氧化铝成型的Pt-SO_4~(2-)/ZrO_2-Al_2O_3上n-C_5~0/C_6~0的异构化性能
|
摘要
采用浸渍法制备了Pt-SO_4~(2-)/ZrO_2-Al_2O_3(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Al_2O_3质量分数为5%～10%。
Pt-SO_4~(2-)/ZrO_2-Al_2O_3(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 25 g to 250 g and the isomerization performance of simplified shaped PSZA was explored. Based on this, the influence of Al_2O_3 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%.
Pt-SO_4~(2-)/ZrO_2-Al_2O_3(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 25 g to 250 g and the isomerization performance of simplified shaped PSZA was explored. Based on this, the influence of Al_2O_3 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%.
引文
[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. SO42-/Mx Oy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 SO42-/Mx Oy 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 H2on 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 SO42-/Al2O3-ZrO2for 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/SO42-/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/SO42-/ZrO2catalyst[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 SO42-/Mx Oy(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 SO42--ZrO2catalysts for nbutane isomerization[J]. Applied Catalysis A:General, 2002, 230(1/2):137-151.
[16] COMELLI R A, VERA C R, PARERA J M. Influence of ZrO2crystalline structure and sulfate ion concentration on the catalytic activity of SO42--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/SO42-/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/SO42-/ZrO2catalyst 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-ZrO2prepared 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 Al2O3introduction method on catalytic performance of Pt-WO3/ZrO2/Al2O3catalyst for nheptane hydroisomerization[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2017, 33(2):210-218.
[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. SO42-/Mx Oy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 SO42-/Mx Oy 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 H2on 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 SO42-/Al2O3-ZrO2for 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/SO42-/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/SO42-/ZrO2catalyst[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 SO42-/Mx Oy(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 SO42--ZrO2catalysts for nbutane isomerization[J]. Applied Catalysis A:General, 2002, 230(1/2):137-151.
[16] COMELLI R A, VERA C R, PARERA J M. Influence of ZrO2crystalline structure and sulfate ion concentration on the catalytic activity of SO42--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/SO42-/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/SO42-/ZrO2catalyst 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-ZrO2prepared 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 Al2O3introduction method on catalytic performance of Pt-WO3/ZrO2/Al2O3catalyst for nheptane hydroisomerization[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2017, 33(2):210-218.