CN105154907A - System and method for preparing oxygen by electrolyzing water based on solid oxide electrolyte - Google Patents
System and method for preparing oxygen by electrolyzing water based on solid oxide electrolyte Download PDFInfo
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- CN105154907A CN105154907A CN201510609573.9A CN201510609573A CN105154907A CN 105154907 A CN105154907 A CN 105154907A CN 201510609573 A CN201510609573 A CN 201510609573A CN 105154907 A CN105154907 A CN 105154907A
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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
-
- 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
- Y02E60/50—Fuel cells
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a system and a method for preparing oxygen by electrolyzing water based on solid oxide electrolyte. The method comprises the following steps: converting alternating current into direct current, and supplying the direct current to a solid oxide electrolysis cell; supplying lean H2/H2O mixed gas to the solid oxide electrolysis cell, reacting on a positive pole and outputting rich H2/H2O mixed gas, and producing high-purity O2 on a negative pole; introducing the rich H2/H2O mixed gas into a positive electrode of a solid oxide fuel cell and carrying out electrochemical reaction to output the lean H2/H2O mixed gas; introducing air and the output lean H2/H2O mixed gas into a heat exchanger I and cooling the lean H2/H2O mixed gas in the heat exchanger I, then inputting the cooled lean H2/H2O mixed gas into a pre-mixer through a pump, and mixing the cooled lean H2/H2O mixed gas with supplemental water; introducing tail gas output by a negative electrode of the solid oxide fuel cell and the heated air in the heat exchanger I into a heat exchanger II, and further introducing the heated air back to the negative electrode to consume O2 in the heated air. According to the system and the method for preparing oxygen by electrolyzing water based on solid oxide electrolyte, the electrolysis cell is combined with the fuel cell, so that the large-scale preparation of high-purity O2 can be implemented; the cost of the system can be reduced; the service life of the system for preparing oxygen by electrolyzing water can be prolonged; and the electric energy generated by renewable energy sources such as wind energy and solar energy can be utilized.
Description
Technical field
The invention belongs to technical field of oxygen generation, particularly a kind of brine electrolysis oxygen generation system based on solid oxide electrolyte and method.
Background technology
The method of high purity oxygen mainly contains three kinds: (1) Deep Cooling Method; (2) pressure swing adsorption process; (3) brine electrolysis oxygen generation method.Wherein brine electrolysis method for producing oxygen through stability is higher, and consume energy lower, the capacity scope of application is wider.But many employing proton exchange membrane ionogen in current electrolysis water oxygen generation system, this kind of ionogen working temperature low (<100 DEG C), portability is better, but system efficiency and life-span are all lower.In order to overcome above shortcoming, this patent adopts the brine electrolysis method for producing oxygen through of solid oxide electrolyte, work at 600 DEG C-1000 DEG C, without the need to noble metal catalyst, can reduce costs, the efficiency of raising system and life-span, and system bulk is little, oxygen scale is easy to amplify, and can obtain the high purity oxygen of high purity 99.995%.The input of electric power can utilize the unstable electric power such as wind energy, sun power, can reduce the cost of oxygen further.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of brine electrolysis oxygen generation system based on solid oxide electrolyte and method, can oxygen generation efficiency be improved, realize extensive high purity oxygen (O
2purity>=99.995%).
To achieve these goals, the technical solution used in the present invention is:
Based on a brine electrolysis oxygen generation system for solid oxide electrolyte, comprising:
AC conversion is direct current by AC/DC transmodulator 1;
Electrolytic tank of solid oxide 2, is connected the electric energy receiving it and export with AC/DC transmodulator 1, be connected the poor H receiving it and provide with premixed device 3
2/ H
2o gas mixture, this poor H
2/ H
2o gas mixture is obtained by reacting rich H at electrolytic tank of solid oxide 2 positive pole
2/ H
2o gas mixture, negative reaction obtains the O that purity is more than or equal to 99.995%
2;
Solid Oxide Fuel Cell 4, is connected the rich H receiving it and obtain with electrolytic tank of solid oxide 2
2/ H
2o gas mixture, this rich H
2/ H
2o gas mixture obtains poor H in the anodic reaction of Solid Oxide Fuel Cell 4
2/ H
2o gas mixture;
Interchanger 1, is connected the poor H receiving it and obtain with Solid Oxide Fuel Cell 4
2/ H
2o gas mixture, is connected admission of air with air source, to poor H
2/ H
2o gas mixture is lowered the temperature, the poor H after cooling
2/ H
2o gas mixture inputs to premixed device 3 by pump 6 supercharging, and the air after intensification inputs to interchanger 7;
Interchanger 27, the air receiving it and provide is provided with interchanger 1, be connected the high-temperature tail gas receiving its negative electrode and export with Solid Oxide Fuel Cell 4, heat up further to air, the air after heating up further inputs to Solid Oxide Fuel Cell 4 negative electrode provides oxygen to it.
Described Solid Oxide Fuel Cell 4 is connected with electrolytic tank of solid oxide 2 provides direct current energy to it.
Described premixed device 3 is connected with supplementary feed.
Present invention also offers a kind of brine electrolysis method for producing oxygen through based on solid oxide electrolyte, comprising:
AC/DC transmodulator 1 is utilized to be provided to electrolytic tank of solid oxide 2 for direct current by AC conversion;
Premixed device 3 is utilized to provide poor H to electrolytic tank of solid oxide 2
2/ H
2o gas mixture, at its positive pole, by the reaction of electrolyzer positive pole by poor H
2/ H
2h in O gas mixture
2o is converted into H
2, export rich H
2/ H
2o gas mixture, is more than or equal to the O of 99.995% simultaneously in its negative pole output purity
2;
By rich for gained H
2/ H
2o gas mixture delivers to the anode of Solid Oxide Fuel Cell 4, by electrochemical reaction by rich H
2/ H
2h in O gas mixture
2be converted into H
2o, exports poor H
2/ H
2o gas mixture;
The poor H that Solid Oxide Fuel Cell 4 is exported
2/ H
2o gas mixture delivers to interchanger 1, sends into air, poor H in interchanger 1 simultaneously
2/ H
2o gas mixture is lowered the temperature in interchanger 1;
By the poor H after cooling in interchanger 1
2/ H
2o gas mixture sends into pump 6, after carrying out supercharging, is input in premixed device 3, mixes with the water of supply in pump 6;
Air after heating up in the tail gas of Solid Oxide Fuel Cell 4 negative electrode output and interchanger 1 is sent into interchanger 27, air is heated up further, then that tail gas is emptying; The air of further intensification sends into the negative electrode of Solid Oxide Fuel Cell 4, at the cathode consumption O wherein of Solid Oxide Fuel Cell 4
2.
Direct current, by DC/DC transformer 8, is input in electrolytic tank of solid oxide 2 by the direct current energy that described Solid Oxide Fuel Cell 4 produces.
The alternating-current that described AC/DC transmodulator 1 transforms is the electric energy that wind energy or sun power produce.
Described electrolytic tank of solid oxide 2, single electrolyzer is formed by positive pole, negative pole and solid oxide electrolyte, then extensive electrolytic tank of solid oxide is formed by multiple electrolyzer by series-parallel connection array mode, operating temperature range is 600 DEG C-1000 DEG C, and working pressure range is 0.1MPa-20MPa;
Described Solid Oxide Fuel Cell 4, single fuel cell is formed by anode, negative electrode and solid oxide electrolyte, then extensive Solid Oxide Fuel Cell is formed by multiple fuel cell by series-parallel connection array mode, operating temperature range is 600 DEG C-1000 DEG C, and working pressure range is 0.1MPa-20MPa.
Described solid oxide electrolyte is the zirconium white (YttriaStabilizedZirconia of stabilized with yttrium oxide, YSZ) zirconium white (ScandiaStabilizedZirconia that, scandium is stable, ScSZ) or gadolinium sesquioxide doping cerium oxide (Gadolinia-DopedCeria, GDC);
Described electrolyzer positive pole adopts Ni catalyst based, and is sintered together with solid oxide electrolyte;
Described electrolyzer negative pole adopts the lanthanum manganate (LSM) of strontium doping, and is sintered together with solid oxide electrolyte;
Described anode of fuel cell adopts Ni catalyst based, and is sintered together with solid oxide electrolyte;
Described fuel battery negative pole adopts the lanthanum manganate (LSM) of strontium doping, and is sintered together with solid oxide electrolyte.
Electrolyzer positive pole reacts, and is H
2o+2e
-→ H
2+ O
2-, wherein O
2-be transported to electrolyzer negative pole by ionogen, electronics is transported to electrolyzer positive pole by external circuit from electrolyzer negative pole.
Electrolyzer negative reaction is O
2-→ O
2+ 2e
-, wherein O
2-be transported to electrolyzer negative pole by ionogen from anode, electronics is transported to electrolyzer positive pole by external circuit from electrolyzer negative pole.
Anode of fuel cell reacts, and is H
2+ O
2-→ H
2o+2e
-, wherein O
2-be transported to anode of fuel cell by ionogen from fuel battery negative pole, electronics is transported to fuel battery negative pole by external circuit from anode of fuel cell.
Fuel battery negative pole reacts, and is O
2+ 2e
-→ O
2-, wherein O
2-transported by ionogen and be transported to anode of fuel cell from fuel battery negative pole, electronics is transported to fuel battery negative pole by external circuit from anode of fuel cell.
Described poor H
2/ H
2o gas mixture is the H that temperature is greater than 100 DEG C
2/ H
2o mixed gas, wherein H
2molar fraction be less than 0.3.
Described rich H
2/ H
2o gas mixture is the H that temperature is greater than 100 DEG C
2/ H
2o mixed gas, wherein H
2molar fraction be greater than 0.7.
Compared with prior art, the present invention adopts soild oxide as ionogen, is combined by electrolyzer with fuel cell, can realize extensive high purity O
2, reduce system cost, improve the life-span of brine electrolysis oxygen generation system, and the electric energy that the renewable energy sources such as wind energy/sun power produce can be utilized.
Accompanying drawing explanation
Accompanying drawing 1 is a kind of brine electrolysis oxygen generation system schematic diagram based on solid oxide electrolyte of the present invention.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with drawings and Examples.
Embodiment 1
As shown in Figure 1, the electric energy produced by wind-power electricity generation is input to AC/DC transmodulator 1, is 140V direct current, and is input in the electrolytic tank of solid oxide 2 be made up of 100 batteries by AC/DC transmodulator 1 by 220V AC conversion; At the positive pole of electrolytic tank of solid oxide 2, by the reaction of electrolyzer positive pole by the 30mol%H from premixed device 3
2700 DEG C of H
2/ H
2h in O gas mixture
2o is converted into H
2, export 80mol%H
2800 DEG C of H
2/ H
2o gas mixture, simultaneously at the high-purity O of negative pole output of electrolytic tank of solid oxide 2
2(O
2>99.995%); 80mol%H
2800 DEG C of H
2/ H
2o gas mixture enters the anode of Solid Oxide Fuel Cell 4, by electrochemical reaction by the H in gas mixture
2be converted into H
2o, exports 30mol%H
2900 DEG C of H
2/ H
2o gas mixture, simultaneously at the cathode consumption of Solid Oxide Fuel Cell 4 from the O in the high temperature air of interchanger 27
2, meanwhile Solid Oxide Fuel Cell 4 outwards exports 70V direct current energy; The 30mol%H that Solid Oxide Fuel Cell 4 anode exports
2900 DEG C of H
2/ H
2o gas mixture enters interchanger 1, enters pump 6 after being cooled to 700 DEG C, after carrying out being pressurized to 1.0MPa, is input in premixed device 3, mixes with the water of supply in pump 6; Tail gas (the N that cathode of solid oxide fuel cell exports
2, O
2) enter interchanger 27, preheating is carried out to freezing air, then emptying; First normal temperature air enters interchanger 1 and is warming up to 200 DEG C, and then enters interchanger 27 and be warming up to 600 DEG C, finally enters the negative electrode of Solid Oxide Fuel Cell 4.The 70V direct current energy that Solid Oxide Fuel Cell 4 produces boosts to 140V by DC/DC transformer 8, is input to by direct current in electrolytic tank of solid oxide 2.
Embodiment 2
As shown in Figure 1, the electric energy produced by solar electrical energy generation is input to AC/DC transmodulator 1, be 280V direct current by AC/DC transmodulator 1 by 220V AC conversion, and be input in the electrolytic tank of solid oxide 2 be made up of 200 batteries, 100 electrolytic tank of solid oxide carry out parallel running; At the positive pole of electrolytic tank of solid oxide 2, by the reaction of electrolyzer positive pole by the 20mol%H from premixed device 3
2750 DEG C of H
2/ H
2h in O gas mixture
2o is converted into H
2, export 70mol%H
2850 DEG C of H
2/ H
2o gas mixture, simultaneously at the high-purity O of negative pole output of electrolytic tank of solid oxide 2
2(O
2>99.995%); 70mol%H
2850 DEG C of H
2/ H
2o gas mixture enters the anode of Solid Oxide Fuel Cell 4, by electrochemical reaction by the H in gas mixture
2be converted into H
2o, exports 20mol%H
2950 DEG C of H
2/ H
2o gas mixture, simultaneously at the cathode consumption of Solid Oxide Fuel Cell 4 from the O in the high temperature air of interchanger 27
2, meanwhile Solid Oxide Fuel Cell 4 outwards exports 140V direct current energy; The 20mol%H that Solid Oxide Fuel Cell 4 anode exports
2900 DEG C of H
2/ H
2o gas mixture enters interchanger 1, enters pump 6 after being cooled to 750 DEG C, after carrying out being pressurized to 35.0MPa, is input in premixed device 3, mixes with the water of supply in pump 6; Tail gas (the N that cathode of solid oxide fuel cell exports
2, O
2) enter interchanger 27, preheating is carried out to freezing air, then emptying; First normal temperature air enters interchanger 1 and is warming up to 250 DEG C, and then enters interchanger 27 and be warming up to 650 DEG C, finally enters the negative electrode of Solid Oxide Fuel Cell 4.The 140V direct current energy that Solid Oxide Fuel Cell 4 produces boosts to 280V by DC/DC transformer 8, is input to by direct current in electrolytic tank of solid oxide 2.
Claims (9)
1., based on a brine electrolysis oxygen generation system for solid oxide electrolyte, it is characterized in that, comprising:
AC conversion is direct current by AC/DC transmodulator (1);
Electrolytic tank of solid oxide (2), is connected with AC/DC transmodulator (1) electric energy receiving it and export, and is connected the poor H receiving it and provide with premixed device (3)
2/ H
2o gas mixture, this poor H
2/ H
2o gas mixture is obtained by reacting rich H at electrolytic tank of solid oxide (2) positive pole
2/ H
2o gas mixture, negative reaction obtains the O that purity is more than or equal to 99.995%
2;
Solid Oxide Fuel Cell (4), is connected the rich H receiving it and obtain with electrolytic tank of solid oxide (2)
2/ H
2o gas mixture, this rich H
2/ H
2o gas mixture obtains poor H in the anodic reaction of Solid Oxide Fuel Cell (4)
2/ H
2o gas mixture;
Interchanger one (5), is connected the poor H receiving it and obtain with Solid Oxide Fuel Cell (4)
2/ H
2o gas mixture, is connected admission of air with air source, to poor H
2/ H
2o gas mixture is lowered the temperature, the poor H after cooling
2/ H
2o gas mixture inputs to premixed device (3) by pump (6) supercharging, and the air after intensification inputs to interchanger (7);
Interchanger two (7), the air receiving it and provide is connected with interchanger one (5), the high-temperature tail gas receiving its negative electrode and export is connected with Solid Oxide Fuel Cell (4), heat up further to air, the air after heating up further inputs to Solid Oxide Fuel Cell (4) negative electrode provides oxygen to it.
2. according to claim 1 based on the brine electrolysis oxygen generation system of solid oxide electrolyte, it is characterized in that, described Solid Oxide Fuel Cell (4) is connected with electrolytic tank of solid oxide (2) provides direct current energy to it.
3. according to claim 1 based on the brine electrolysis oxygen generation system of solid oxide electrolyte, it is characterized in that, described premixed device (3) is connected with supplementary feed.
4., based on a brine electrolysis method for producing oxygen through for solid oxide electrolyte, it is characterized in that:
AC/DC transmodulator (1) is utilized AC conversion to be direct current and to provide to electrolytic tank of solid oxide (2);
Premixed device (3) is utilized to provide poor H to electrolytic tank of solid oxide (2)
2/ H
2o gas mixture, at its positive pole, by the reaction of electrolyzer positive pole by poor H
2/ H
2h in O gas mixture
2o is converted into H
2, export rich H
2/ H
2o gas mixture, is more than or equal to the O of 99.995% simultaneously in its negative pole output purity
2;
By rich for gained H
2/ H
2o gas mixture delivers to the anode of Solid Oxide Fuel Cell (4), by electrochemical reaction by rich H
2/ H
2h in O gas mixture
2be converted into H
2o, exports poor H
2/ H
2o gas mixture;
By the poor H that Solid Oxide Fuel Cell (4) exports
2/ H
2o gas mixture delivers to interchanger one (5), sends into air, poor H in interchanger one (5) simultaneously
2/ H
2o gas mixture is cooling in interchanger one (5);
By the poor H in interchanger one (5) after cooling
2/ H
2o gas mixture sends into pump (6), after carrying out supercharging, is input in premixed device (3), mixes with the water of supply in pump (6);
Air after heating up in the tail gas of Solid Oxide Fuel Cell (4) negative electrode output and interchanger one (5) is sent into interchanger two (7), air is heated up further, then that tail gas is emptying; The air of further intensification sends into the negative electrode of Solid Oxide Fuel Cell (4), at the cathode consumption O wherein of Solid Oxide Fuel Cell (4)
2.
5. according to claim 4 based on the brine electrolysis method for producing oxygen through of solid oxide electrolyte, it is characterized in that, direct current, by DC/DC transformer (8), is input in electrolytic tank of solid oxide (2) by the direct current energy that described Solid Oxide Fuel Cell (4) produces.
6. according to claim 4 based on the brine electrolysis method for producing oxygen through of solid oxide electrolyte, it is characterized in that, the alternating-current that described AC/DC transmodulator (1) transforms is the electric energy that wind energy or sun power produce.
7. according to claim 4 based on the brine electrolysis method for producing oxygen through of solid oxide electrolyte, it is characterized in that, described electrolytic tank of solid oxide (2), single electrolyzer is formed by positive pole, negative pole and solid oxide electrolyte, then extensive electrolytic tank of solid oxide is formed by multiple electrolyzer by series-parallel connection array mode, operating temperature range is 600 DEG C-1000 DEG C, and working pressure range is 0.1MPa-20MPa;
Described Solid Oxide Fuel Cell (4), single fuel cell is formed by anode, negative electrode and solid oxide electrolyte, then extensive Solid Oxide Fuel Cell is formed by multiple fuel cell by series-parallel connection array mode, operating temperature range is 600 DEG C-1000 DEG C, and working pressure range is 0.1MPa-20MPa.
8., according to claim 7 based on the brine electrolysis method for producing oxygen through of solid oxide electrolyte, it is characterized in that,
Described solid oxide electrolyte is the zirconium white (YttriaStabilizedZirconia of stabilized with yttrium oxide, YSZ) zirconium white (ScandiaStabilizedZirconia that, scandium is stable, ScSZ) or gadolinium sesquioxide doping cerium oxide (Gadolinia-DopedCeria, GDC);
Described electrolyzer positive pole adopts Ni catalyst based, and is sintered together with solid oxide electrolyte;
Described electrolyzer negative pole adopts the lanthanum manganate (LSM) of strontium doping, and is sintered together with solid oxide electrolyte;
Described anode of fuel cell adopts Ni catalyst based, and is sintered together with solid oxide electrolyte;
Described fuel battery negative pole adopts the lanthanum manganate (LSM) of strontium doping, and is sintered together with solid oxide electrolyte.
9., according to claim 4 based on the brine electrolysis method for producing oxygen through of solid oxide electrolyte, it is characterized in that,
Described poor H
2/ H
2o gas mixture is the H that temperature is greater than 100 DEG C
2/ H
2o mixed gas, wherein H
2molar fraction be less than 0.3.Described rich H
2/ H
2o gas mixture is the H that temperature is greater than 100 DEG C
2/ H
2o mixed gas, wherein H
2molar fraction be greater than 0.7.
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| CN105845962A (en) * | 2016-03-30 | 2016-08-10 | 华中科技大学 | Solid oxide fuel cell and solid oxide electrolysis cell combined power generation system |
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