CN100433430C - 硫－空气燃料电池及其在硫酸生产中的应用 - Google Patents
硫－空气燃料电池及其在硫酸生产中的应用 Download PDFInfo
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- CN100433430C CN100433430C CNB2005100226386A CN200510022638A CN100433430C CN 100433430 C CN100433430 C CN 100433430C CN B2005100226386 A CNB2005100226386 A CN B2005100226386A CN 200510022638 A CN200510022638 A CN 200510022638A CN 100433430 C CN100433430 C CN 100433430C
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 229910017563 LaCrO Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910009580 YMnO Inorganic materials 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical group [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 238000010960 commercial process Methods 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明提供硫—空气燃料电池及其在硫酸生产中的应用，属于化工生产节能技术领域。该电池结构与固体氧化物氢氧燃料电池一致，该电池负极是将气态S以电化学方式直接氧化成SO3，并使反应的化学能转化为电能。硫的氧化在电池密闭系统内进行，不存在废气排放。该电池可以作为以硫为原料生产硫酸的合成器，用于硫酸工业化生产，实现硫酸生产、化学发电和环境保护三位一体的结合起来。
Description
技术领域：
本发明属于化工生产节能技术领域，具体涉及硫-空气燃料电池及在硫酸生产中的应用。
背景技术：
硫酸是一种用途极为广泛的化工产品。近年来，以硫磺为原料生产硫酸的产量逐年增大。目前，硫磺生产硫酸的方法与硫铁矿生产硫酸的方法基本一致，都是先通空气焙烧原料生成SO2，再用空气在钒催化剂和425～600℃温度下，进一步氧化SO2成SO3，随后用稀硫酸吸收SO3生成浓硫酸。为了提高硫的利用率和减少环境污染，还需要进行两转两吸的流程，，是一项极为复杂的生产过程。这种硫酸生产工艺伴随的尾气总是存在一定量残留的SO2排放到大气中，也是大气污染源之一。
S和O2反应生成SO3的反应为：
S(g)+3/2O2(g)＝SO3(g) ΔrGm θ(298K)＝-609.3kJ/mol
上述反应如在电池装置中进行，化学能转换为电能。采用该电池用于工业化生产硫酸，每生产1kg浓硫酸可发电1.7度。根据文献检索，未发现有关硫-空气燃料电池以及该电池在硫酸生产中的应用等方面的相关文献报道，在实际工业生产中也没有使用。
发明内容：
本发明提供一种硫-空气燃料电池，用作以硫为原料生产硫酸的反应器，实现化学发电、环境保护与硫酸生产三位一体。该电池装置结构与固体氧化物氢氧燃料电池一致，其特征是：将气态S以电化学方式直接氧化生成SO3，使反应的化学能转化为电能。生成的SO3经稀硫酸吸收生成浓硫酸。硫的氧化在电池密闭系统内进行，生产过程中不存在尾气排放，不存在环境污染。
该二氧化硫-空气电池结构简图见说明书附图。电池正极的电极反应为：
O2(g)+4e＝2O2-
正极反应生成的O2-通过固体电解质传递到负极，电池负极的电极反应为：
S(g)-6e+3O2-＝SO3(g)
电池反应为：
S(g)+3/2O2(g)＝SO3(g) Eθ(298K)＝1.05V
硫-空气燃料电池负极通入气态S，分压为0.5---300kPa，流速3-1500cm3/min；电池正极通入空气或O2，氧气分压为20--270kPa，流速5-1500cm3/min；电池工作温度为300--1000℃，电池负极出口气体经冷却系统，回收未反应完全的硫重新作为原料；冷却后的气体经稀硫酸吸收SO3生成浓硫酸产品。
电池负极反应中存在着反应中间体SO2，其中部分随SO3气体流出，在经稀硫酸吸收SO3时得到分离并返回负极重新参加反应。
上述硫-空气燃料电池不用改变电池装置结构，可以使用硫或硫化氢或二氧化硫或它们的混合物为燃料，经电化学氧化直接生成三氧化硫。
硫-空气燃料电池由于整个硫的氧化在密闭系统内进行，不存在尾气排放，环保效果明显。硫-空气燃料电池可作为工业化生产硫酸的合成器，将硫酸的工业化生产、化学发电和环境保护三位一体的结合起来，节省了能源，大大降低了生产成本。如果我国采用二氧化硫-空气电池装置用于硫酸的工业化生产，每年可发电300亿度。
附图说明：
图：本发明硫-空气燃料电池结构及生产硫酸工艺流程示意图
图：1、电池负极电极；2、固体电解质；3、电池正极电极；4、冷却系统；5、SO3吸收系统；6、硫加热升华系统。
具体实施方式：
见说明书附图所示，装备硫-空气燃料电池，电池正极电极为掺有20％银粉的YMnO3材料压片组成，固体电解质选用钙钛矿结构La0.8Sr0.2GaO2.9材料组成，电池负极电极为掺有45％LaCrO3的YSZ(氧化钇稳定的氧化锆)材料压片组成。电池负极通入S(g)，分压为110kPa，流速10cm3/min；电池正极通入空气，压力为100kPa，氧气分压为21kPa，空气流速500cm3/min；电池工作温度为500℃。电池输出电压为0.9V。
Claims (2)
1、硫-空气燃料电池，其特征是：所述的燃料电池的正极电极为掺有20％银粉的YMnO3材料压片组成，固体电解质选用钙钛矿结构La0.8Sr0.2GaO2.9材料组成，电池负极电极为掺有45％LaCrO3的氧化钇稳定的氧化锆材料压片组成；电池正极通入空气，电池负极通入硫蒸汽，电池的工作温度为500℃，该电池负极是将气态S以电化学方式直接氧化成SO3，并使反应的化学能转化为电能。
2、权利要求1所述硫-空气燃料电池在硫酸生产中的应用，其特征在于该电池作为以硫为原料合成硫酸的反应器，用于硫酸的工业化生产。
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| EP2095452A4 (en) * | 2006-10-31 | 2010-09-22 | Wesley Martin Lang | ELECTROCHEMICAL CELLS WITH SULFUR AS A FUEL |
| CN101325265B (zh) * | 2008-06-27 | 2010-07-28 | 安徽工业大学 | 一种二氧化硫-空气固体氧化物燃料电池制备方法 |
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| US20030215696A1 (en) * | 2002-05-14 | 2003-11-20 | Chuang Karl T. | Electrode catalysts for H2S fuel cell |
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| US20030215696A1 (en) * | 2002-05-14 | 2003-11-20 | Chuang Karl T. | Electrode catalysts for H2S fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| 燃料电池. A.O.麦克杜格尔著，江船译，5-11，国防工业出版社. 1983 |
| 燃料电池. A.O.麦克杜格尔著，江船译，5-11，国防工业出版社. 1983 * |
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