PHR系列固定床渣油加氢催化剂的研制开发与工业应用

doi:10.16085/j.issn.1000-6613.2017-0854

化工进展 ›› 2018, Vol. 37 ›› Issue (10): 3867-3872.DOI: 10.16085/j.issn.1000-6613.2017-0854

PHR系列固定床渣油加氢催化剂的研制开发与工业应用

谭青峰¹, 聂士新², 程涛¹, 赵元生¹, 夏恩冬¹, 崔瑞利¹, 赵愉生¹, 姚元勋^2,

1 中国石油天然气股份有限公司石油化工研究院, 北京 102206;
2 大连西太平洋石油化工有限公司, 辽宁大连 116600

收稿日期:2017-05-10 修回日期:2017-10-28 出版日期:2018-10-05 发布日期:2018-10-05
通讯作者: 谭青峰(1977-),男,博士,高级工程师,研究方向为渣油加氢。
作者简介:谭青峰(1977-),男,博士,高级工程师,研究方向为渣油加氢。E-mail:tanqingfeng@petrochina.com.cn。

Development and application of PHR fixed-bed residue hydrotreating catalysts

TAN Qingfeng¹, NIE Shixin², CHENG Tao¹, ZHAO Yuansheng¹, XIA Endong¹, CUI Ruili¹, ZHAO Yusheng¹, YAO Yuanxun^2,

1 Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, China;
2 Dalian West Pacific Petrochemical Company Limited, Dalian 116600, Liaoning, China

Received:2017-05-10 Revised:2017-10-28 Online:2018-10-05 Published:2018-10-05

摘要/Abstract

摘要： 中国石油石油化工研究院通过深入研究渣油原料的结构组成与加氢转化行为特征，成功开发出包括保护剂、脱金属剂、脱硫剂和脱残炭剂4大类共12个牌号的PHR系列固定床渣油加氢催化剂。在保护剂中构建了"毫米-微米-纳米"多级孔体系，其微米级孔（PHR-402、PHR-403催化剂）与纳米级孔（PHR-404催化剂）均为双峰分布，微米级孔（PHR-402、PHR-403催化剂）主要分布在1μm附近区域和30~200μm的较宽泛区域，纳米级孔（PHR-404催化剂）的集中孔径则分别约为13nm和250nm，纳米级孔中大于100nm的孔比例达到35%。脱金属剂具有双峰分布的孔结构及内高外低的活性金属含量分布，其"扩散孔"孔径达到微米级（2300nm），大于100nm的孔比例超过20%。工业应用结果表明，PHR系列渣油加氢催化剂具有高而稳定的脱硫、脱氮、脱残炭等活性，催化剂内部孔结构的利用率高，且床层压降更低，有利于延长装置运转周期。

关键词: 催化剂, 固定床, 加氢, 扩散, 保护剂, 脱金属剂, 双峰孔

Abstract: Through the study of the structural and composition of residual oil and its conversion behavior under hydrotreatment conditions, Petrochemical Research Institute (PRI) of PetroChina has developed 12 kinds of PHR fixed-bed residue hydrotreating catalysts, which can be classified as guard catalysts, hydrodemetallization (HDM) catalysts, hydrodesulfurization (HDS) catalysts and hydrodecarbonation(HDCCR) catalysts. The PHR guard catalysts feature multi-scale pore system as they contain milli-, micro-and nano-pores. The pores at both micrometre (existed in PHR-402 and PHR-403 catalysts) and nanometre(existed in PHR-404 catalyst) levels exhibit dual-peak distribution. The micro-pores(existed in PHR-402 and PHR-403 catalysts) are sized around 1μm and between 30-200μm, respectively. The nano-pores(existed in PHR-404 catalysts) are sized at about 13nm and 250nm, respectively. Those nano-pores with pore size above 100nm take over 35% of all the nano-pores. The PHR HDM catalysts have dual-peak distribution in pore size as well, and metals distribute in an inner high and outer low manner. The diffusion pores can achieve micrometre scale(up to 2300nm) with over 20% pores bigger than 100nm. The industrial application results of PHR catalysts suggest that they have excellent activity and stability on the HDS, hydrodenitrogenation(HDN) and HDCCR of residue oils. The efficient use of inner pores of catalysts is achieved. In addition, the process pressure drop of the PHR catalysts is extremely low, which is an advantage for the long term operation of hydrotreating units.

Key words: catalyst, fixed bed, hydrogenation, diffusion, guard catalyst, hydrodemetallization catalyst, dual-peak distribution pore

中图分类号:

TE624

谭青峰, 聂士新, 程涛, 赵元生, 夏恩冬, 崔瑞利, 赵愉生, 姚元勋. PHR系列固定床渣油加氢催化剂的研制开发与工业应用[J]. 化工进展, 2018, 37(10): 3867-3872.

TAN Qingfeng, NIE Shixin, CHENG Tao, ZHAO Yuansheng, XIA Endong, CUI Ruili, ZHAO Yusheng, YAO Yuanxun. Development and application of PHR fixed-bed residue hydrotreating catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3867-3872.

参考文献

[1] 方向晨. 国内外渣油加氢处理技术发展现状及分析[J]. 化工进展, 2011, 30(1):95-104. FANG X C. Development of residuum hydroprocessing technologies[J]. Chemical Industry and Engineering Progress, 2011, 30(1):95-104.
[2] 石亚华, 牛传峰, 高永灿, 等. 渣油加氢技术的研究Ⅱ.渣油加氢与催化裂化双向组合技术(RICP)的开发[J]. 石油炼制与化工, 2005, 36(11):21-24. SHI Y H, NIU C F, GAO Y C, et al. Study on residue hydrotreating technologyⅡ. Development of bi-direction integration technology of VR hydrotreating with catalytic cracking[J]. Petroleum Processing and Petrochemicals, 2005, 36(11):21-24.
[3] 胡大为, 杨清河, 戴立顺, 等. 第三代渣油加氢RHT系列催化剂的开发及应用[J]. 石油炼制与化工, 2013, 44(1):11-15. HU D W, YANG Q H, DAI L S, et al. Development and commercial application of the third generation catalysts for resid hydrotreating[J]. Petroleum Processing and Petrochemicals, 2013, 44(1):11-15.
[4] 胡长禄, 赵愉生, 刘纪端, 等. 渣油固定床加氢处理技术的研究开发[J]. 炼油设计, 2001, 31(6):39-43. HU C L, ZHAO Y S, LIU J D, et al. Development of residue fixed-bed hydrotreating technologies[J]. Petroleum Refinery Engineering, 2001, 31(6):39-43.
[5] 刘喜来, 隋宝宽, 赵愉生. FZC-24B型渣油加氢脱金属催化剂的开发[J]. 石化技术与应用, 2007, 25(5):391-394. LIU X L, SUI B K, ZHAO Y S, et al. Development of FZC-24B type catalyst for residues hydrodemetallization[J]. Petrochemical Technology & Application, 2007, 25(5):391-394.
[6] 张春兰, 陈淑芬, 张远欣. 催化裂化催化剂的发展历程及研究进展[J]. 石油化工应用, 2013, 32(2):5-9. ZHANG C L, CHEN S F, ZHANG Y X. Development process and research progress of catalytic cracking catalyst[J]. Petrochemical Industry Application, 2013, 32(2):5-9.
[7] 李大东, 聂红, 孙丽丽. 加氢处理工艺与工程[M]. 2版. 北京:中国石化出版社, 2016:510. LI D D, NIE H, SUN L L. Hydrotreating process and engineering[M]. 2nd ed. Beijing:China Petrochemical Press, 2016:510.
[8] MARAFI A, HAUSER A, STANISLAUS A. Deactivation patterns of Mo/Al₂O₃ and NiMoP/Al₂O₃ catalysts in atmospheric residue hydrodesulphurization[J]. Catalysis Today, 2007, 125(3/4):192-202.
[9] 程涛, 赵愉生, 谭青峰, 等. PHR系列固定床渣油加氢脱金属催化剂的研制[J]. 化工进展, 2016, 35(10):3219-3225. CHENG T, ZHAO Y S, TAN Q F, et al. Development of PHR fix-bed residue hydrodemetallization catalysts[J]. Chemical Industry and Engineering Progress, 2016, 35(10):3219-3225.
[10] LIMBACH K W, WEI J. Effect of nonuniform activity on hydrodemetallation catalyst[J]. AIChE Journal, 1988, 34(2):305-313.

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PHR系列固定床渣油加氢催化剂的研制开发与工业应用

Development and application of PHR fixed-bed residue hydrotreating catalysts

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