氧化铝成型的Pt-SO4 2-/ZrO2-Al2O3上n-C5 0/C6 0的异构化性能

doi:10.16085/j.issn.1000-6613.2018-1659

摘要/Abstract

摘要：

采用浸渍法制备了Pt-SO₄ ^2-/ZrO₂-Al₂O₃（PSZA）催化剂，考察了黏结剂拟薄水铝石的来源对PSZA异构化活性和机械强度的影响，确定了较为适合的黏结剂来源。对氢氧化锆母体制备进行从25g放大10倍至250g，研究放大催化剂的异构化性能。在此基础上考察了Al₂O₃黏结剂含量对PSZA异构化活性和机械强度的影响。采用XRD、TG、XRF等手段对催化剂进行了表征，结果表明：拟薄水铝石的来源不同，结晶度不同，制备的催化剂的异构化活性与机械强度均有差别，拟薄水铝石的结晶度越高，制备的催化剂上的硫含量越低，异构化活性越高，机械强度也越高。此外，放大10倍制备的催化剂异构化性能没有明显变化。黏结剂含量对催化剂的初始异构化活性没有明显影响，而反应稳定性随着黏结剂含量的提高大幅度降低。兼顾催化剂的异构化活性与机械强度，较适宜的Al₂O₃质量分数为5%～10%。

关键词: Pt-SO₄ ^2-/ZrO₂-Al₂O₃, 催化剂, 氧化铝, 加氢, 机械强度

Abstract:

Pt-SO₄ ^2-/ZrO₂-Al₂O₃（PSZA） catalyst was prepared by impregnation method. The effects of binder pseudoboehmite sources on the isomerization activity and mechanical strength of PSZA were investigated, and the suitable source of binder was determined. Also，the preparation of the zirconium hydroxide was scaled up about 10 times from 25g to 250g and the isomerization performance of simplified shaped PSZA was explored. Based on this, the influence of Al₂O₃ binder content was investigated. The catalysts were characterized by XRD, TG, XRF, and so on. The experimental results demonstrated that pseudoboehmite from different sources had different crystallinity, which led to PSZA with different isomerization activity and mechanical strength. The high crystallinity of the pseudoboehmite provided the catalyst with low sulfur content, high isomerization activity and high mechanical strength. In addition, the catalyst prepared with large scale did not show significant change in the isomerization performance of the catalyst. The binder content in the studied range had no significant effect on the initial isomerization activity of the catalyst, but the reaction stability decreased greatly with the increase of the binder content. When the isomerization activity and mechanical strength of the catalyst were both desirable, a suitable alumina content was 5%～10%.

Key words: PSZA, catalyst, alumina, hydrogenation, mechanical strength

中图分类号:

TQ032.4

倪海微, 宋月芹, 周思侬, 章红艳, 徐俊, 周晓龙. 氧化铝成型的Pt-SO₄ ^2-/ZrO₂-Al₂O₃上n-C₅ ⁰/C₆ ⁰的异构化性能[J]. 化工进展, 2019, 38(06): 2806-2812.

Haiwei NI, Yueqin SONG, Sinong ZHOU, Hongyan ZHANG, Jun XU, Xiaolong ZHOU. n-C₅ ⁰/C₆ ⁰ isomerization performance over alumina-shaped Pt-SO₄ ^2-/ZrO₂-Al₂O₃ catalyst[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2806-2812.

图/表 13

参考文献 24

1	HINO M , KOBAYASHI S , ARATA K . Reactions of butane and isobutane catalyzed by zirconium oxide treated with sulfate ion. Solid superacid catalyst[J]. Journal of the American Chemical Society, 1979, 101(21): 6439-6441.
2	CLEARFIELD A , SERRETTE G P D , KHAZI-SYED A H . Nature of hydrous zirconia and sulfated hydrous zirconia[J]. Catalysis Today, 1994, 20(2): 295-312.
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.
	ZHAO W K , FAN J , ZHU B C , et al . Isomerization process for producing clean gasoline and the catalyst[J]. Chemical Industry and Engineering Progress, 2016, 35(8): 2455-2463.
4	孟瑶, 李锋, 宋华 . SO₄ ^2-/M _x O _y 型固体超强酸酸中心结构及其在轻质烷烃异构化反应中的机理研究进展[J]. 化工进展, 2015, 34(11): 3906-3914.
	MENG Y , LI F , SONG H . Advance in surface characteristics of SO₄ ^2-/M _x O _y solid superacid and its isomerization mechanisms for light alkane[J]. Chemical Industry and Engineering Progress, 2015, 34(11): 3906-3914.
5	DUCHET J C , GUILLAUME D , MONNIER A , et al . Isomerization of n-hexane over sulfated zirconia: influence of hydrogen and platinum[J]. Journal of Catalysis, 2001, 198(2): 328-337.
6	KIM S Y, GOODWIN J G , HAMMACHE S , et al . The impact of Pt and H₂ on n-butane isomerization over sulfated zirconia: changes in intermediates coverage and reactivity[J]. Journal of Catalysis, 2001, 201(1): 1-12.
7	EBITANI K , KONISHI J , HATTORI H . Skeletal isomerization of hydrocarbons over zirconium oxide promoted by platinum and sulfate ion[J]. Journal of Catalysis, 1991, 130(1): 257-267.
8	GAO Z , XIA Y D , HUA W M , et al . New catalyst of SO₄ ^2-/Al₂O₃-ZrO₂ for n-butane isomerization[J]. Topics in Catalysis, 1998, 6(1): 101-106.
9	徐俊, 王昭晖, 宋月芹, 等 . 成型工艺条件对Pt/SO₄ ^2-/ZrO₂催化剂异构化性能的影响[J]. 石油炼制与化工, 2016, 47(1): 32-38.
	XU J , WANG Z H , SONG Y Q , et al . Effect of extrusion conditions on isomerization performance of Pt/SO₄ ^2-/ZrO₂ catalyst[J]. Petroleum Processing and Petrochemicals, 2016, 47(1): 32-38.
10	HUA W M , XIA Y D , YUE Y H , et al . Promoting effect of Al on SO₄ ^2-/M _x O _y (M=Zr, Ti, Fe) catalysts[J]. Journal of Catalysis, 2000, 196(1): 104-114.
11	李雪礼, 娄来银, 谭争国, 等 . 拟薄水铝石的性质及其在催化裂化催化剂中的应用[J]. 石化技术与应用, 2014, 32(1): 9-13.
	LI X L , LOU L Y , TAN Z G , et al . Character of pseudo-boehmite and its application in preparation of catalytic cracking catalyst[J]. Petrochemical Technology & Application, 2014, 32(1): 9-13.
12	苗壮, 史建公, 郝建薇, 等 . 拟薄水铝石的胶溶性与结构的关系[J]. 石油学报(石油加工), 2016, 32(3): 493-500.
	MIAO Z , SHI J G , HAO J W , et al . Relationship between peptization and structure of pseudo-boehmite[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2016, 32(3): 493-500.
13	周翔, 田辉平, 许本静 . 拟薄水铝石粉体性质对黏结性能的影响[J]. 工业催化, 2012, 20(9): 31-35.
	ZHOU X , TIAN H P , XU B J . Influence of powder properties of pseudoboehmite on binding efficiency[J]. Industrial Catalysis, 2012, 20(9): 31-35.
14	KIM S Y, GOODWIN J G , GALLOWAY D . n-Butane isomerization on sulfated zirconia: active site heterogeneity and deactivation[J]. Catalysis Today, 2000, 63(1): 21-32.
15	VERA C R , PIECK C L , SHIMIZU K , et al . Tetragonal structure, anionic vacancies and catalytic activity of SO₄ ^2--ZrO₂ catalysts for n-butane isomerization[J]. Applied Catalysis A: General, 2002, 230(1/2): 137-151.
16	COMELLI R A , VERA C R , PARERA J M . Influence of ZrO₂ crystalline structure and sulfate ion concentration on the catalytic activity of SO₄ ^2--ZrO₂ [J]. Journal of Catalysis, 1995, 151(1): 96-101.
17	BIKMETOVA L I , SMOLIKOV M D , ZATOLOKINA E V , et al . Supported sulfated zirconia catalysts for isomerization of n-hexane[J]. Procedia Engineering, 2016, 152: 87-93.
18	SUN Y Y , WALSPURGER S , LOUIS B , et al . Investigation of factors influencing catalytic activity for n-butane isomerization in the presence of hydrogen on Al-promoted sulfated zirconia[J]. Applied Catalysis A: General, 2005, 292: 200-207.
19	MARCUS R L , GONZALEZ R D , KUGLER E L , et al . Isomerization of n-butane: conversion as a function of sulfate loading on sulfated zirconia catalysts[J]. Chemical Engineering Communications, 2003, 190(12): 1601-1619.
20	徐俊 . Pt/SO₄ ^2-/ZrO₂催化剂成型及其异构化性能研究[D]. 上海: 华东理工大学, 2016.
	XU J . Study on the shaping of Pt/SO₄ ^2-/ZrO₂ catalyst and its isomerization performances[D]. Shanghai: East China University of Science and Technology, 2016.
21	谭经品 . 催化剂工业放大中的一些技术问题[J]. 石油炼制与化工, 1993(9): 26-32.
	TAN J P . Some technological problems concerning catalyst scale-up[J]. Petroleum Processing and Petrochemicals, 1993(9): 26-32.
22	张静, 阎松 . 沉淀法制备ZrO₂中制备方法对氧化锆晶相的影响[J]. 石油化工高等学校学报, 2011, 24(1): 30-33.
	ZHANG J , YAN S . Influence of preparation conditions on the crystal phase of nano-ZrO₂ prepared by precipitation[J]. Journal of Petrochemical Universities, 2011, 24(1): 30-33.
23	IVANOV V K , BARANCHIKOV A Y , KOPITSA G P , et al . pH control of the structure, composition, and catalytic activity of sulfated zirconia[J]. Journal of Solid State Chemistry, 2013, 198(2): 496-505.
24	王昭晖, 董姝妙, 宋月芹, 等 . Al₂O₃的引入方法对Pt-WO₃/ZrO₂/Al₂O₃催化剂正庚烷异构化性能的影响[J]. 石油学报(石油加工), 2017, 33(2): 210-218.
	WANG Z H , DONG S M , SONG Y Q , et al . Effect of Al₂O₃ introduction method on catalytic performance of Pt-WO₃/ZrO₂/Al₂O₃ catalyst for n-heptane hydroisomerization[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2017, 33(2): 210-218.

氧化物种类	氧化物质量分数/%
氧化物种类	拟薄水铝石1	拟薄水铝石2	拟薄水铝石3
Al₂O₃	98.67	99.65	98.74
CaO	0.66	0.01	0.29
SiO₂	0.25	0.05	0.31
MgO	0.12	—	0.18
其他	0.30	0.29	0.48

氧化物种类	氧化物质量分数/%
氧化物种类	拟薄水铝石1	拟薄水铝石2	拟薄水铝石3
Al₂O₃	98.67	99.65	98.74
CaO	0.66	0.01	0.29
SiO₂	0.25	0.05	0.31
MgO	0.12	—	0.18
其他	0.30	0.29	0.48

催化剂	机械强度/N·cm^-1
PSZ_SA₁-30	263
PSZ_SA₂-30	246
PSZ_SA₃-30	210

催化剂	机械强度/N·cm^-1
PSZ_SA₁-30	263
PSZ_SA₂-30	246
PSZ_SA₃-30	210

催化剂	产物分布质量分数/%
催化剂	C₄ ^-	iC₅ ⁰	nC₅ ⁰	2,2-DMB	2,3-DMB	2-MP	3-MP	nC₆ ⁰	其他
PSZ_SA₁-30	21.3	33.9	15.2	8.3	4.1	8.4	4.3	2.4	2.1
PSZ_SA₂-30	21.0	33.4	17.6	6.4	3.9	8.0	4.0	2.5	3.2
PSZ_SA₃-30	20.1	30.9	21.5	4.6	4.0	8.3	4.1	3.0	3.5

氧化铝成型的Pt-SO₄ ^2-/ZrO₂-Al₂O₃上n-C₅ ⁰/C₆ ⁰的异构化性能

n-C₅ ⁰/C₆ ⁰ isomerization performance over alumina-shaped Pt-SO₄ ^2-/ZrO₂-Al₂O₃ catalyst

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[9]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[10]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[11]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[12]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[13]	毛善俊, 王哲, 王勇. 基团辨识加氢：从概念到应用[J]. 化工进展, 2023, 42(8): 3917-3922.
[14]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[15]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.

催化剂	机械强度/N·cm^-1
PSZ_LA₁-3	86
PSZ_LA₁-5	176
PSZ_LA₁-10	210
PSZ_LA₁-30	260

催化剂	机械强度/N·cm^-1
PSZ_LA₁-3	86
PSZ_LA₁-5	176
PSZ_LA₁-10	210
PSZ_LA₁-30	260