Progress in preparation research and industrial application of SO42-/ZrO2catalysts for light paraffin isomerization

doi:10.16085/j.issn.1000-6613.2019-0112

Abstract

Abstract:

Sulfated zirconia solid acid (SO₄^2-/ZrO₂) provides the great potential as a new-generation catalyst for light paraffin isomerization, which combines the high catalytic activity, regenerability with the environmental-friendly character. The progresses of industrial application of light naphtha catalyzed by sulfated zirconia are summarized, including the current market situation, commercial technologies and technical economy. The research progresses on the catalyst preparation technologies reported in the patents and literature are also reviewed. The effects of crucial preparation parameters on their influences on the catalysts structure and isomerization performance are deeply discussed, including precipitation and calcination conditions of precursor, the addition and modification of promoters, pretreatment conditions of catalysts and influence of water content of raw materials. Finally, the challenges of catalyst preparation and industrialization are analyzed and the corresponding suggestions are given. We also propose the future direction of the catalysts development, that is to broaden the adoption of raw materials, develop the new synthesis techniques and promoters, and the catalyst regeneration technology.

Key words: light paffafin, isomerization, catalyst, preparation, industrial application

摘要：

硫酸化氧化锆固体酸（SO₄^2-/ZrO₂）烷烃异构化催化剂兼具高活性、可再生和环境友好的优点，具有广阔的应用前景。本文综述了SO₄^2-/ZrO₂催化剂在轻质烷烃异构化中的工业应用进展，包括市场现状、现有技术、经济性等方面，并对专利和文献中报道的催化剂制备技术进行了论述总结。重点针对催化剂的关键制备参数以及对催化剂结构和异构化性能的影响进行了深入分析和探讨，包括氢氧化物前体的沉淀和焙烧条件、助剂的添加和改性作用、催化剂预处理条件和原料水含量的影响等。最后对催化剂开发和工业化中的难点给出了分析和建议，并展望了未来的催化剂发展方向，指出拓宽催化剂的原料适应性、发展新型制备技术和助剂体系、结合催化剂再生等工艺研究是未来的发展方向。

关键词: 轻质烷烃, 异构化, 催化剂, 制备, 工业应用

CLC Number:

TQ426.6

Rui WANG,Xue YANG,Ping MIAO. Progress in preparation research and industrial application of SO₄^2-/ZrO₂catalysts for light paraffin isomerization[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4930-4940.

王锐,阳雪,缪平. SO₄^2-/ZrO₂轻质烷烃异构化催化剂的制备和工业应用进展[J]. 化工进展, 2019, 38(11): 4930-4940.

Figures/Tables 6

References 80

1	张晓华, 孙会东, 邢定峰, 等. 浅谈轻石脑油异构化在国内炼油厂的应用[J]. 石油规划设计, 2015, 26(5): 26-28.
	ZHANGXiaohua, SUNHuidong, XINGDingfeng, et al. The application of light naphtha isomerization in domestic refineries [J]. Petroleum Planning & Engineering, 2015, 26(5): 26-28.
2	马爱增, 于中伟, 张秋平, 等. 从石脑油和轻烃资源增产汽油的技术及措施[J]. 石油炼制与化工, 2009, 40(11): 1-7.
	MAAizeng, YUZhongwei, ZHANGQiuping, et al. Technologies for increasing gasoline production from naphtha and light hydrocarbons[J]. Petroleum Processing and Petrochemicals, 2009, 40(11): 1-7.
3	赵文康, 樊洁, 朱博超, 等. 异构化制清洁汽油工艺及催化剂[J]. 化工进展, 2016, 35(8): 2455-2463.
	ZHAOWenkang, FANJie, ZHUBochao, et al. Isomerization process for producing clean gasoline and the catalyst[J]. Chemical Industry and Engineering Progress, 2016, 35(8): 2455-2463.
4	KIMURAT. Development of Pt/SO₄^2-/ZrO₂, catalyst for isomerization of light naphtha[J]. Catalysis Today, 2003, 81(1): 57-63.
5	钱伯章. 新型异构化催化剂获应用[J]. 精细石油化工进展, 2004, 34(7): 19.
	QIANBozhang. Application of new type isomerization catalyst [J]. Advances in Fine Petrochemicals, 2004, 34(7): 19.
6	Worldwide Refinery Processing. Review: 4Q 2014 review fluid catalytic cracking and isomerization[R]. US: Hydrocarbon Publishing Company, 2013.
7	田爱珍, 杨周侠, 汪毅, 等. 轻石脑油异构化工艺技术研究进展[J]. 应用化工, 2015(3): 558-562.
	TIANAizhen, YANGZhouxia, WANGYi, et al. Advanced research progress of light naphtha isomerization technology[J]. Applied Chemical Industry, 2015(3): 558-562.
8	威海市环境保护科学研究所有限公司. 山东金诚石化集团有限公司油品质量(国Ⅴ)升级及配套改造项目环境影响评价变更报告[EB/OL]. 2016-04. .
	Weihai Environment Protection Science Institute Company Limited. Report on the change of environmental impact assessment on the project “fuel quality upgrading (national Ⅴ) and its associated revamping” of shandong jincheng petrochemical group company limited[EB/OL]. 2016-04. .
9	许建耘. 用于C₅、C₆和C₇轻石脑油的异构化技术Isomalk[J]. 石油炼制与化工, 2015(7): 77.
	XUJianyun. C5, C₆, C₇ light naphtha isomerization technology isomalk[J]. Petroleum Processing and Petrochemicals, 2015(7): 77.
10	SHAKUNA N, FEDOROVAM L. Isomerization of light gasoline fractions: the efficiency of different catalysts and technologies[J]. Catalysis in Industry, 2014, 6(4): 298-306.
11	钱伯章. GTC技术公司在中国转让异构化工艺[J]. 石油炼制与化工, 2014(7): 86.
	QIANBozhang. GTC licensed isomerization technology to company in China[J]. Petroleum Processing and Petrochemicals, 2014(7): 86.
12	SULLIVAND, METROS, PUJADÓP R. Isomerization in petroleum processing[M]. Berlin: Springer International Publishing, 2014.
13	杜云散. C₅/C₆固体酸异构化的反应建模与工艺条件研究[J]. 科技创新导报, 2018(26): 93-96.
	DUYunsan. Study on the reaction modeling and process parameters for C₅/C₆ isomerization catalyzed by solid acid[J]. Science and Technology Innovation Herald, 2018(26): 93-96.
14	王昊, 刘彦, 李劭, 等. C₅/C₆烷烃异构化装置的技术流程选择[J]. 当代化工, 2019, 48(1): 166-169.
	WANGHao, LIUYan, LIShao, et al. Process selection of C₅/C₆ isomerization unit[J]. Contemporary Chemical Industry, 2019, 48(1): 166-169.
15	中国石化石油化工科学研究院科研处. “固体超强酸C₅/C₆异构化技术开发及工业试验”项目通过评审[J]. 石油炼制与化工, 2017, 48(6): 13.
	Research Office of Sinopec Research Institute of Petroleum Processing. Project of “solid acid C₅/C₆isomerization development and industrial” passed evaluation[J]. Petroleum Processing and Petrochemicals, 2017, 48(6): 13.
16	中国石化石油化工科学研究院科研处. 国内首套固体超强酸C₅、C₆异构化装置顺利投产[J]. 石油炼制与化工, 2016(11): 72.
	Research Office of Sinopec Research Institute of Petroleum Processing. First solid superacid acid C₅/C₆ isomerization unit in China started production successfully[J]. Petroleum Processing and Petrochemicals, 2016(11): 72.
17	章红艳, 宋月芹, 倪海微, 等. 固体超强酸C₅/C₆异构化催化剂成型及寿命研究[J]. 石油炼制与化工, 2018, 49(9): 82-89.
	ZHANGHongyan, SONGYueqin, NIHaiwei, et al. Modeling and lifetime test of solid superacid catalyst for n-C₅/C₆ isomerization[J]. Petroleum Processing and Petrochemicals, 2018, 49(9):82-89.
18	倪海微, 宋月芹, 周思侬, 等. 氧化铝成型的Pt-SO₄^2-/ZrO₂-Al₂O₃上n-C₅⁰/C₆⁰的异构化性能[J]. 化工进展, 2019, 38(6): 2806-2812.
	NIHaiwei, SONGYueqin, ZHOUSinong, et al. n-C₅⁰/C₆⁰isomerization performance over alumina-shaped Pt-SO₄^2-/ZrO₂-Al₂O₃catalyst[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2806-2812.
19	BABAS, SHIBATAY, KAWAMURAT, et al. Solid strong acid catalyst process for the production of the same and use there of: US5036035A[P]. 1991-07-30.
20	GILLESPIER D, COHNM J. High-activity isomerization catalyst and process: US6706659B2[P]. 2004-03-16.
21	潘晖华, 于中伟, 濮仲英. 一种固体超强酸催化剂及制备方法: CN1168533C[P]. 2004-09-29.
	PANHuihua, YUZhongwei, PUZhongying. A solid superacid catalysts and its preparation method: CN1168533C[P]. 2004-09-29.
22	SCHMIDTF. New catalyst preparation technologies-observed from an industrial viewpoint[J]. Applied Catalysis A: General, 2001, 221(1): 15-21.
23	范书信, 于中伟, 濮仲英. 固体超强酸催化剂及其制备方法: CN1159099C[P]. 2004-07-28.
	FANShuxin, YUZhongwei, PUZhongying. Solid superacid catalysts and its preparation method: CN1159099C[P]. 2004-07-28.
24	SHAKUNA N, FedorovaM L. Method of isomerization of light gasoline fractions: RU2321575[P]. 2006-06-19.
25	亚历山德·尼基托维奇·沙昆. 轻汽油馏分的异构化方法: CN101365667B[P]. 2009-02-11.
	SHAKUNA N. Method of isomerization of light gasoline fractions: CN101365667B[P]. 2009-02-11.
26	URZHUNTSEVG A, OVCHINNIKOVAE V, CHUMACHENKOV A, et al. Isomerization of n-butane over Pd-SO₄^2-/ZrO₂ catalyst: prospects for commercial application[J]. Chemical Engineering Journal, 2014, 238: 148-156.
27	LIX, NAGAOKAK, LERCHERJ A. Labile sulfates as key components in active sulfated zirconia for n-butane isomerization at low temperatures[J]. Journal of Catalysis, 2004, 227(1): 130-137.
28	KLOSEB S, JENTOFTF C, JOSHIP, et al. In situ spectroscopic investigation of activation, start-up and deactivation of promoted sulfated zirconia catalysts[J]. Catalysis Today, 2006, 116(2): 121-131.
29	汪颖军, 刘成双, 李小辉. SO₄^2-/ZrO₂催化烷烃异构化反应的研究进展[J]. 石油化工, 2010, 39(1): 94-106.
	WANGYingjun, LIUChengshuang, LIXiaohui. Research progress of SO₄^2-/ZrO₂catalyst in alkanes isomerization[J]. Petrochemical Technology, 2010, 39(1): 94-106.
30	缪长喜, 陈建民, 高滋. SO₄^2-/ZrO₂超强酸制备方法的改进[J]. 高等学校化学学报, 1995(4): 591-594.
	MIAOChangxi, CHENJianmin, GAOZi. An improvement on the preparation of SO₄^2-/ZrO₂ superacid [J]. Chemical Journal of Chinese Universities, 1995(4): 591-594.
31	范书信. 正戊烷异构化固体超强酸催化剂的研究[D]. 北京: 中国石化石油化工科学研究院, 2001.
	FANShuxin. Study on solid superacid catalyst for n-pentane isomerization[D]. Beijing: Sinopec Research Institute of Petroleum Processing, 2001.
32	SERRAJ M, CHICAA, CORMAA. Development of a low temperature light paraffin isomerization catalysts with improved resistance to water and sulphur by combinatorial methods[J]. Applied Catalysis A: General, 2003, 239(1): 5-42.
33	BELSKAYAO B, DANILOVAI G, KAZAKOVM O, et al. Investigation of active metal species formation in Pd-promoted sulfated zirconia isomerization catalyst[J]. Applied Catalysis A: General, 2010, 387(1): 1-12.
34	乐晓光, 徐俊, 宋月芹, 等. 制备条件对Pt/SO₄^2-/ZrO₂-Al₂O₃异构化性能的影响[J]. 化工进展, 2015, 34(2): 419-424.
	LEXiaoguang, XUJun, SONGYueqin, et al. Effect of preparation conditions on isomerization performance of Pt/SO₄^2-/ZrO₂-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2015, 34(2): 419-424.
35	曹崇江. Al、Ga促进的SO₄^2-/ZrO₂烷烃异构化催化剂研究[D]. 南京:南京工业大学, 2005.
	CAOChongjiang. Studies on Al- and Ga- promoted sulfated zirconia for alkane isomerization [D]. Nanjing: Nanjing University of Technology, 2005.
36	AFANASIEVP, THIOLLIERA, BREYSSEM, et al. Control of the textural properties of zirconium oxide[J]. Topics in Catalysis, 1999, 8(3/4): 147-160.
37	李文, 殷元骐. 制备条件对ZrO₂晶相结构的影响[J]. 分子催化, 1999(4): 275-276.
	LIWen, YINYuanqi. Effect of preparation conditions on the crystalline structure of ZrO₂[J]. Journal of Molecular Catalysis (China), 1999(4): 275-276.
38	CORMAA, FORNESV, JUANRAJADELLM I, et al. Influence of preparation conditions on the structure and catalytic properties of SO₄^2-/ZrO₂ superacid catalysts[J]. Applied Catalysis A: General, 1994, 25(51): 151-163.
39	KUZNETSOVP N, KUZNETSOVAL I, TVERDOKHLEBOVV P, et al. Method of preparing n-butane-into-isobutane isomerization catalyst: RU2236291C1[P]. 2002-12-26.
40	KUZNETSOVP N, KUZNETSOVAL I, KAZBANOVAA V. Catalytic isomerisation of alkanes on anion-modified forms of zirconium dioxide[J]. Chemistry for Sustainable Development, 2010, 18: 253-264.
41	XUJ, YINGJ Y. A highly active and selective nanocomposite catalyst for C₇₊ paraffin isomerization[J]. Angewandte Chemie, 2006, 118(40): 6852-6856.
42	王泽彬, 孙越, 王岷, 等. 粉末状氢氧化锆的制备[J]. 稀有金属快报, 2005, 24(1): 28-29.
	WANGZebin, SUNYue, WANGMin, et al. Production of zirconium hydroxide powder[J]. Rare Metals Letters, 2005, 24(1): 28-29.
43	潘晖华, 于中伟, 濮仲英. 水热法改性氢氧化锆制备Pt-SO₄^2-/ZrO₂固体酸催化剂Ⅰ. 水热温度的影响[J]. 催化学报, 2003, 24(3):193-197.
	PANHuihua, YUZhongwei, PUZhongying. Preparation of Pt-SO₄^2-/ZrO₂ solid acid catalyst through hydrothermal modification of zirconium hydroxide Ⅰ. Influence of hydrothermal temperature[J]. Chinese Journal of Catalysis, 2003, 24(3): 193-197.
44	曹崇江, 陈长林, 徐南平. 水热改性SO₄^2-/Al₂O₃/ZrO₂的制备及其对正丁烷异构化反应的催化性能[J]. 应用化学, 2007, 24(11): 1240-1244.
	CAOChongjiang, CHENChanglin, XUNanping. Preparation of SO₄^2-/Al₂O₃/ZrO₂ through digestion modification and its catalytic activity in n-butane isomerization[J]. Chinese Journal of Applied Chemistry, 2007, 24(11): 1240-1244.
45	尹双凤, 徐柏庆. 碱液回流老化制备高表面积二氧化锆[J]. 催化学报, 2002, 23(3): 214-218.
	YINShuangfeng, XUBoqing. Preparation of high surface area zirconia by reflux-digestion in basic solutions[J]. Chinese Journal of Catalysis, 2002, 23(3): 214-218.
46	YINShuangfeng, XUBoqing. On the preparation of high-surface-area nano-zirconia by reflux-digestion of hydrous zirconia gel in basic solution[J]. ChemPhysChem, 2003, 4(6): 277-281.
47	BUSTOM, SHIMIZUK, VERAC R, et al. Influence of hydrothermal aging on the catalytic activity of sulfated zirconia[J]. Applied Catalysis A: General, 2008, 348(2): 173-182.
48	LIX, NAGAOKAK, OLINDOR, et al. Synthesis of highly active sulfated zirconia by sulfation with SO₃[J]. Journal of Catalysis, 2006, 238(1): 39-45.
49	LIX, NAGAOKAK, SIMONL J, et al. Influence of calcination procedure on the catalytic property of sulfated zirconia[J]. Catalysis Letters, 2007, 113(1/2): 34-40.
50	HAHNA H P, RESSLERT, JENTOFTR E, et al. The role of the "glow phenomenon" in the preparation of sulfated zirconia catalysts[J]. Chemical Communications, 2001, 6(6): 537-538.
51	HAHNA H P, JENTOFTR E, RESSLERT, et al. Rapid genesis of active phase during calcination of promoted sulfated zirconia catalysts[J]. Journal of Catalysis, 2005, 236(2): 324-334.
52	EBITANIK, KONISHIJ, HATTORIH. Skeletal isomerization of hydrocarbons over zirconium oxide promoted by platinum and sulfate ion[J]. Journal of Catalysis, 1991, 130(1): 257-267.
53	DAVISB H, KEOGHR A, SRINIVASANR. Sulfated zirconia as a hydrocarbon conversion catalyst[J]. Catalysis Today, 1994, 20(2): 219-256.
54	GARINF, ANDRIAMASINOROD, ABDULSAMADA, et al. Conversion of butane over the solid superacid ZrO₂/SO₄^2- in the presence of hydrogen[J]. Journal of Catalysis, 1991, 131(1): 199-203.
55	SIGNORETTOM, PINNAF, STRUKULG, et al. Platinum-promoted and unpromoted sulfated zirconia catalysts prepared by a one-step aerogel procedure[J]. Journal of Catalysis, 1997, 167(2): 522-532.
56	杨丹. 贵金属改性SO₄^2-/ZrO₂催化剂制备和异构化性能的研究[D]. 上海: 华东理工大学, 2014.
	YANGDan. Preparation and isomerization performance of SO₄^2-/ZrO₂ catalyst modified by noble metals[D]. Shanghai: East China University of Science and Technology, 2014.
57	VIJAYS, WolfE.E. A highly active and stable platinum-modified sulfated zirconia catalyst: 1. Preparation and activity for n-pentane isomerization[J]. Applied Catalysis A: General, 2004, 264(1): 117-124.
58	VIJAYS, WOLFE E, MILLERJ T, et al. A highly active and stable platinum-modified sulfated zirconia catalyst: Part 2. EXAFS studies of the effect of pretreatment on the state of platinum[J]. Applied Catalysis A: General, 2004, 264(1):125-130.
59	SONGH, WANGN, SONGH L, et al. La–Ni modified S₂O₈^2-/ZrO₂-Al₂O₃ catalyst in n-pentane hydroisomerization[J]. Catalysis Communications, 2015, 59: 61-64.
60	HSU C Y, HEIMBUCHC R, ARMESC T, et al. A highly active solid superacid catalyst for n-butane lsomerization: a sulfated oxide containing iron, manganese and zirconium[J]. Journal of the Chemical Society Chemical Communications, 1992: 1645-1646.
61	GAOZ, XIAY, HUAW, et al. New catalyst of SO₄^2-/Al₂O₃-ZrO₂, for n-butane isomerization[J]. Topics in Catalysis, 1998, 6(1/2/3/4):101-106.
62	HUAW, XIAY, YUEY, et al. Promoting Effect of Al on SO₄^2-/M_xO_y(M=Zr,Ti,Fe) catalysts[J]. Journal of Catalysis, 2000, 196(1): 104-114.
63	XIAY, HUAW, MIAOC, et al. n-butane isomerization on Al-promoted sulfated zirconia catalysts[J]. Chinese Journal of Catalysis, 1998, 19(2): 97-98.
64	夏勇德, 华伟明. A1促进SO₄^2-/M_xO_y(M=Zr,Ti,Fe)固体强酸的研究[J]. 化学学报, 2000, 58(1): 86-91.
	XIADeyong, HUAWeiming. Studies on strong solid acids of Al-Promoted SO₄^2-/M_xO_y(M=Zr,Ti,Fe)[J]. Acta Chimica Sinica, 2000, 58(1): 86-91.
65	JENTOFTF C, HAHNA, KRÖHNERTJ, et al. Incorporation of manganese and iron into the zirconia lattice in promoted sulfated zirconia catalysts[J]. Journal of Catalysis, 2004, 224(1): 124-137.
66	KLOSEB S, JENTOFTF C, SCHLÖGLR, et al. Effect of Mn and Fe on the reactivity of sulfated zirconia toward H₂ and n-butane: a diffuse reflectance IR spectroscopic investigation[J]. Langmuir, 2005, 21(23): 10564-10572.
67	LIP, CHENI, PENNER-HAHNJ E. Effect of dopants on zirconia stabilization—An X-ray absorption study: 1, Trivalent dopants [J]. Journal of the American Ceramic Society, 1994, 77(1): 128.
68	ARATAK. Solid superacids[J]. Advances in Catalysis, 1990, 37: 165-211.
69	田静, 宋月芹, 冯敏超, 等. 活化条件对正己烷在Pt/SO₄^2-/ZrO₂-Al₂O₃上的异构化活性影响[J]. 化工进展, 2012, 31(12): 2714-2719.
	TIANJing, SONGYueqin, FENGMinchao, et al. Effect of activation condition on n-hexane isomerization performance of Pt/SO₄^2-/ZrO₂-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2012, 31(12): 2714-2719.
70	任坚强, 于中伟, 孙义兰, 等. 一种固体超强酸催化剂的预处理方法: CN102649093B[P]. 2014-05-28.
	RENJianqiang, YUZhongwei, SUNYilan, et al. Method for pretreatment of solid superacid catalyst: CN102649093B[P]. 2014-05-28.
71	FEDOROVAM L, SHAKUNA N. Method of isomerising light petrol fractions with catalyst preactivation: RU2394804C2[P]. 2008-09-26.
72	SONGS X, KYDDR A. The effect of pretreatment procedures on the activities of Fe- and Mn-promoted sulfated zirconia catalysts[J]. Catalysis Letters, 1998, 51(1/2): 95-100.
73	张娟娟. 正已烷异构化Pt- SO₄^2-/ZrO₂固体超强酸催化剂的研究[D]. 上海: 华东理工大学, 2011.
	ZHANGJuanjuan. Study on n-hexane isomerization over Pt-SO₄^2-/ZrO₂solid acid catalyst[D]. Shanghai: East China University of Science and Technology, 2011.
74	SONGS X, KYDDR A. Activation of sulfated zirconia catalysts effect of water content on their activity in n-butane isomerization[J]. Journal of the Chemical Society Faraday Transactions, 1998, 94(9): 1333-1338.
75	GONZÁLEZM R, KOBEJ M, FOGASHK B, et al. Promotion of n-butane isomerization activity by hydration of sulfated zirconia[J]. Journal of Catalysis, 1996, 160(2): 290–298.
76	ANDERSONG C, ROSINR R, STINEM A. New solutions for light Paraffin isomerization[R]. Des Plaines: UOP LLC, 2004.
77	张锐, 刘耀芳. 水对SO₄^2-/ZrO₂型固体超强酸催化正戊烷异构化反应的影响[J]. 石油与天然气化工, 2000(2): 53-55.
	ZHANGRui, LIUYaofang. The influence of water on SO₄^2-/ZrO₂ typed solid super acid catalyzed pentane isomerization[J]. Chemical Engineering of Oil and Gas, 2000(2): 53-55.
78	孔晓翠. 固体超强酸催化正戊烷异构化失活因素的考察[D]. 北京: 石油化工科学研究院, 1998.
	KONGXiaocui. Investigation on deactivation of solid superacid catalyst in n-pentane isomerization reaction[D]. Beijing: Research Institute of Petroleum Processing, 1998.
79	FURUTAS. The effect of electric type of platinum complex ion on the isomerization activity of Pt-loaded sulfated zirconia-alumina[J]. Applied Catalysis A: General, 2003, 251(2): 285-293.
80	任坚强, 于中伟, 张新宽, 等. 因原料水含量过高而失活的固体超强酸催化剂的活化方法: CN104437591A[P]. 2016-08-24.
	RENJianqiang, YUZhongwei, ZHANGXinkuan, et al. A method of activation on the solid superacid catalysts deactivated due to the high water content in the feed: CN104437591A[P]. 2016-08-24.

序号	装置	产能 /万吨	技术来源/工艺名称	年份	说明
1	宁夏宝塔化纤	26	UOP/Par-Isom	2015	合同签约
2	庆阳石化	20	UOP/Par-Isom	2017	工程建设
3	中石油克拉玛依	15	UOP/Par-Isom	2017	工程建设
4	山东金诚石化	25	UOP/Par-Isom	2017	工程竣工
5	山东汇丰石化集团	22	UOP/Par-Isom	2018	工程竣工
6	湛江东兴石油	18	中国石化石油化工科学研究院	2016	开车运行
7	恒力石化	50	GTC/Isomalk-2	2015	合同执行
8	山东诚信化工	42	GTC/Isomalk-2	2018	合同执行
9	山东利丰达生物科技	8	GTC/Isomalk-2	2018	合同执行
10	山东东方华龙工贸集团	33	GTC/Isomalk-2	2018	合同执行
11	利华益集团股份	22	UOP/Par-Isom	2017	试车运行
12	珠海市虹彩精细化工	20	UOP/Par-Isom	2018	环评公示

序号	装置	产能 /万吨	技术来源/工艺名称	年份	说明
1	宁夏宝塔化纤	26	UOP/Par-Isom	2015	合同签约
2	庆阳石化	20	UOP/Par-Isom	2017	工程建设
3	中石油克拉玛依	15	UOP/Par-Isom	2017	工程建设
4	山东金诚石化	25	UOP/Par-Isom	2017	工程竣工
5	山东汇丰石化集团	22	UOP/Par-Isom	2018	工程竣工
6	湛江东兴石油	18	中国石化石油化工科学研究院	2016	开车运行
7	恒力石化	50	GTC/Isomalk-2	2015	合同执行
8	山东诚信化工	42	GTC/Isomalk-2	2018	合同执行
9	山东利丰达生物科技	8	GTC/Isomalk-2	2018	合同执行
10	山东东方华龙工贸集团	33	GTC/Isomalk-2	2018	合同执行
11	利华益集团股份	22	UOP/Par-Isom	2017	试车运行
12	珠海市虹彩精细化工	20	UOP/Par-Isom	2018	环评公示

参数	Penex OT 氯化型	Par-Isom OT SO₄^2-/ZrO₂	Penex DIH 氯化型	Par-Isom DIH SO₄^2-/ZrO₂
原料流量/桶·天^-1	10000	10000	10000	10000
辛烷值	83.4	83.4	88.0	88.0
辛烷桶	81040	81040	84520	84500
总CAPEX/×10⁶USD	36.5	32.7	56.9	47.5
公用消耗	基础	基础×0.56	基础×1.82	基础×1.36

参数	Penex OT 氯化型	Par-Isom OT SO₄^2-/ZrO₂	Penex DIH 氯化型	Par-Isom DIH SO₄^2-/ZrO₂
原料流量/桶·天^-1	10000	10000	10000	10000
辛烷值	83.4	83.4	88.0	88.0
辛烷桶	81040	81040	84520	84500
总CAPEX/×10⁶USD	36.5	32.7	56.9	47.5
公用消耗	基础	基础×0.56	基础×1.82	基础×1.36

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[6]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[7]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[8]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[9]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[10]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[11]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[12]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[13]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[14]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[15]	MAO Shanjun, WANG Zhe, WANG Yong. Group recognition hydrogenation: From concept to application [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3917-3922.

Progress in preparation research and industrial application of SO₄^2-/ZrO₂catalysts for light paraffin isomerization

SO₄^2-/ZrO₂轻质烷烃异构化催化剂的制备和工业应用进展

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 80

Related Articles 15

Recommended Articles

Metrics

Comments