硫化氢直接分解制取氢气和硫黄研究进展

doi:10.16085/j.issn.1000-6613.2017.04.039

摘要/Abstract

摘要： 硫化氢直接分解制取氢气和硫黄，不仅可以使石油、天然气、煤和矿产加工等生产过程中产生的硫化氢得到有效治理、解决环境污染问题，还能在回收硫黄的同时获得清洁能源——氢能。本文综述了热分解（直接热分解、催化热分解、超绝热分解）、电化学分解、光催化分解以及等离子体分解等硫化氢直接分解制取氢气和硫黄技术，对各种方法的基本原理、热力学依据进行了简要介绍，并详细阐述了各种技术的国内外研究现状，从研究方法、技术特点、反应性能、优缺点以及这些技术未来研究的可能突破点等方面展开深入分析。最后对硫化氢直接分解制氢技术的发展方向进行了展望，指出将膜技术、催化技术及等离子体技术相结合，不断发展和探索新技术将是硫化氢分解制氢技术的未来发展趋势。

关键词: 制氢, 热解, 回收

Abstract: Direct decomposition of hydrogen sulfide is an effective way not only to treat the waste gas in coal,petroleum,natural gas and mineral processing industries for solving the environmental pollution problems but also to produce sulfur and a clean energy,hydrogen. In this paper,the research progress of hydrogen and sulfur produced from direct decomposition of hydrogen sulfide including themolysis(directly high-temperature thermolysis,catalytic thermolysis and superadiabatic thermolysis),electrochemical technology,photocatalytic decomposition and plasma technology are reviewed. Fundamental principle and themodynamic basis of methods involved are briefly introduced. Then, a detailed description of research status focused on research methods,technique feature,reaction performance,advantage and disadvantage,and potential breakthrough point,etc. is given. The future development trend is prospected at the end of this review as well. A prospect is put forward that continuously exploring and developting new technologies such as combining membrane technology,catalytic technology and plasma technology would be the future trend in the field of hydrogen production from H₂S decomposition.

Key words: hydrogen production, pyrolysis, recovery

中图分类号:

TQ125.1

张婧, 张铁, 孙峰, 徐伟, 石宁. 硫化氢直接分解制取氢气和硫黄研究进展[J]. 化工进展, 2017, 36(04): 1448-1459.

ZHANG Jing, ZHANG Tie, SUN Feng, XU Wei, SHI Ning. Research progress on hydrogen and sulfur production from direct decomposition of hydrogen sulfide[J]. Chemical Industry and Engineering Progress, 2017, 36(04): 1448-1459.

参考文献

[1] AL-SHAMMA L,NAMAN S. The production and separation of hydrogen and sulfur from thermal decomposition of hydrogen sulfide over vanadium oxide/sulfide catalysts[J]. Int. J. Hydrogen Energy,1990,15(1):1-5.
[2] AKAMATSU K,NAKANE M,SUGAWARA T,et al. Development of a membrane reactor for decomposing hydrogen sulfide into hydrogen using a high-performance amorphous silica membrane[J]. Journal of Membrane Science,2008,325(1):16-19.
[3] GULDAL N,FIGEN H,BAYKARA S. New catalysts for hydrogen production from H₂S:preliminary results[J]. Int. J. Hydrogen Energy,2015,40(24):7452-7458.
[4] MIZUTA S,KONDO W,FUJII K,et al. Hydrogen production from hydrogen sulfide by the iron-chlorine hybrid process[J]. Industrial & Engineering Chemistry Research,1991,30(7):1601-1608.
[5] ANANI A,MAO Z,WHITE R E,et al. Electrochemical production of hydrogen and sulfur by low-temperature decomposition of hydrogen sulfide in an aqueous alkaline solution[J]. Journal of the Electrochemical Society,1990,137(9):2703-2709.
[6] KALINA D,MAAS JR E T. Indirect hydrogen sulfide conversion——Ⅰ. An acidic electrochemical process[J]. Int. J. Hydrogen Energy,1985,10(3):157-162.
[7] KALE B,BAEG J O,YOO J S,et al. Synthesis of a novel photocatalyst,ZnBiVO₄,for the photodecomposition of H₂S[J]. Canadian Journal of Chemistry,2005,83(6/7):527-532.
[8] YAN H,YANG J,MA G,et al. Visible-light-driven hydrogen production with extremely high quantum efficiency on Pt-PdS/CdS photocatalyst[J]. Journal of Catalysis,2009,266(2):165-168.
[9] BAI X F,CAO Y,WU W. Photocatalytic decomposition of H₂S to produce H₂ over CdS nanoparticles formed in HY-zeolite pore[J]. Renewable Energy,2011,36(10):2589-2592.
[10] ZONG X,HAN J,SEGER B,et al. An integrated photoelectrochemical-chemical loop for solar-driven overall splitting of hydrogen sulfide[J]. Angewandte Chemie International Edition,2014,53(17):4399-4403.
[11] ZHAO G B,JOHN S,ZHANG J J,et al. Production of hydrogen and sulfur from hydrogen sulfide in a nonthermal-plasma pulsed corona discharge reactor[J]. Chemical Engineering Science,2007,62(8):2216-2227.
[12] SUBRAHMANYA M C,RENKEN A,KIWI MINSKER L. Non-thermal plasma catalytic reactor for hydrogen production by direct decomposition of H₂S[J]. Journal of Optoelectronics and Advanced Materials,2008,10(8):1991-1993.
[13] JOHN S,HAMANN J C,MUKNAHALLIPATNA S S,et al. Energy efficiency of hydrogen sulfide decomposition in a pulsed corona discharge reactor[J]. Chemical Engineering Science,2009,64(23):4826-4834.
[14] NUNNALLY T,GUTSOL K,RABINOVICH A,et al. Dissociation of H₂S in non-equilibrium gliding arc "tornado" discharge[J]. Int. J. Hydrogen Energy,2009,34(18):7618-7625.
[15] LINGA REDDY E,KARUPPIAH J,BIJU V,et al. Catalytic packed bed non-thermal plasma reactor for the extraction of hydrogen from hydrogen sulfide[J]. International Journal of Energy Research,2013,37(11):1280-1286.
[16] ZHAO L,WANG Y,SUN Z,et al. Synthesis of highly dispersed metal sulfide catalysts via low temperature sulfidation in dielectric barrier discharge plasma[J]. Green Chemistry,2014,16(5):2619-2626.
[17] REDDY E L,BIJU V,SUBRAHMANYAM C. Hydrogen production from hydrogen sulfide in a packed-bed DBD reactor[J]. Int. J. Hydrogen Energy,2012,37(10):8217-8222.
[18] SLIMANE R B,LAU F S,DIHU R J,et al. Production of hydrogen by superadiabatic decomposition of hydrogen sulfide[C]//proceedings of the Proc 14th World Hydrogen Energy Conference,US:NREL,2002:1-15.
[19] FARAJI F,SAFARIK I,STRAUSZ O P,et al. The direct conversion of hydrogen sulfide to hydrogen and sulfur[J]. Int. J. Hydrogen Energy,1998,23(6):451-456.
[20] FUKUDA K,DOKIYA M,KAMEYAMA T,et al. Catalytic decomposition of hydrogen sulfide[J]. Industrial & Engineering Chemistry Fundamentals,1978,17(4):243-248.
[21] KAMEYAMA T,DOKIYA M,FUKUDA K,et al. Differential permeation of hydrogen sulfide through a microporous Vycor-type glass membrane in the separation system of hydrogen and hydrogen sulfide[J]. Separation Science and Technology,1979,14(10):953-957.
[22] KAMEYAMA T,FUKUDA K,FUJISHIGE M,et al. Production of hydrogen from hydrogen sulfide by means of selective diffusion membranes[J]. Hydrogen Energy Progress,1981,1:569-579.
[23] KAMEYAMA T,DOKIYA M,FUJISHIGE M,et al. Possibility for effective production of hydrogen from hydrogen sulfide by means of a porous Vycor glass membrane[J]. Industrial & Engineering Chemistry Fundamentals,1981,20(1):97-99.
[24] KAMEYAMA T,DOKIYA M,FUJISHIGE M,et al. Production of hydrogen from hydrogen sulfide by means of selective diffusion membranes[J]. Int. J. Hydrogen Energy,1983,8(1):5-13.
[25] EDLUND D J,PLEDGER W A. Thermolysis of hydrogen sulfide in a metal-membrane reactor[J]. Journal of Membrane Science,1993,77(2/3):255-264.
[26] 张谊华,滕玉美. 硫化铁催化剂的制备,表征及对H₂S制H₂反应的研究[J]. 华东理工大学学报(自然科学版),1995,21(6):738-742. ZHANG Y H,TENG Y M. The preparation and characterization of iron sulfide catalyst and it's reactivity for thermochemical decomposition of H₂S to H₂[J]. Journal of East China University of Science and Technology,1995,21(6):738-742.
[27] RESHETENKO T,KHAIRULIN S,ISMAGILOV Z,et al. Study of the reaction of high-temperature H₂S decomposition on metal oxides(γ-Al₂O₃,α-Fe₂O₃,V₂O₅)[J]. Int. J. Hydrogen Energy,2002,27(4):387-394.
[28] RICARDO B V. Catalytic membrane reactor that is used for the decomposition of hydrogen sulphide into hydrogen and sulphur and the separation of the products of said decomposition:EP 1411029[P]. 2004-04-21.
[29] STARTSEV A. Low-temperature catalytic decomposition of hydrogen sulfide into hydrogen and diatomic gaseous sulfur[J]. Kinet Catal.,2016,57(4):511-522.
[30] STARTSEV A,KRUGLYAKOVA O,CHESALOV Y A,et al. Low temperature catalytic decomposition of hydrogen sulfide into hydrogen and diatomic gaseous sulfur[J]. Top. Catal.,2013,56(11):969-980.
[31] STARTSEV A N,KRUGLYAKOVA O V. Diatomic gaseous sulfur obtained at low temperature catalytic decomposition of hydrogen sulfide[J]. Journal of Chemistry and Chemical Engineering,2013,7(11):1007-1013.
[32] STARTSEV A,KRUGLYAKOVA O,CHESALOV Y A,et al. Low-temperature catalytic decomposition of hydrogen sulfide on metal catalysts under layer of solvent[J]. Journal of Sulfur Chemistry,2016,37(2):229-240.
[33] BINGUE J P,SAVELIEV A V,FRIDMAN A,et al. Hydrogen sulfide filtration combustion:comparison of theory and experiment[J]. Experimental Thermal and Fluid Science,2002,26(2):409-415.
[34] SLIMANE R,LAU F,KHINKIS M,et al. Conversion of hydrogen sulfide to hydrogen by superadiabatic partial oxidation:thermodynamic consideration[J]. Int. J. Hydrogen Energy,2004,29(14):1471-1477.
[35] 凌忠钱,周昊,钱欣平,等. 多孔介质内H₂S贫氧燃烧制氢数值模拟[J]. 环境科学学报,2006,26(1):22-26. LING Z Q,ZHOU H,QIAN X P,et al. Numerical simulation of hydrogen production in porous media from hydrogen sulfide by partialoxidation[J]. Acta Scientiae Circumstantiae,2006,26(1):22-26.
[36] 李国能,周昊,钱欣平,等. 多孔介质内H₂S超绝热燃烧制氢的数值模拟[J]. 化工学报,2006,57(9):2175-2179. LI G N,ZHOU H,QIAN X P,et al. Modeling hydrogen production in super-adiabatic com bustion of hydrogen sulfide in porous media[J]. Journal of Chemical Industry and Engineering (China),2006,57(9):2175-2179.
[37] 凌忠钱. 多孔介质内超绝热燃烧及硫化氢高温裂解制氢的试验研究和数值模拟[D]. 杭州:浙江大学,2008. LING Z Q. Experimental study and numerical simulation on super-adiabatic combustion and hydrogen production based on pyrolysis of H₂S in porous media[D]. Hangzhou:Zhejiang University,2008.
[38] SHIH Y S,LEE J L. Continuous solvent extraction of sulfur from the electrochemical oxidation of a basic sulfide solution in the CSTER system[J]. Industrial & Engineering Chemistry Process Design and Development,1986,25(3):834-836.
[39] KALINA D W,MAAS JR E T. Indirect hydrogen sulfide conversion-Ⅱ. A basic electrochemical process[J]. Int. J. Hydrogen Energy,1985,10(3):163-167.
[40] 罗文利,赵永丰. 从硫化氢中回收氢气和硫黄的方法[J]. 石油大学学报(自然科学版),1994,18(4):95-101. LUO W L,ZHAO Y F. A method for the recovery of hydrogen and element sulfur from hydrogen sulfide[J]. Journal of the University of Petroleum,China,1994,18(4):95-101.
[41] 李发永,曹作刚,张海鹏,等. 由硫化氢制取硫黄及氢气扩大实验研究[J]. 化工进展,2001,20(7):38-41. Li F Y,CAO Z G,ZHANG H P,et al. Experimental study on transforming refinery acid tail gas into sulphur and hydrogen[J]. Chemical Industry and Engineering Progress,2001,20(7):38-41.
[42] 袁长忠,邢定峰,俞英. 硫化氢间接电解制氢中试阴极动力学研究[J]. 化工学报,2005,56(7):1317-1321. YUAN C Z,XING D F,YU Y. Macroscopic kinetics of cathodic reaction in pilot-scale hydrogen production from indirect electrolysis of hydrogen sulfide[J]. Journal of Chemical Industry and Engineering (China),2005,56(7):1317-1321.
[43] SERPONE N,BORGARELLO E,GR TZEL M. Visible light induced generation of hydrogen from H₂S in mixed semiconductor dispersions; improved efficiency through inter-particle electron transfer[J]. Journal of the Chemical Society,Chemical Communications,1984,6:342-344.
[44] BORGARELLO E,SERPONE N,GR TZEL M,et al. Hydrogen production through microheterogeneous photocatalysis of hydrogen sulfide cleavage. The thiosulfate cycle[J]. Int. J. Hydrogen Energy,1985,10(11):737-741.
[45] KHAN M T,BHARDWAJ R,BHARDWAJ C. Photodecomposition of H₂S by silver doped cadmium sulfide and mixed sulfides with ZnS[J]. Int. J. Hydrogen Energy,1988,13(1):7-10.
[46] DE G C,ROY A M,BHATTACHARYA S S. Photocatalytic production of hydrogen and concomitant cleavage of industrial waste hydrogen sulphide[J]. Int. J. Hydrogen Energy,1995,20(2):127-131.
[47] 马贵军,鄢洪建,宗旭,等. 气-固相光催化分解硫化氢制氢[J]. 催化学报,2008,29(4):313-315. MA G J,YAN H J,ZONG X,et al. Photocatalytic splitting of H₂S to produce hydrogen by gassolid phase reaction[J]. Chinese Journal of Catalysis,2008,29(4):313-315.
[48] SO W W,KIM K J,MOON S J. Photo-production of hydrogen over the CdS-TiO₂ nano-composite particulate films treated with TiCl₄[J]. Int. J. Hydrogen Energy,2004,29(3):229-234.
[49] JANG J S,LI W,OH S H,et al. Fabrication of CdS/TiO₂ nano-bulk composite photocatalysts for hydrogen production from aqueous H₂S solution under visible light[J]. Chemical Physics Letters,2006,425(4):278-282.
[50] RUBAN P,SELLAPPA K. Concurrent hydrogen production and hydrogen sulfide decomposition by solar photocatalysis[J]. Clean——Soil,Air,Water,2016,44(9999):1-13.
[51] SUBRAMANIAN E,BAEG J O,KALE B B,et al. Visible light driven ZnFe₂Ta₂O₉catalyzed decomposition of H₂S for solar hydrogen production[J]. Bull. Korean Chem. Soc.,2007,28(11):2089-2092.
[52] KANADE K,BAEG J O,MULIK U,et al. Nano-CdS by polymer-inorganic solid-state reaction:visible light pristine photocatalyst for hydrogen generation[J]. Materials Research Bulletin,2006,41(12):2219-2225.
[53] WANG Z,CI X,DAI H,et al. One-step synthesis of highly active Ti-containing Cr-modified MCM-48 mesoporous material and the photocatalytic performance for decomposition of H₂S under visible light[J]. Appl. Surf. Sci.,2012,258(20):8258-8263.
[54] KIM H H. Nonthermal plasma processing for air-pollution control:a historical review,current issues,and future prospects[J]. Plasma Processes and Polymers,2004,1(2):91-110.
[55] TRAUS I,SUHR H,HARRY J,et al. Application of a rotating high-pressure glow discharge for the dissociation of hydrogen sulfide[J]. Plasma Chemistry and Plasma Processing,1993,13(1):77-91.
[56] HELFRITCH D. Pulsed corona discharge for hydrogen sulfide decomposition[J]. IEEE Transactions on Industry Applications,1993,29(5):882-886.
[57] TRAUS I,SUHR H. Hydrogen sulfide dissociation in ozonizer discharges and operation of ozonizers at elevated temperatures[J]. Plasma Chemistry and Plasma Processing,1992,12(3):275-285.
[58] REDDY E L,KARUPPIAH J,SUBRAHMANYAM C. Kinetics of hydrogen sulfide decomposition in a DBD plasma reactor operated at high temperature[J]. Journal of Energy Chemistry,2013,22(3):382-386.
[59] REDDY E L,BIJU V,SUBRAHMANYAM C. Production of hydrogen from hydrogen sulfide assisted by dielectric barrier discharge[J]. Int. J. Hydrogen Energy,2012,37(3):2204-2209.
[60] REDDY E L,BIJU V,SUBRAHMANYAM C. Production of hydrogen and sulfur from hydrogen sulfide assisted by nonthermal plasma[J]. Applied Energy,2012,95:87-92.
[61] ZHAO L,WANG Y,JIN L,et al. Decomposition of hydrogen sulfide in non-thermal plasma aided by supported CdS and ZnS semiconductors[J]. Green Chemistry,2013,15(6):1509-1513.
[62] ZHAO L,WANG Y,LI X,et al. Hydrogen production via decomposition of hydrogen sulfide by synergy of non-thermal plasma and semiconductor catalysis[J]. Int. J. Hydrogen Energy,2013,38(34):14415-14423.
[63] RUSANOV V D,FRIDMAN A A. The physics of a chemically active plasma[J]. Moscow Izdatel Nauka,1984,1:416-429.
[64] FRIDMAN A. Plasma chemistry[M]. Oxford:Cambridge University Press,2008:738-749.
[65] DALAINE V,CORMIER J,PELLERIN S,et al. H₂S destruction in 50 Hz and 25 kHz gliding arc reactors[J]. Journal of Applied Physics,1998,84(3):1215-1221.
[66] GUTSOL K,NUNNALLY T,RABINOVICH A,et al. Mechanisms of non-equilibrium dissociation of hydrogen sulfide in low-temperature plasma[C]//Proceedings of the 2010 IEEE International Conference on Plasma Science,Norfolk:IEEE,2010.
[67] KRASHENINNIKOV E,RUSANOV V,SANYUK S,et al. Dissociation of hydrogen sulfide in an RF discharge[J]. Soviet Physics——Technical Physics,1986,31(6):645-648.
[68] ASISOV R,VAKAR A,GUTSOL A,et al. Plasmachemical methods of energy carrier production[J]. Int. J. Hydrogen Energy,1985,10(7):475-477.
[69] BAGAUTDINOV A,ZHIVOTOV V,KALACHEV I,et al. Dissociation of hydrogen sulfide in a mixture with carbon dioxide gas in a high-power microwave discharge[J]. Soviet Physics——Technical Physics,1991,36(4):488-490.
[70] BAGAUTDINOV A,JIVOTOV V,EREMENKO J,et al. Plasma chemical production of hydrogen from H₂S-containing gases in MCW discharge[J]. Int. J. Hydrogen Energy,1995,20(3):193-195.
[71] BAGAUTDINOV A,ZHIVOTOV V,KALACHEV I,et al. Investigations of the radial distributions of gas-flows in a high-power microwave-discharge[J]. High Energy Chemistry,1993,27(4):305-310.
[72] BAGAUTDINOV A,JIVOTOV V,EREMENKO Y,et al. Plasmachemical hydrogen production from natural gases containing hydrogen sulfide[J]. Hydrogen Energy Progress,1998,1:683-690.
[73] COX B G,CLARKE P F,PRUDEN B B. Economics of thermal dissociation of H₂S to produce hydrogen[J]. Int. J. Hydrogen Energy,1998,23(7):531-544.
[74] 董永治,王涵慧,俞稼镛. 微波等离子体方法分解H₂S制氢[J]. 太阳能学报,1997,18(2):142-145. DONG Y Z,WANG H H,YU J Y. Hydrogen production by H₂S microwave plasma dissociation[J]. Acta Energiae Solaris Sinica,1997,18(2):142-145.
[75] 汪建华,徐尧,高建保,等. 常压微波等离子体微波功率对硫化氢分解效率的影响[J]. 武汉工程大学学报,2013,35(3):34-37. WANG J H,XU Y,GAO J B,et al. Influence of microwave power on decomposition of hydrogen sulfide by atmospheric microwave plasma[J]. Journal of Wuhan Institute of Technology,2013,35(3):34-37.
[76] 徐尧,汪建华,高建保,等. 大气微波等离子体射流处理H₂S废气[J]. 强激光与粒子束,2013,25(11):2909-2913. XU Y,WANG J H,GAO J B,et al. Treatment of waste H₂S by atomospheric pressure microwave plasma jet[J]. High Power Laser and Particle Beams,2013,25(11):2909-2913.