and the employed equipment of this technology, belongs to the water electrolysis hydrogen producing technical field.
In the prior art, water electrolysis hydrogen producing all is to adopt hybrid technical process, be the main frame of electrolytic solution in water electrolysis hydrogen producing equipment--in the electrolyzer, contain liquid hydrogen gas and oxygen at negative electrode cell (hydrogen side cell) and anode cell (oxygen lateral cell) output respectively under the direct current effect, electrolysis produces contains liquid hydrogen gas and contains liquid oxygen gas and hydrogen, carrier of oxygen are separated with circulation alkali liquor with oxygen separator through hydrogen separator respectively; Hydrogen after the separation and oxygen enters the cooling of hydrogen comprehensive tower and oxygen comprehensive tower respectively, catch and export to the user after dripping; After isolating two-way raffinate (catholyte and the anolyte) mixing of hydrogen and oxygen, after through filter and water cooler, filtering, cooling off, the blowback electrolyzer is interior as the electrolysis of circular electrolyte participation next round again.The main deficiency of prior art is: in hybrid circulation process, the mixing raffinate of isolating hydrogen and oxygen returns the hydrogen side cell and the oxygen lateral cell of electrolyzer, hydrogen and oxygen remaining in the electrolytic solution that returns can discharge under action of high temperature, simultaneously, because the decline of flow velocity, hydrogen of carrying secretly in the electrolytic solution and oxygen can further be separated, the hydrogen that produces after these gases and the electrolysis, oxygen mix together, thereby cause the hydrogen exported and the reduction of oxygen purity, the output hydrogen purity is 99.6%-99.8%, and the output oxygen purity is 99.0%-99.2%; In the mixed cycle flow process, the circulation of elecrolyte flow can not be too big, otherwise the separating effect of hydrogen, oxygen separator is descended, thereby cause gas purity further to reduce; The increase of circulation of elecrolyte amount is restricted, and also easily causes each electrolytic chamber's non-uniform temperature, and the electrolyzer direct current consumption is increased, and general hybrid circulating consumption is: 4.5-5.0kWh/m 3H 2
April 6 nineteen eighty-two, disclosed US4323442 patent also provided a kind of anolyte loop, the technology that catholyte loop is provided with respectively, this technology by in the electrolyzer downstream one control a certain amount of catholyte loop alkaline stream anode liquid loop with catholyte flow director coupled anolyte flow director, or the device pneumatic outlet be equipped with by differential pressure transmitter, the variable valve of setter control makes a little higher than anolyte loop pressure of catholyte loop pressure, be convenient to the electrolyzer electrolyte inside and partly be penetrated into corresponding anolyte compartment by each cathode compartment, with the holding anode liquid proportion close with catholyte by barrier film.This patent need add flow director or pressure unit, differential pressure transmitter and flow-compensated device for making catholyte flow to the anode cell, has that sports equipment is many, a complex structure, shortcoming that reliability is low.
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of realize catholyte and simple and easy to do technical process and the equipment of anolyte difference round-robin in the whole electrolyte circulation system are proposed, various flow controls or differential pressure control device are not set, can solve catholyte and anolyte proportion inequality, carry the problem with dissolved hydrogen, carrier of oxygen secretly, the hydrogen of output, the purity of carrier of oxygen are improved greatly, power consumption descends, and device structure is simple, and cost is low.
The object of the present invention is achieved like this, and technological process of the present invention is: electrolytic solution is electrolysis in electrolyzer, and electrolysis produces and contains liquid hydrogen gas and contain liquid oxygen gas; Contain liquid hydrogen gas and produce hydrogen and hydrogeneous raffinate, contain liquid oxygen gas and produce oxygen and contain the oxygen raffinate through separating through separating; Hydrogeneous raffinate passes through the hydrogen side cell of independent filtration and process of cooling blowback electrolyzer separately, contain the oxygen lateral cell that the oxygen raffinate passes through independent filtration and process of cooling blowback electrolyzer separately, form hydrogeneous electrolytic solution thus and contain independently circulation of hydrogen side and the working cycle of oxygen side separately of oxygen electrolytic solution, have migration tube to be connected between oxygen separator and the hydrogen separator.
The equipment flowsheet of this technological process comprises electrolyzer 1, hydrogen separator 2, hydrogen comprehensive tower 3, oxygen separator 4, oxygen comprehensive tower 5, hydrogen side pump 6, hydrogen side strainer 7, hydrogen side water cooler 8, oxygen side pump 9, oxygen side strainer 10 and oxygen side water cooler 11 as shown in Figure 1.The hydrogen output tube of electrolyzer connects hydrogen separator, and the hydrogen output tube of hydrogen separator is connected with the hydrogen comprehensive tower, and hydrogen is by 12 outputs of the hydrogen output tube on the hydrogen comprehensive tower; The oxygen output tube of electrolyzer connects oxygen separator, and the oxygen output tube of oxygen separator is connected with the oxygen comprehensive tower, and oxygen is by 13 outputs of the oxygen output tube on the oxygen comprehensive tower; Hydrogen side pump, hydrogen side strainer that the return line 14 hydrogeneous alkali lye of process (electrolytic solution) of hydrogen separator use separately return liquid mouth 15 with hydrogen side water cooler with the hydrogen side of electrolyzer and are connected, and the return line 16 of oxygen separator returns liquid mouth 17 with oxygen side water cooler with the oxygen side of electrolyzer through oxygen side pump, the oxygen side strainer that contains the independent use of oxonium base liquid (electrolytic solution) and is connected; Between oxygen separator and hydrogen separator, be connected to migration tube 18.
Because the present invention adopted above-mentioned discrete circulating water electrolytic hydrogen producing technology, its major advantage is: 1. output gas purity height, hydrogen purity 〉=99.9%, oxygen purity 〉=99.5%; 2. direct current energy consumption is low, is generally 4.3-4.8kWh/m 3H 23. speed of circulation is fast, than the fast 2-3 of hybrid recycle unit doubly, and saves water coolant 20%-30%; 4. each electrolytic chamber's temperature of electrolyzer is even, long service life, and the time between overhaul is average more than 10 years.
The drawing of accompanying drawing of the present invention is described as follows:
Fig. 1 is a processing unit schema of the present invention;
Fig. 2 is the synoptic diagram of electrolyzer of the present invention;
Fig. 3 is the side-view of electrolyzer of the present invention;
Fig. 4 is the sectional view of electrolyzer of the present invention;
Fig. 5 is the pole plate synoptic diagram of electrolyzer;
Fig. 6 is the sectional view of the pole plate of electrolyzer;
Fig. 7 is the middle plate synoptic diagram of electrolyzer.
The invention will be further described below in conjunction with embodiment and accompanying drawing.In an embodiment, electrolyzer is made of end pole plate 19, diaphragm pad 20, pole plate 21, middle plate 22 shown in Fig. 2,3.Pole plate as shown in Figure 5 and Figure 6, the middle part is divided into hydrogen side cell 24 and oxygen lateral cell 25 by division plate 23 with cavity; The hydrogen delivery outlet 26 and the hydrogen side liquid hole 27 that communicate with hydrogen side cell are arranged on the frame of pole plate, the oxygen delivery outlet 28 and the oxygen side liquid hole 29 that communicate with oxygen lateral cell are arranged on the frame of pole plate, have on the frame of pole plate the hydrogen side liquid backflow hole 31 that communicates with hydrogeneous electrolyte cavities 30 on the middle plate and with middle plate on contain the oxygen side liquid backflow hole 33 that oxygen electrolyte cavities 32 communicates.Diaphragm pad is the thin slice that has hydrogen delivery outlet, hydrogen side liquid hole, oxygen delivery outlet, oxygen side liquid hole, hydrogen side liquid backflow hole and oxygen side liquid backflow hole.Middle plate is a flat cavity that hydrogeneous electrolyte cavities is arranged, and the oxygen of containing electrolyte cavities is arranged in hydrogeneous electrolyte cavities, has hydrogen side liquid hole and hydrogen side liquid backflow hole on the hydrogeneous electrolyte cavities, contains aerobic side liquid hole and oxygen side liquid backflow hole on the oxygen electrolyte cavities.The end pole plate is the plate body that has hydrogen delivery outlet, oxygen delivery outlet, hydrogen side liquid backflow hole and oxygen side liquid backflow hole.End pole plate and middle plate and the stacked fastening formation electrolyzer of separately multi-disc pole plate, diaphragm pad, the hydrogen delivery outlet on the electrolyzer end pole plate, oxygen delivery outlet, hydrogen side liquid backflow hole and oxygen side liquid backflow hole return the liquid mouth as hydrogen delivery port, oxygen delivery port, the hydrogen side of electrolyzer and return the liquid mouth with the oxygen side and be connected with external system respectively.

Claims (3)

1, a kind of discrete circulating water electrolytic process for making hydrogen, the electrolysis in electrolyzer of its electrolytic solution, electrolysis produces and contains liquid hydrogen gas and contain liquid oxygen gas, contain liquid hydrogen gas and produce hydrogen and hydrogeneous raffinate through separating, containing liquid oxygen gas produces oxygen and contains the oxygen raffinate through separating, raffinate after filtration, cooling back blowback electrolyzer, hydrogeneous raffinate and contain the oxygen raffinate separately, it is characterized in that: hydrogeneous raffinate passes through the hydrogen side cell of independent filtration and process of cooling blowback electrolyzer separately, contain the oxygen lateral cell that the oxygen raffinate passes through independent filtration and process of cooling blowback electrolyzer separately, form hydrogeneous electrolytic solution and contain independently circulation of hydrogen side and the working cycle of oxygen side separately of oxygen electrolytic solution, have migration tube to be connected between oxygen separator and the hydrogen separator.
2, a kind of discrete circulating water electrolytic hydrogen producer comprises electrolyzer, hydrogen separator, hydrogen comprehensive tower, oxygen separator, oxygen comprehensive tower, pump, strainer and water cooler; The hydrogen output tube of electrolyzer connects hydrogen separator, the hydrogen output tube of hydrogen separator is connected with the hydrogen comprehensive tower, hydrogen is by the hydrogen output tube on hydrogen comprehensive tower output, and the electrolytic solution in the hydrogen separator returns the liquid import by return line via what pump, strainer and water cooler flowed back to electrolyzer; The oxygen output tube of electrolyzer connects oxygen separator, the oxygen output tube of oxygen separator is connected with the oxygen comprehensive tower, oxygen is exported by the oxygen output tube on the oxygen comprehensive tower, electrolytic solution in the oxygen separator returns the liquid import by return line via what pump, strainer and water cooler flowed back to electrolyzer, the liquid import of returning of electrolyzer is divided into that separate hydrogen side is returned the liquid mouth and the oxygen side is returned the liquid mouth, it is characterized in that: hydrogen side pump, hydrogen side strainer that the return line of hydrogen separator uses separately through hydrogeneous electrolytic solution return the liquid mouth with hydrogen side water cooler with the hydrogen side of electrolyzer and are connected; The return line of oxygen separator returns liquid mouth with oxygen side water cooler with the oxygen side of electrolyzer through oxygen side pump, the oxygen side strainer that contains the independent use of oxonium base liquid and is connected, and is connected to migration tube between oxygen separator and hydrogen separator.
3, according to the described discrete circulating water electrolytic of claim 2 hydrogen producer, it is characterized in that: electrolyzer is made of end pole plate, diaphragm pad, pole plate and middle plate; Above-mentioned pole plate middle part is divided into hydrogen side cell and oxygen lateral cell by division plate with cavity, the hydrogen delivery outlet and the hydrogen side liquid hole that communicate with hydrogen side cell are arranged on the frame of pole plate, the oxygen delivery outlet and the oxygen side liquid hole that communicate with oxygen lateral cell are arranged on the pole plate frame, also have on the frame of pole plate the hydrogen side liquid backflow hole that communicates with hydrogeneous electrolyte cavities on the middle plate and with middle plate on contain the oxygen side liquid backflow hole that the oxygen electrolyte cavities communicates; Above-mentioned diaphragm pad is the thin slice that has hydrogen delivery outlet, hydrogen side liquid hole, oxygen delivery outlet, oxygen side liquid hole, hydrogen side liquid backflow hole and oxygen side liquid backflow hole; Above-mentioned middle plate is a flat cavity that hydrogeneous electrolyte cavities is arranged, and the oxygen of containing electrolyte cavities is arranged in hydrogeneous electrolyte cavities, and hydrogen side liquid hole and hydrogen side liquid backflow hole are arranged on the hydrogeneous electrolyte cavities, contains aerobic side liquid hole and oxygen side liquid backflow hole on the oxygen electrolyte cavities; Above-mentioned end pole plate is the plate body that has hydrogen delivery outlet, oxygen delivery outlet, hydrogen side liquid backflow hole and oxygen side liquid backflow hole; End pole plate and middle plate and the stacked fastening formation electrolyzer of separately multi-disc pole plate, diaphragm pad.
CN95116125A 1995-09-30 1995-09-30 Split circulation hydrolytic hydrogen-making technology and equipment thereof Expired - Lifetime CN1044626C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2377972T3 (en) * 2010-04-19 2014-08-29 H Tec Systems Gmbh Device for electric generation of hydrogen
CN103046068B (en) * 2013-01-08 2015-06-17 陕西华秦新能源科技有限责任公司 Combined inner and outer air-cooling hydrogen production electrolyzer by water electrolysis
JP6588768B2 (en) * 2015-08-20 2019-10-09 デノラ・ペルメレック株式会社 Electrolysis apparatus and electrolysis method
JP6955031B2 (en) * 2017-04-24 2021-10-27 ヘラー・エレクトロライザー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＨｏｅｌｌｅｒ Ｅｌｅｃｔｒｏｌｙｚｅｒ ＧｍｂＨ How to operate a water electrolyzer
US11505872B2 (en) * 2018-07-27 2022-11-22 Tokuyama Corporation Gas production apparatus and gas production method
CN112458488B (en) * 2020-10-27 2023-02-17 中国船舶重工集团公司第七一八研究所 Water-cooled electrolytic cell polar plate
CN113430534B (en) * 2021-06-23 2022-04-08 阳光电源股份有限公司 Hydrogen production method, hydrogen production system, hydrogen production electrolyte circulation method and hydrogen production electrolyte circulation device
CN114525520B (en) * 2022-03-07 2024-01-30 阳光氢能科技有限公司 Hydrogen production system hot standby control method and hydrogen production system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2549471A1 (en) * 1975-11-05 1977-05-12 Dornier System Gmbh Electrolysis of water at high temps. to produce hydrogen - using superheated steam for reduced electricity usage
US4323442A (en) * 1979-07-05 1982-04-06 Creusot-Loire Electrolysis installation for the production of gas
CN1051401A (en) * 1990-09-03 1991-05-15 张学明 High-efficient electrolytic apparatus for producing hydrogen and oxygen
CN1092478A (en) * 1993-02-22 1994-09-21 日本英泰克株式会社 Electrolyzed water producing method and device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2549471A1 (en) * 1975-11-05 1977-05-12 Dornier System Gmbh Electrolysis of water at high temps. to produce hydrogen - using superheated steam for reduced electricity usage
US4323442A (en) * 1979-07-05 1982-04-06 Creusot-Loire Electrolysis installation for the production of gas
CN1051401A (en) * 1990-09-03 1991-05-15 张学明 High-efficient electrolytic apparatus for producing hydrogen and oxygen
CN1092478A (en) * 1993-02-22 1994-09-21 日本英泰克株式会社 Electrolyzed water producing method and device thereof

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