CN100565988C - A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode - Google Patents
A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode Download PDFInfo
- Publication number
- CN100565988C CN100565988C CNB2008100221070A CN200810022107A CN100565988C CN 100565988 C CN100565988 C CN 100565988C CN B2008100221070 A CNB2008100221070 A CN B2008100221070A CN 200810022107 A CN200810022107 A CN 200810022107A CN 100565988 C CN100565988 C CN 100565988C
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- CN
- China
- Prior art keywords
- sulfur
- oxide fuel
- fuel cell
- anode
- solid oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 9
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical group O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006256 anode slurry Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 description 5
- 239000006257 cathode slurry Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
Classifications
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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
- Y02E60/50—Fuel cells
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- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a kind of preparation method of sulfur-oxygen solid oxide fuel cell anode, belong to new fuel cell and Chemical Manufacture field of energy-saving technology.The sulfur-oxygen solid oxide fuel cell solid electrolyte is Y
2O
3The ZrO that mixes
2, negative electrode is La
0.7Sr
0.3MnO
3, anode is La
0.8Ca
0.2CrO
3Sulfur-oxygen solid oxide fuel cell adopts sulfur vapor as battery fuel, and working temperature is 700-900 ℃, and product is a sulfur trioxide gas.Sulfur-oxygen solid oxide fuel cell can be used as the synthesizer of suitability for industrialized production sulfuric acid, realizes gas washing in SA production, Chemically generation and the Trinitarian combination of environmental protection.
Description
Technical field:
The invention belongs to new fuel cell and Chemical Manufacture field of energy-saving technology, be specifically related to the preparation of sulfur-oxygen solid oxide fuel cell anode.
Background technology:
Chemical industry is high energy-consuming industry, and how to reduce the energy consumption of Chemical Manufacture be one of key problem of China's chemical research to sophistication.Sulfuric acid is a kind of purposes chemical products very widely, exists always in the existing sulfuric acid production process that a large amount of chemical energy are converted into heat energy and the problem that is wasted, and how reclaiming these energy is one of directions of sulfuric acid production process reform.
S and O
2Reaction generates SO
3Reaction be:
S
(g)+3/2O
2(g)＝SO
3(g)Δ
rG
m θ(973K)＝-460.3kJ/mol E
0(973K)＝0.80V
Δ
rG
m θ(1173K)＝-416.6kJ/mol?E
0(973K)＝0.72V
Above-mentioned reaction is as carrying out in cell apparatus, and chemical energy can be exchanged into electric energy.It is raw material that patent (CN1805195A) has proposed with sulphur, is the method for sulfuric acid synthesizer with Solid Oxide Fuel Cell, realizes gas washing in SA production, Chemically generation and the Trinitarian combination of environmental protection, estimates every year and can generate electricity 30,000,000,000 degree.It is raw material that patent (CN1812184A) has proposed with sulfur dioxide, and adopting Proton Exchange Membrane Fuel Cells is the sulfuric acid synthesizer, and sulfuric acid industry production and Chemically generation are combined, and estimates every year and can generate electricity 20,000,000,000 degree.
Summary of the invention:
Sulfur-oxygen solid oxide fuel cell is to transform to form on the basis of hydrogen-oxygen Solid Oxide Fuel Cell.Sulfur-oxygen solid oxide fuel cell is that employing sulphur is fuel, and product is a sulfur trioxide.The key technology of sulfur-oxygen solid oxide fuel cell is the anode preparation of battery, the invention provides a kind of preparation method of sulfur-oxygen solid oxide fuel cell anode.
The sulfur-oxygen solid oxide fuel cell anode slurry preparation step is: according to La
0.8Ca
0.2CrO
3Stoichiometric proportion takes by weighing La
2O
3, CaCO
3And Cr
2O
3Grind, compressing tablet is pulverized after 1200 ℃ of roastings again, and getting 360 order minus sieves, to add 3% polyvinyl butyral resin be binding agent, and 10% ethyl cellulose is a pore forming agent, and through ball milling after 10 hours, 50 ℃ of oven dry are dispersed in and are La in the terpinol
0.8Ca
0.2CrO
3Anode slurry.
Sulfur-oxygen solid oxide fuel cell cathode slurry preparation process is: according to La
0.7Sr
0.3MnO
3Stoichiometric proportion takes by weighing La
2O
3, SrCO
3And MnCO
3Grind, compressing tablet is pulverized after 1200 ℃ of roastings again, and the polyvinyl butyral resin of getting 360 order minus sieves adding 3% is a binding agent, and 10% ethyl cellulose is a pore forming agent, behind ball milling 10h, and 50 ℃ of oven dry, being dispersed in the terpinol is La
0.7Sr
0.3MnO
3Cathode slurry.
The solid electrolyte of sulfur-oxygen solid oxide fuel cell adopts Y
2O
3The ZrO that mixes
2, Y wherein
2O
3Molar percentage be 8%, with Y
2O
3The ZrO that mixes
2The powder compressing tablet after 1500 ℃ of roastings, applies La on the one side of solid electrolyte sheet base
0.7Sr
0.3MnO
3Cathode slurry applies La on the another side
0.8Ca
0.2CrO
3Anode slurry, the sheet base after the coating is through 1400 ℃ of roastings.The negative electrode bubbling air or the oxygen of sulfur-oxygen solid oxide fuel cell, oxygen partial pressure are 20-100kPa, flow velocity 100-500cm
3/ min; Anode feeds sulfur vapor as battery fuel, and dividing potential drop is 100-120kPa, flow velocity 70-200cm
3/ min, cell reaction product are sulfur trioxide gas, and battery operated temperature is 700-900 ℃.
The sulfur-oxygen solid oxide fuel cell anode exit gas is through cooling system, reclaim unreacted completely sulphur again as raw material.Cooled gas absorbs SO through dilute sulfuric acid
3Generate concentrated sulfuric acid product, the SO that unreacted is complete and residual
2Gas can not be absorbed by dilute sulfuric acid and and SO
3Separate, and return anode and participate in reaction again.
There is not exhaust emissions in sulfur-oxygen solid oxide fuel cell because the oxidation of whole sulphur is carried out in closed system, environment protecting is obvious.Sulfur-oxygen solid oxide fuel cell can be used as the synthesizer of suitability for industrialized production sulfuric acid, and the suitability for industrialized production of sulfuric acid, Chemically generation and environmental protection Trinity ground are combined, and has saved the energy, greatly reduces production cost.
Description of drawings:
Fig. 1 is the sulfur-oxygen solid oxide fuel cell structure and produces the sulfur process schematic flow sheet
Among the figure, 1 is galvanic anode, and 2 is solid electrolyte, and 3 is cell cathode, and 4 is cooling system, and 5 is SO
3Absorption system, 6 is sulphur heating sublimation system.
Embodiment:
Example 1
Sulfur-oxygen solid oxide fuel cell is shown in Figure of description, and solid electrolyte adopts YSZ (Y
2O
3The ZrO that mixes
2, Y
2O
3Molar percentage be 8%) behind the powder compressing tablet, on the one side of solid electrolyte sheet base, apply La
0.7Sr
0.3MnO
3Cathode slurry applies La on the another side
0.8Ca
0.2CrO
3Anode slurry, the sheet base after the coating is through 1400 ℃ of roastings.Galvanic anode feeds S
(g), dividing potential drop is 120kPa, flow velocity 200cm
3/ min; Cell cathode aerating oxygen, pressure are 100kPa, flow velocity 100cm
3/ min; Battery operated temperature is 900 ℃, and cell output voltage is 0.67V.
Example 2
Sulfur-oxygen solid oxide fuel cell is shown in Figure of description, and solid electrolyte adopts YSZ (Y
2O
3The ZrO that mixes
2, Y
2O
3Molar percentage be 8%) behind the powder compressing tablet, on the one side of solid electrolyte sheet base, apply La
0.7Sr
0.3MnO
3Cathode slurry applies La on the another side
0.8Ca
0.2CrO
3Anode slurry, the sheet base after the coating is through 1400 ℃ of roastings.Galvanic anode feeds S
(g), dividing potential drop is 100kPa, flow velocity 70cm
3/ min; Cell cathode bubbling air, pressure are 100kPa, and oxygen partial pressure is 21kPa, flow velocity 500cm
3/ min; Battery operated temperature is 700 ℃, and cell output voltage is 0.63V.
Claims (2)
1. the anode of a sulfur-oxygen solid oxide fuel cell, it is characterized in that: this battery anode material is La
0.8Ca
0.2CrO
3, battery operated temperature is 700-900 ℃, and galvanic anode feeds sulfur vapor, and product is a sulfur trioxide.
2. the preparation method of the anode of sulfur-oxygen solid oxide fuel cell according to claim 1 is characterized in that the preparation process of sulfur-oxygen solid oxide fuel cell anode is: according to La
0.8Ca
0.2CrO
3Stoichiometric proportion takes by weighing La
2O
3, CaCO
3And Cr
2O
3Grind, compressing tablet is pulverized after 1200 ℃ of roastings again, and getting 360 order minus sieves, to add 3% polyvinyl butyral resin be binding agent, and 10% ethyl cellulose is a pore forming agent, and through ball milling after 10 hours, 50 ℃ of oven dry are dispersed in and are La in the terpinol
0.8C
0.2CrO
3Anode slurry applies La on the one side of solid electrolyte sheet base
0.8Ca
0.2CrO
3Anode slurry, the sheet base after the coating is through 1400 ℃ of roastings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100221070A CN100565988C (en) | 2008-06-24 | 2008-06-24 | A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100221070A CN100565988C (en) | 2008-06-24 | 2008-06-24 | A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101320811A CN101320811A (en) | 2008-12-10 |
| CN100565988C true CN100565988C (en) | 2009-12-02 |
Family
ID=40180736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2008100221070A Expired - Fee Related CN100565988C (en) | 2008-06-24 | 2008-06-24 | A kind of preparation method for sulfur oxygen solid-oxide fuel battery anode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100565988C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901915B (en) * | 2010-07-12 | 2012-10-03 | 安徽工业大学 | Preparation of sulfur-oxygen solid oxide fuel cell anode |
| CN101916872B (en) * | 2010-08-27 | 2012-07-04 | 安徽工业大学 | Method for preparing cell slice of sulfur-oxygen solid oxide fuel cell |
| CN102142565B (en) * | 2011-02-24 | 2013-11-13 | 安徽工业大学 | Cathode material of YCrO3-base sulfur-oxygen fuel cell |
| CN102142564B (en) * | 2011-02-24 | 2014-04-02 | 安徽工业大学 | LaFeO3-base cathode material of sulfur-oxygen fuel cell |
-
2008
- 2008-06-24 CN CNB2008100221070A patent/CN100565988C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101320811A (en) | 2008-12-10 |
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Owner name: ANHUI ENERGY CHEMICAL FUEL CELL CO.,LTD. Free format text: FORMER OWNER: ANHUI UNIVERSITY OF TECHNOLOGY Effective date: 20111101 |
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Free format text: CORRECT: ADDRESS; FROM: 243002 MAANSHAN, ANHUI PROVINCE TO: 241006 WUHU, ANHUI PROVINCE |
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Effective date of registration: 20111101 Address after: 241006 Anhui city of Wuhu Province Silver Lake Road No. 38 Patentee after: Anhui Nenghua Fuel Cell Co., Ltd. Address before: 243002 Anhui province Ma'anshan Huashan Lake District Road No. 59 Patentee before: Anhui University of Technology |
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Granted publication date: 20091202 Termination date: 20160624 |