H2S/H2硫化温度对MoP/SiO2催化剂硫醚化性能的影响

王立稳; 李风旭; 李明丰; 褚阳; 陈吉祥

H₂S/H₂硫化温度对MoP/SiO₂催化剂硫醚化性能的影响

1.
天津大学化工学院催化科学与工程系, 天津市应用催化科学与工程重点实验室, 天津 300350
2.
中国石化石油化工科学研究院, 北京 100083

基金项目:

石油化工催化材料与反应工程国家重点实验室 RIPP, SINOPEC

详细信息

通讯作者:
陈吉祥, E-mail:jxchen@tju.edu.cn

中图分类号: O643
计量
- 文章访问数: 92
- HTML全文浏览量: 38
- PDF下载量: 9
- 被引次数: 0
出版历程
- 收稿日期: 2018-10-17
- 修回日期: 2019-03-23
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-05-10

Effect of H₂S/H₂ sulfuration temperature on performance of MoP/SiO₂ catalyst for thioetherification

1.
Department of Catalysis Science and Engineering, Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
2.
Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China

Funds:

The project was supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering RIPP, SINOPEC

摘要

摘要: 以负载磷酸钼为前驱体，采用程序升温还原法制备了MoP/SiO₂催化剂，以体积分数3%H₂S/H₂对其进行了硫化处理，利用XRD、CO化学吸附、NH₃-TPD、HRTEM-EDX、ICP-AES以及XPS等手段对催化剂进行了表征，研究了硫化温度对MoP/SiO₂催化剂结构和异戊二烯与正丁硫醇硫醚化性能的影响。结果表明，即使在400℃硫化处理也未改变MoP/SiO₂催化剂中MoP体相结构；随着硫化温度提高，催化剂表面酸量增加、金属位数量减少，降低了催化剂C-S键氢解及异戊二烯深度加氢活性，但同时也提高了催化剂烯烃聚合活性。经120℃硫化处理的MoP/SiO₂兼具较佳硫醚化及异戊二烯选择加氢性能。
- 磷化钼 /
- 硫化温度 /
- 硫醚化 /
- 选择加氢
Abstract: The MoP/SiO₂ catalyst was prepared from the supported Mo phosphate by the H₂-TPR method and treated with 3%H₂S/H₂ at different temperatures. The as-prepared catalysts were characterized by means of XRD, HRTEM-EDX, XPS, NH₃-TPD, ICP-AES and CO chemisorption and tested for the thioetherification of isoprene and n-butylmercaptan. The effects of sulfuration temperature on the MoP/SiO₂ catalyst structure and thioetherification performance were investigated. The results showed that the MoP phase was still stable even at the sulfuration temperature of 400 ℃. As the sulfuration temperature increased, the acid amount of the catalysts increased while the surface metal site density decreased. As a result, in the thioetherification of isoprene and n-butylmercaptan, the C-S bond hydrogenolysis and the over-hydrogenation of isoprene were suppressed on the sulfurized catalysts, while the olefin polymerization was promoted. Relatively, the MoP/SiO₂ catalyst sulfurized at 120 ℃ had better performance for the thioetherification and the selective hydrogenation of isoprene.
- molybdenum phosphide /
- sulfuration temperature /
- thioetherification /
- selective hydrogenation

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图 1 不同温度3%H₂S/H₂处理的MoP/SiO₂催化剂的XRD谱图

a: MoP; b: MoP-120S; c: MoP-200S; d: MoP-300S; e: MoP-400S

Figure 1 XRD patterns of the MoP catalysts treated with 3%H₂S/H₂ at different temperatures

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图 2 MoP(a)、MoP-120S(b)与MoP-400S(c)催化剂的HRTEM照片

Figure 2 HRTEM images of the catalysts (a): MoP; (b): MoP-120S; (c): MoP-400S

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图 3 MoP、MoP-120S和MoP-400S催化剂中Mo 3d的XPS谱图

Figure 3 XPS spectra of Mo 3d on MoP, MoP-120S and MoP-400S

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图 4 MoP、MoP-120S和MoP-400S催化剂中P 2p的XPS谱图

Figure 4 XPS spectra of P 2p on MoP, MoP-120S and MoP-400S

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图 5 MoP、MoP-120S和MoP-400S催化剂中S 2p的XPS谱图

Figure 5 XPS spectra of S 2p on MoP, MoP-120S and MoP-400S

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图 6 不同温度3%H₂S/H₂处理的MoP/SiO₂催化剂的NH₃-TPD谱图

a: MoP; b: MoP-120S; c: MoP-200S; d: MoP-300S; e: MoP-400S

Figure 6 NH₃-TPD profiles of the catalysts treated with 3%H₂S/H₂ at different temperatures

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图 7 硫醚化过程中发生的反应示意图

Figure 7 Reactions during thioetherification process

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图 8 硫化温度对MoP/SiO₂催化剂正丁硫醇转化率的影响

Figure 8 Effect of sulfuration temperature on n-butanethiol conversion over MoP/SiO₂ catalyst

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图 9 硫化温度对MoP/SiO₂催化剂C4组分选择性的影响

Figure 9 Effect of sulfuration temperature on the selectivity to C4 hydrocarbons over MoP/SiO₂ catalysts

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图 10 硫化温度对MoP/SiO₂催化剂异戊二烯转化率的影响

Figure 10 Effect of sulfuration temperature on isoprene conversion over MoP/SiO₂ catalysts

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图 11 硫化温度对MoP/SiO₂催化剂C5组分(实线)与单烯烃选择性(虚线)的影响

Figure 11 Effect of sulfuration temperature on the selectivity of C5 hydrocarbons (solid line) and mono-olefin component (dash line) over MoP/SiO₂ catalysts

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表 1 MoP、MoP-120S与MoP-400S中Mo:P及Mo:P:S原子比

Table 1 Mo:P and Mo:P:S atomic ratios in MoP, MoP-120S and MoP-400S

Catalyst	Mo:P:S (atomic ratio)
MoP	1:0.86:0
MoP-120S	1:0.84:0.14
MoP-400S	1:0.67:0.28

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表 2 MoP、MoP-120S与MoP-400S表面原子比

Table 2 Mo:P and Mo:(P+S) atomic ratios on MoP, MoP-120S and MoP-400S

Catalyst	Mo:P (atomic ratio)	Mo:(P+S) (atomic ratio)
MoP	1.03	1.03
MoP-120S	1.09	1.09
MoP-400S	1.12	0.92

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表 3 不同温度H₂S/H₂处理的MoP/SiO₂催化剂的相对酸量与CO吸附量

Table 3 Relative acid amounts and CO uptakes of MoP/SiO₂ catalysts treated with H₂S/H₂ at different temperatures

Catalyst	Relative acid amount^a	CO uptake/ (μmol·g^-1)
MoP	1.00	89
MoP-120S	1.49	50
MoP-200S	1.82	30
MoP-300S	1.95	26
MoP-400S	2.49	17
^a: designing the acid amount of MoP as 1.00

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参考文献(26)

[1]	BRUNET S, MEY D, PÉROT G, BOUCHY G, DIEHL F. On the hydrodesulfurization of FCC gasoline:A review[J]. Appl Catal A:Gen, 2005, 278(2):143-172. doi: 10.1016/j.apcata.2004.10.012
[2]	SONGC.Anoverviewofnewapproachestodeepdesulfurizationforultra-cleangasoline, dieselfuelandjetfuel[J].Catal Today, 2003, 86(1):211-263. https://www.onacademic.com/detail/journal_1000034202600910_0952.html
[3]	PETTITI I, BOTTO I L, CABELLO C I, COLONNA C, FATICANTI M, MINELLI G, PORTA P, THOMAS H J. Anderson-type heteropolyoxomolybdates in catalysis 2. EXAFS study on λ-Al₂O₃-supported Mo, Co and Ni sulfided phases as HDS catalysts[J]. Appl Catal A:Gen, 2001, 220(1):113-121.
[4]	孟祥东, 周洪涛, 孙守华.催化裂化汽油选择性加氢脱硫装置的工艺选择[J].石化技术与应用, 2014, 32(4):332-336. doi: 10.3969/j.issn.1009-0045.2014.04.012 MENG Xiang-dong, ZHOU Hong-tao, SUN Shou-hua. Process selection of selective hydrodesulfurization unit of catalytic cracking gasoline[J]. Petrochem Technol Appl, 2014, 32(4):332-336. doi: 10.3969/j.issn.1009-0045.2014.04.012
[5]	肖招金, 黄星亮.镍基催化剂上硫醇与异戊二烯硫醚化反应的研究[J].分子催化, 2005, 19(4):280-284. doi: 10.3969/j.issn.1001-3555.2005.04.009 XIAO Zhao-jin, HUANG Xing-liang. Study of mercaptans and isoprene thioetherfication reaction on nickel catalyst[J]. J Mol Catal (China), 2005, 19(4):280-284. doi: 10.3969/j.issn.1001-3555.2005.04.009
[6]	肖招金, 黄星亮.制备条件对Ni/Al₂O₃催化剂二烯硫醚化性能的研究[J].石油化工, 2004, 33(s1):381-382. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syhg2004z1154 XIAO Zhao-jin, HUANG Xing-liang. Effect of preparation conditions on the catalytic properties of Ni/Al₂O₃ catalyst in the diene thioetherfication reaction[J]. Petrochem Technol, 2004, 33(s1):381-382. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syhg2004z1154
[7]	肖招金, 黄星亮, 童宗文.制备条件对二烯硫醚化催化剂Ni/Al₂O₃催化性能的影响[J].石油炼制与化工, 2006, 37(5):24-28. doi: 10.3969/j.issn.1005-2399.2006.05.006 XIAO Zhao-jin, HUANG Xing-liang, TONG Zong-wen. Effect of preparation conditions on the catalytic properties of Ni/Al₂O₃ catalyst in the diene thioetherfication reaction[J]. Pet Process Petrochem, 2006, 37(5):24-28. doi: 10.3969/j.issn.1005-2399.2006.05.006
[8]	申志兵, 柯明, 张君涛, 张智平, 梁生荣. Mo-Ni/Al₂O₃催化剂对FCC汽油硫醚化反应的催化性能[J].石油学报(石油加工), 2015, 31(6):1269-1274. doi: 10.3969/j.issn.1001-8719.2015.06.003 SHEN Zhi-bing, KE Ming, ZHANG Jun-tao, ZHANG Zhi-ping, LIANG Sheng-rong. Catalytic performance of Mo-Ni/Al₂O₃ for thioetherfication of FCC gasoline[J]. Acta Pet Sin(Pet Process Sect), 2015, 31(6):1269-1274. doi: 10.3969/j.issn.1001-8719.2015.06.003
[9]	SHEN Z B, KE M, YU P, HU H Q, SONG Z Z, JIANG Q Z. Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al₂O₃ catalysts[J]. J Mol Catal A:Chem, 2015, 396:120-127. doi: 10.1016/j.molcata.2014.09.034
[10]	SHEN Z B, KE M, YU P, LIU S D, SONG Z Z, JIANG Q Z. Catalytic activities of mo-modified Ni/Al₂O₃ catalysts for thioetherification of mercaptans and di-olefins in fluid catalytic cracking naphtha[J]. Transition Met Chem, 2012, 37(6):587-593. doi: 10.1007/s11243-012-9625-0
[11]	HUANG D Q, KE M, BAO X J, LIU H Y. Fe-promoted Ni/Al₂O₃ thioetherification catalysts with enhanced low temperature activity for removing mercaptans from liquefied petroleum gas[J]. Ind Eng Chem Res, 2016, 55(5):1192-1201. doi: 10.1021/acs.iecr.5b03797
[12]	OYAMA S T. Novel catalysts for advanced hydroprocessing:Transition metal phosphides[J]. J Catal, 2003, 216(1):343-352. http://cn.bing.com/academic/profile?id=8ca04206cbb6816a006940f96b887358&encoded=0&v=paper_preview&mkt=zh-cn
[13]	OYAMA S T, GOTT T, ZHAO H Y, LEE Y K. Transition metal phosphide hydroprocessing catalysts:A review[J]. Catal Today, 2009, 143(1):94-107. http://d.old.wanfangdata.com.cn/NSTLQK/NSTL_QKJJ0226572816/
[14]	LEE Y K, OYAMA S T. Bifunctional nature of a SiO₂ -supported Ni₂P catalyst for hydrotreating:EXAFS and FTIR studies[J]. J Catal, 2006, 239(2):376-389. doi: 10.1016/j.jcat.2005.12.029
[15]	CHEN J X, SHI H, LI L, LI K L. Deoxygenation of methyl laurate as a model compound to hydrocarbons on transition metal phosphide catalysts[J]. Appl Catal B:Environ, 2014, 144(2):870-884. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=00b3e67f7ee6f634b85d8c66a8128355
[16]	REN T Y, LI M F, CHU Y, CHEN J X. Thioetherification of isoprene and butanethiol on transition metal phosphides[J]. J Energy Chem, 2018, 27(3):930-939. doi: 10.1016/j.jechem.2017.07.017
[17]	PHILLIPS D C, SAWHILL S J, SELF R, BUSSELL M E. Synthesis, characterization, and hydrodesulfurization properties of silica-supported molybdenum phosphide catalysts[J]. J Catal, 2002, 207(2):266-273. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=0cf89dcb3cf46344a2cd0f0502028982
[18]	CHEN J X, YANG Y, SHI H, LI M F, CHU Y, PAN Z Y, YU X B. Regulating product distribution in deoxygenation of methyl laurate on silica-supported Ni-Mo phosphides:Effect of Ni/Mo ratio[J]. Fuel, 2014, 129(7):1-10. http://cn.bing.com/academic/profile?id=fac1698e18875be086a43c6b56897eea&encoded=0&v=paper_preview&mkt=zh-cn
[19]	LI K L, WANG R J, CHEN J X. Hydrodeoxygenation of anisole over silica-supported Ni₂P, MoP, and NiMoP catalysts[J]. Energy Fuels, 2011, 25(3):854-863. doi: 10.1021/ef101258j
[20]	ZHANG Z N, TANG M X, CHEN J X. Effects of P/Ni ratio and Ni content on performance of λ-Al₂O₃-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons[J]. Appl Surf Sci, 2016, 360(4):353-364. http://www.sciencedirect.com/science/article/pii/S016943321502601X
[21]	SUN F X, WU W C, WU Z L, GUO J, WEI Z B, YANG Y X, JIANG Z X, TIAN F P, LI C. Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported MoP, Ni₂P, and NiMoP catalysts[J]. J Catal, 2004, 228(2):298-310. doi: 10.1016/j.jcat.2004.09.002
[22]	WU Z L, SUN F X, WU W C, FENG Z C, LIANG C H, WEI Z B, LI C. On the surface sites of MoP/SiO₂ catalyst under sulfiding conditions:Ir spectroscopy and catalytic reactivity studies[J]. J Catal, 2004, 222(1):41-52. http://cn.bing.com/academic/profile?id=6520cd12ec9960d32386c397be1f78f6&encoded=0&v=paper_preview&mkt=zh-cn
[23]	BAI J, LI X, WANG A J, PRINS R WANG Y. Different role of H₂S and dibenzothiophene in the incorporation of sulfur in the surface of bulk MoP during hydrodesulfurization[J]. J Catal, 2013, 300(3):197-200. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=f55bf796bc845fe997533f8536141dfd
[24]	SHEN Z B, KE M, YU P, HU H Q, SONG Z Z, JIANG Q Z. Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al₂O₃catalysts[J]. J Mol Catal A:Chem, 2015, 396:120-127. doi: 10.1016/j.molcata.2014.09.034
[25]	WILSON R L, KEMBALL C. Catalytic reactions of methyl mercaptan on disulfides of molybdenum and tungsten[J]. J Catal, 1964, 3(5):426-437. doi: 10.1016/0021-9517(64)90145-9
[26]	周志远, 黄星亮, 张燕, 李健.二烯硫醚化酸性催化剂研究[C]//全国青年催化学术会议.北京: 中国石化出版社, 2007. ZHOU Zi-yuan, HUANG Xing-liang, ZHANG Yan, LI Jian. Study on the acid catalysts for diene thioetherification[C]//National Youth Catalysis Conference. Beijing: China Petrochemical Press, 2007.