磷改性对Pt/HZSM-5催化剂的酸性调变及临氢异构化性能的影响

石油炼制与化工 ›› 2017, Vol. 48 ›› Issue (11): 12-17.

磷改性对Pt/HZSM-5催化剂的酸性调变及临氢异构化性能的影响

崔程鑫,张孔远,肖常林,刘晨光

中国石油大学（华东）重质油国家重点实验室 CNPC催化重点实验室

收稿日期:2017-05-05 修回日期:2017-06-10 出版日期:2017-11-12 发布日期:2017-10-25
通讯作者: 张孔远 E-mail:zkyuana@126.com
基金资助:

EFFECTS OF PHOSPHORUS MODIFICATION ON ACIDITY OF Pt/HZSM-5 CATALYST AND ITS HYDROISOMERIZATION PERFORMANCE

Received:2017-05-05 Revised:2017-06-10 Online:2017-11-12 Published:2017-10-25
Supported by:

摘要/Abstract

摘要： 采用等体积浸渍法制备了不同P含量改性的Pt-P/HZSM-5异构化催化剂，通过低温N2吸附-脱附、XRD、NH3-TPD和Py-IR等手段对催化剂试样进行了表征，在连续固定床反应装置上考察了催化剂的临氢异构化反应性能。结果表明：加入少量的P能够显著地调变催化剂的酸量和酸强度分布，使弱酸量增加，强酸量减少，Br?nsted酸量提高；Pt-P/HZSM-5催化剂显著抑制了裂解反应的发生，提高了反应的异构化率和DMB（二甲基丁烷）选择性。在反应压力1.5 MPa、氢油体积比500、体积空速1 h-1和反应温度280 ℃的条件下，P质量分数1%、Pt质量分数0.4%的Pt-P/HZSM-5催化剂的性能最优，正己烷转化率达到75.78%，异构化率为75.36%，裂解率为3.69%，DMB（二甲基丁烷）选择性为6.65%。

关键词: Pt-P/HZSM-5, 磷酸氢二铵, 正己烷, 异构化

Abstract: The Pt-P/HZSM-5 isomerization catalysts were prepared by incipient wetness impregnation and characterized by N2 adsorption-desorption, XRD, NH3-TPD, and Py-IR. The isomerization performance of the prepared catalysts was evaluated in a continuous fixed bed reactor. The results showed that the addition of a small amount of phosphorus can significantly change the acid amount and acid strength distribution of Pt/HZSM-5. The strong acid sites decrease and the weak acid and Br?nsted acid sites increase. Pt-P/HZSM-5 catalysts significantly inhibit the cracking reaction and improve the isomerization rate and dimethylbutane selectivity. At 1.5 MPa, 280 ℃ and H2/oil volume ratio of 500, LHSV of 1 h-1, the Pt-P/HZSM-5 catalyst with 1% P and 0.4% Pt gives the best isomerization results of 75.78% n-hexane conversion rate, 75.36% isomerization rate, 3.69% cracking rate and 6.65% dimethylbutane selectivity.

Key words: Pt-P/HZSM-5, diammonium phosphate, hexane, isomerization

中图分类号:

崔程鑫张孔远肖常林刘晨光. 磷改性对Pt/HZSM-5催化剂的酸性调变及临氢异构化性能的影响[J]. 石油炼制与化工, 2017, 48(11): 12-17.

参考文献

[1]曹洪湘.车用燃料清洁化—我国炼油工业面临的挑战和对策[J].石油炼制与化工, 2008, 39(1):1-8
[2]Leu Lijen, Hou Liangyuan, Kang Benchang, et al.Synthesis of zeolite β and catalytic isomerization of n-hexane over PtHβ catalysts[J].Appl Catal, 1991, 69(1):49-63
[3]Weyda H, K?hler E.Modern refining concepts-an update on naphtha-isomerization to modern gasoline manufacture[J].Catal Today, 2003, 81(1):51-55
[4] 曾昭槐.择形催化[M].北京: 中国石化出版社, 1994：2-21.
[5] 顾伯锷.工业催化过程导论[M]. 北京: 高等教育出版社, 1990: 119-200.
[6] Warren W Kaeding, Westfield, Stephen A Butter, et al.Conversion of methanol and dimethyl ether: US, 3911041[P]. 1975-10-07．
[7]Warren W Kaeding, Stephen A Butter.Production of chemicals from methanolLow molecular weight olefins[J].Journal of Catalysis, 1980, 61(1):155-164
[8]任行涛, 曹建秋, 王震宇, 等.磷改性Hβ分子筛对正癸烷异构化反应的催化性能[J].催化学报, 2005, 26(3):238-242
[9]赵尹, 王海彦, 魏民, 等.磷改性β沸石催化剂上催化裂化轻汽油的醚化[J].燃料化学学报, 2004, 32(2):225-228
[10]谢有畅, 唐有祺.氧化物和盐类在分子筛内外表面及孔穴中的自发分散及其应用[J].北京大学学报自然科学版, 1998, 34(2):302-308
[11]EY Choi, IS Nam, YG Kim.TPD Study of Mordenite-Type Zeolites for Selective Catalytic Reduction of NO by NH3[J].Journal of Catalysis, 1996, 161(2):597-604
[12]J.A.Lercher,GRumplanayr. Controlled decrease of acid strength by orthophosphoric acid on ZSM-5[J].Appl. Catal, 1986, 25(1):215-222
[13]钟海军, 柳云骐, 安高军, 等.硅改性Hβ沸石催化萘异丙基化反应[J].石油化工, 2007, 36(5):479-484
[14]Emeis C A.Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J].J Catal, 1993, 141(2):347-354
[15]赵国良, 滕佳伟, 谢在库, 等.氟硅酸铵改性的HZSM-5催化剂的表征及其烃裂解催化性能[J].催化学报, 2005, 26(12):1083-1087
[16]朱玉霞, 林伟, 田辉平, 等.固体酸催化剂酸性分析方法的研究进展[J].石油化工, 2006, 35(7):607-614
[17]Blomsma E, Martens J A, Jacobs P A.Mechanisms of heptane isomerization on bifunctional PdH-Beta zeolites[J].J Catal, 1996, 159(2):323-331
[18]徐铁钢, 吴显军, 王刚, 等.轻质烷烃异构化催化剂研究进展[J].化工进展, 2015, 34(2):397-401