Progress of simultaneous removal of hydrogen sulfide and phosphine from crude acetylene

doi:10.16085/j.issn.1000-6613.2015.02.037

Abstract

Abstract: The removal technologies of H₂S and PH₃ from crude acetylene gas are summarized. Specific methods as well as the advantages and disadvantages of wet process and dry process respectively are presented. Compared with the dry process,the wet process is more mature with the advantages of low price and easy operation,so it is widely used in removing H₂S and PH₃ from crude acetylene gas. However,the wet process will produce a large amount of wastewater,causing both environmental pollution and waste of water resources. At the same time,dissolved acetylene gas discharged into the sewage causes serious safety risks. Compared with the wet process,the dry process has the advantages of high removal efficiency,safety and pollution free. The dry process after improvement can remove H₂S and PH₃ from crude acetylene gas effectively with easy regeneration of purifying agent,and can overcome the shortcomings of the wet proces. Therefore,removal technology of H₂S and PH₃ from crude acetylene gas with the dry process has broad application prospect. However,the relevant mechanism of simultaneous removal of H₂S and PH₃ should be further studied.

Key words: crude acetylene gas, hydrogen sulfide(H₂S), phosphine(PH₃), simultaneous removal technologies, catalysis, recovery, safety

摘要： 综述了粗乙炔气净化处理硫化氢和磷化氢技术的研究进展,分别介绍了湿法工艺和干法工艺的具体方法以及存在的优缺点。湿法工艺相比干法更加成熟,兼具价格低廉和易于操作等优点,因而被广泛应用于粗乙炔气中硫磷的净化。然而,湿法工艺会产生大量废水,存在污染环境又浪费水资源的问题。同时溶解有乙炔气的废水排入下水管道,又存在严重的安全隐患。相比湿法工艺,干法工艺具有净化效率高、安全无污染的优点。研究表明,干法工艺经过改进,能有效地净化粗乙炔气中的H₂S和PH₃,并能有效克服湿法工艺存在的缺点,并且干法工艺的净化剂易于再生。因此,干法同时脱除粗乙炔气中的H₂S和PH₃具有较为广阔的应用前景。然而,干法工艺同时脱除H₂S和PH₃的相关机理还有待进一步研究。

关键词: 粗乙炔气, 硫化氢, 磷化氢, 同时脱除技术, 催化作用, 回收, 安全

CLC Number:

X511

LI Shan, HAO Jiming, LI Kai, TANG Lihong, LIU Ye. Progress of simultaneous removal of hydrogen sulfide and phosphine from crude acetylene[J]. Chemical Industry and Engineering Progree, 2015, 34(02): 534-541.

李山, 郝吉明, 李凯, 汤立红, 刘烨. 粗乙炔中H₂S、PH₃同时脱除技术研究进展[J]. 化工进展, 2015, 34(02): 534-541.

References

[1] 崔小明,聂颖. 干法乙炔生产技术的研究开发现状[J]. 化工科技市场,2009,32(10):1-5.
[2] Shan Tugen. Gas purfication process and practice for dissolved acetylene[J]. Low-Temperature and Specialty Gases,2010,28(2):14-16.
[3] 许亮,韩彦娟,张凯. 清洁工序废次钠水回收工艺改进[J]. 中国氯碱,2010(9):36-37.
[4] 王虎,黄德辉,张军. 次氯酸钠法净化乙炔气工艺的研究[J]. 辽宁化工,2008,27(7): 72-473.
[5] 赵树恒,陈广春,宁建英. 乙炔清净工序的改进[J]. 聚氯乙烯,2005(6):35-36.
[6] 王卫霞,耿彩军. 乙炔清净废水再利用研究[J]. 化学工程师,2007,139(4):34-35.
[7] 高建业. 次氯酸钠法净化工业粗乙炔工艺中废碱液的综合利用[J]. 山西化工,2005,25(1):61-62.
[8] 吴建华,丁玲,李太祥. 乙炔清净次氯酸钠溶液的循环新工艺[J]. 河南化工,2010,27(11):28-32.
[9] 唐红建,秦明月. 乙炔清净次氯酸钠废水的回用[J]. 聚氯乙烯,2013,41(9):41-43.
[10] 张伟,苗国敏,王延利. 乙炔清净用次氯酸钠溶液的配制[J]. 中国氯碱,2009(1):31-32.
[11] 赵永禄,赵辉,赵冠民. 乙炔清净工序废次氯酸钠的循环利用[J]. 聚氯乙烯,2009,37(5):39-41.
[12] 秦龙,秦国昌,徐素霞. 湿法乙炔生产中清净废液的回收利用[J]. 中国氯碱,2013(1):19-20.
[13] 侯德顺. 乙炔制备实验时洗液选择的探讨[J]. 辽宁化工,2009,38(6):384-385.
[14] 高建业. 电石渣水在次氯酸钠法净化乙炔气中的利用[J]. 科技情报开发与经济,2006,16(8):261-262.
[15] 赵小勇. 浓硫酸清净粗乙炔气工艺[J]. 聚氯乙烯,2009,37(7):39-40.
[16] 蔡生吉,张海青,康金福. 两种粗乙炔净化工艺的对比[J]. 云南化工,2010,37(5):34-37.
[17] 唐国龙. 聚氯乙烯乙炔浓硫酸清净项目投资概算[J]. 山西科技,2010,25(2):80-81.
[18] 齐有慧,张海全. 浓硫酸清净乙炔工艺的应用[J]. 聚氯乙烯,2010,38(11):10-11,46.
[19] 李群生,于颖. 聚氯乙烯工业生产新技术及其应用[J]. 聚氯乙烯,2012,40(10):1-6.
[20] 寻克义. 降低溶解乙炔硫磷含量的做法及思考[J]. 中国科技财富,2010(20):216.
[21] 杨文书. 溶解乙炔气中杂质的清除[J]. 河北化工,2010,33(5):36-37.
[22] 付汉卿,黄伟国,谢文晓. 氯水处理工艺改进[J]. 氯碱化工,2008,44(9):24-25.
[23] 于丽丽,唐晓龙,易红宏,等. 稀土对低浓度硫化氢液相催化氧化效率的影响[J]. 环境科学学报,2009,29(5):12-14.
[24] Baaziz W,Truong-Phuoc L,Duong-Viet C. Few lyer grapheme decorated with homogeneous magnetic Fe₃O₄ nanoparticles with tunable covering densities[J]. Journal of Materials Chemistry A,2014,2(8):2690-2700.
[25] Yi H H,Tang X L,Ning P,et al. Liquid phase catalytic oxidation of low-concentration H₂S in cerium doped absorption solution[J]. Journal of Rare Earths,2007,25:253-256.
[26] Shields M A,Dowling N I,Clark P D. Catalytic H₂S conversion and SO₂ production over iron oxide and iron oxide/gamma-Al₂O₃ in liquid sulfur[J]. Industrial & Engineering Chemistry Research,2007,46(23):7721-7728.
[27] Lee E K,Jung K D,Joo O S,et al. Liquid-phase oxidation of hydrogen sulfide to sulfur over CuO/MgO catalyst[J]. Reaction Kinetics and Catalysis Letters,2005,87(1):115-120.
[28] 李军燕,宁平,瞿广飞. Cu(Ⅱ)-Co(Ⅱ)液相催化氧化净化PH₃研究[J]. 武汉理工大学学报,2007,29(10):63-65,9.
[29] 李军燕,宁平,瞿广飞. PH₃液相催化氧化净化[J]. 昆明理工大学学报:理工版,2007,32(3):80-82,6.
[30] Monakhov K Y,Gourlaouen C. On the insertion of ML₂ (M=Ni,Pd,Pt; L=PH₃) into the E-Bi bond (E=C,Si,Ge,Sn,Pb) of a bicyclo[1. 1. 1]Pentane motif:A case for a carbenoid-stabilized Bi(0) species?[J]. Organo Metallics,2012,31(12):4415-4428.
[31] 宁平,易玉敏,瞿广飞. PdCl2-CuCl2液相催化氧化净化黄磷尾气中PH₃[J]. 中南大学学报:自然科学版,2009,40(2):340-345.
[32] 严召,童志权,张俊丰. Zn/Fe体系湿法催化氧化高效脱除沼气中H₂S的研究[J]. 环境工程学报,2008(1):135-139.
[33] Rakmak N,Wiyaratn W,Bunyakan C,et al. Synthesis of Fe/MgO nano-crystal catalysts by sot-gel method for hydrogen sulfide removal[J]. Chemical Engineering Journal,2010,162(1):84-90.
[34] Muthuraman G,Chung S J,Moon I S. The combined removal of methyl mercaptan and hydrogen sulfide via an electro-reactor process using a low concentration of continuously regenerable Ag(Ⅱ) active catalyst[J]. Journal of Hazardous Materials,2011,193:257-263.
[35] Govindan M,Chung S J,Jang J W,et al. Removal of hydrogen sulfide through an electrochemically assisted scrubbing process using an active Co(Ⅲ) catalyst at low temperatures[J]. Chemical Engineering Journal,2012,209:601-606.
[36] 杨丽娜,易红宏,唐晓龙. Fe-Cu混合氧化物催化湿式氧化低浓度磷化氢实验研究[J]. 中南大学学报:自然科学版,2009,40(6):1505-1509.
[37] 杨宇静,明大增,李志祥. 硫化氢分解制氢的研究进展[J]. 无机盐工业,2013,45(2):5-7,14.
[38] Gurunathan K,Baeg J O,Lee S M,et al. Visible light assisted highly efficient hydrogen production from H₂S decomposition by CuGaO₂ and CuGa1-xInxO₂ delafossite oxides bearing nanostructured co-catalysts[J]. Catalysis Communications,2008,9(3):395-402.
[39] Zakharov I I,Startsev A N,Voroshina O V,et al. The molecular mechanism of low-temperature decomposition of hydrogen sulfide under conjugated chemisorption-catalysis conditions[J]. Russian Journal of Physical Chemistry,2006,80(9):1403-1410.
[40] Albenze E J,Shamsi A. Density functional theory study of hydrogen sulfide dissociation on Bi-metallic Ni-Mo catalysts[J]. Surface Science,2006,600(16):3202-3216.
[41] Ishihara A,Mochizuki H,Lee J,et al. Development of hydrodesulfurization catalysts using molybdenum complex with molybdenum-sulfur bonds (Part 1)-Effect of activation method on catalytic activity[J]. Journal of the Japan Petroleum Institute,2005,48(3):137-144.
[42] Ling L X,Song J J,Zhao S P,et al. DFT study on the effects of defect and metal-doping on the decomposition of H₂S on the alpha-Fe₂O₃(0001) surface[J]. R. S. C Advances,2014,4(43):22411-22418.
[43] Li L,Han C,Han X. Catalytic decomposition of toxic chemicals over metal-promoted carbon nanotubes[J]. Environmental Science &Technology,2011,45(2):726-731.
[44] Li Lili,Chen Can,Chen Long,et al. Catalytic decomposition of toxic chemicals over iron group metals supported on carbon nanotubes[J]. Environmental Science & Technology,2014,48(6):3372-3377.
[45] Li L L,Zhang B G. The nature of PH₃ decomposition reaction over amorphous CoNiBP alloy supported on carbon nanotubes[J]. Industrial & Engineering Chemistry Research,2010,9(4):1658-1662.
[46] Han C X,Ren J L,Tang X J,et al. Preparation of nanometer FeCuP alloy and its application in decomposition of PH₃[J]. Chinese Chemical Letters,2007,18(10):1285-1288.
[47] Han C X,Lin X M,Zhang B G. Effect of support TiO₂ on the characteristics of Co-P amorphous alloy[J]. Acta Chimica Sinica,2007,65(9):793-797.
[48] Wang X,Ning P,Shi Y. Adsorption of low concentration phosphine in yellow phosphorous off-gas by impregnated activated carbon[J]. Journal of Hazardous Materials,2009,171(1-3):588-593.
[49] Ma L P,Ning P,Zhang Y. Experimental and modeling of fixed-bed reactor for yellow phosphorous tail gas purification over impregnated activated carbon[J]. Chemical Engineering Journal,2008,137(3):471-479.
[50] Quinn R,Dahl T A,Diamond B W. Removal of arsine from synthesis gas using a copper on carbon adsorbent[J]. Industrial & Engineering Chemistry Research,2006,45(18):6272-6278.
[51] Fang H B,Zhao J T,Fang Y T,et al. Selective oxidation of hydrogen sulfide to sulfur over activated carbon-supported metal oxides[J]. Fuel,2013,108:143-148.
[52] Sun F G,Liu J,Chen H C. Nitrogen-rich mesoporous carbons:Highly efficient,regenerable metal-free catalysts for low-temperature oxidation of H₂S[J]. Acs Catalysis,2013,3(5):862-870.
[53] 蒋明,宁平,徐浩东,等. 改性活性炭吸附净化低浓度磷化氢[J]. 高校化学工程学报,2012(4):685-691.
[54] 高红,张勇,宁平. 金属改性脱除PH₃和H₂S动力学及反应机理研究[J]. 环境工程学报,2009,3(2):301-305.
[55] 徐浩东,宁平,蒋明,等. 净化PH₃和H₂S气体改性活性炭的制备与表征[J]. 环境科学学报,2008,18(7):1365-1369.
[56] Rupp E C,Granite E J,Stanko D C. Laboratory scale studies of Pd/gamma-Al₂O₃ sorbents for the removal of trace contaminants from coal-derived fuel gas at elevated temperatures[J]. Fuel,2013,108:131-136.