改性沸石用于半再生重整催化剂的研究
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摘要
本文研究了含改性沸石的固定床半再生重整催化剂。研究表明，引入改性沸石可以改善重整催化剂的催化性能，提高其活性和稳定性—。
在重整催化剂中引入适当量、适当硅铝比的分子筛，可以改善催化剂的性能：分子筛上引入适量的磷，可以调变分子筛的酸分布，使分子筛的强酸中心向中强酸和弱酸转化；引入改性的分子筛，可以为催化剂提供部分酸性，减少反应过程中的补氯量：催化剂中加入改性的丝光沸石、β沸石，对催化性能的影响有所不同，引入丝光沸石可以提高芳构化活性及加氢裂解活性，加入改性的β沸石降低了加氢裂解活性，提高了异构化活性。加入改性沸石对催化剂的比表面积和金属分散状态没有明显改变，但对孔径分布有一定的影响。
Modified mordenites and Beta zeolites and their applications in Pt-Re reforming catalysts have been investigated in this thesis.
The results showed that the incorporation of appropriate concentration zeolites whose Si02/Al203 (mol)ratio equals to 27 into the Pt-Re reforming catalysts can improve their activity, stability and coke resistance .The addition of phosphorus can significantly alter the acid strength distribution of zeolite . The number of strong acid sites is reduced, but the concentration of medium and weak strength acid sites is progressively increased with increasing phosphorous level . Ion exchange of zeolite also affects the characterization of the samples . The Pt-Re reforming catalyst can reduce the amount of chlorine addition in the reforming process . It is due to the function of acid sites modified by zeolites .The reaction performance varies among the catalysts with mordenites and those with Beta zeolites. No obvious changes of metal grain size and specific surface of the catalysts were observed, but pore-size distribution was changed to some extent.
在重整催化剂中引入适当量、适当硅铝比的分子筛，可以改善催化剂的性能：分子筛上引入适量的磷，可以调变分子筛的酸分布，使分子筛的强酸中心向中强酸和弱酸转化；引入改性的分子筛，可以为催化剂提供部分酸性，减少反应过程中的补氯量：催化剂中加入改性的丝光沸石、β沸石，对催化性能的影响有所不同，引入丝光沸石可以提高芳构化活性及加氢裂解活性，加入改性的β沸石降低了加氢裂解活性，提高了异构化活性。加入改性沸石对催化剂的比表面积和金属分散状态没有明显改变，但对孔径分布有一定的影响。
Modified mordenites and Beta zeolites and their applications in Pt-Re reforming catalysts have been investigated in this thesis.
The results showed that the incorporation of appropriate concentration zeolites whose Si02/Al203 (mol)ratio equals to 27 into the Pt-Re reforming catalysts can improve their activity, stability and coke resistance .The addition of phosphorus can significantly alter the acid strength distribution of zeolite . The number of strong acid sites is reduced, but the concentration of medium and weak strength acid sites is progressively increased with increasing phosphorous level . Ion exchange of zeolite also affects the characterization of the samples . The Pt-Re reforming catalyst can reduce the amount of chlorine addition in the reforming process . It is due to the function of acid sites modified by zeolites .The reaction performance varies among the catalysts with mordenites and those with Beta zeolites. No obvious changes of metal grain size and specific surface of the catalysts were observed, but pore-size distribution was changed to some extent.
引文
1 董福根．催化重整通讯，1997，2：44
2 赵仁殿．世界石油工业，1997，4：36
3 古阶祥著．沸石．中国建筑出版社，1980
4 USP4447316
5 USP4517306
6 徐如人，庞文琴等编．沸石分子筛的结构与合成．吉林大学出版社，1987
7 武克瑞．石油化工．1990，19，415
8 郑坚，董家禄等．中国稀土学报．1998，16(2)：170
9 USP4447316
10 USP4435283. 1993
11 Breck D W. Zeolite Molecular Sieve. New York: Wiley 1974
12 Meier W M. Molecular Sieves. London: Society of the Chemical Indusrry, 1968:10
13 USP3511773
14 USP3679575
15 USP3523914
16 潘惠芳等．石油学报(石油加工)．1996，12(3)：1～7
17 Stanislas A. et al. Appl Catal. 1988,39:239～253
18 USP330869. 1967
19 Martens J A et al. Zeolites. 1984,4:98
20 Martens J A el al. Zeolites. 1996,6:334
21 Newsam J M et al. Proc Roy Soc Lond. 1988:A420～375
22 Treacy M M J et al. Nature. 1988:249～332
23 Higgins J B et al. Zeolites. 1988,8:446
24 Meier W M, Olson D H. In Atlas of Zeolites Structure Types. London. Butterworth-Heinemann, 1992:58.
25 USP3728408.1973
26 USP4501926.1983
27 Tsai TC et al. Appl Catal. 1991,77:199
28 Tsai TC et al. Appl Catal. 1991,77:209
29 Parikh P A et al. Appl Catal A: General. 1992,90:1
30 Mitra A et al. Appl Catal A: General. 1997,53:233
31 Pradhan A R et al. Appl Catal A: General. 1993,106:143
32 王延吉等．分子催化．1996，10(1)：6
33 Wang I et al. Ind Eng Chem Res. 1990,29,2005
34 Das J et al. Appl Catal A: General. 1994,116:71
35 Gray M Robber et al. Microprous and Mesoporous Naterials. 1998,20:307
36 沈建平等，高等学校化学学报．1995，16(6)，：934～947
37 USP5227569. 1993
38 I. Ferio et al. Appl catal A: Genernal. 1991,183:303
39 潘履让等，石油学报(石油加工)．1988，9，4(3)：61～66
40 王军等．精细石油化工．1994，2：21
41 Fejes P et al. Zeolites. 1985, 5: 45
42 高滋、何鸣元等编．沸石催化与分离技术．北京．中国石化出版社．1999：47
43 李海涛等．石油炼制．1992．10：28
44 Biwas J et al. Catal Rev-Sci Eng. 1988, 30(2): 161
45 J R安德森著．金属催化剂的结构．北京：化学工业出版社，1985：53
46 朱洪法．石油化工催化剂基础知识．北京：中国石化出版社．1995：386
47 Arena F et al. J Chem Soc Faraday Trans. 1992,88(22):3353
48 Gates B C et al. Chemistry of Catalytic Process. New York. McGraw-Hill. 1985
2 赵仁殿．世界石油工业，1997，4：36
3 古阶祥著．沸石．中国建筑出版社，1980
4 USP4447316
5 USP4517306
6 徐如人，庞文琴等编．沸石分子筛的结构与合成．吉林大学出版社，1987
7 武克瑞．石油化工．1990，19，415
8 郑坚，董家禄等．中国稀土学报．1998，16(2)：170
9 USP4447316
10 USP4435283. 1993
11 Breck D W. Zeolite Molecular Sieve. New York: Wiley 1974
12 Meier W M. Molecular Sieves. London: Society of the Chemical Indusrry, 1968:10
13 USP3511773
14 USP3679575
15 USP3523914
16 潘惠芳等．石油学报(石油加工)．1996，12(3)：1～7
17 Stanislas A. et al. Appl Catal. 1988,39:239～253
18 USP330869. 1967
19 Martens J A et al. Zeolites. 1984,4:98
20 Martens J A el al. Zeolites. 1996,6:334
21 Newsam J M et al. Proc Roy Soc Lond. 1988:A420～375
22 Treacy M M J et al. Nature. 1988:249～332
23 Higgins J B et al. Zeolites. 1988,8:446
24 Meier W M, Olson D H. In Atlas of Zeolites Structure Types. London. Butterworth-Heinemann, 1992:58.
25 USP3728408.1973
26 USP4501926.1983
27 Tsai TC et al. Appl Catal. 1991,77:199
28 Tsai TC et al. Appl Catal. 1991,77:209
29 Parikh P A et al. Appl Catal A: General. 1992,90:1
30 Mitra A et al. Appl Catal A: General. 1997,53:233
31 Pradhan A R et al. Appl Catal A: General. 1993,106:143
32 王延吉等．分子催化．1996，10(1)：6
33 Wang I et al. Ind Eng Chem Res. 1990,29,2005
34 Das J et al. Appl Catal A: General. 1994,116:71
35 Gray M Robber et al. Microprous and Mesoporous Naterials. 1998,20:307
36 沈建平等，高等学校化学学报．1995，16(6)，：934～947
37 USP5227569. 1993
38 I. Ferio et al. Appl catal A: Genernal. 1991,183:303
39 潘履让等，石油学报(石油加工)．1988，9，4(3)：61～66
40 王军等．精细石油化工．1994，2：21
41 Fejes P et al. Zeolites. 1985, 5: 45
42 高滋、何鸣元等编．沸石催化与分离技术．北京．中国石化出版社．1999：47
43 李海涛等．石油炼制．1992．10：28
44 Biwas J et al. Catal Rev-Sci Eng. 1988, 30(2): 161
45 J R安德森著．金属催化剂的结构．北京：化学工业出版社，1985：53
46 朱洪法．石油化工催化剂基础知识．北京：中国石化出版社．1995：386
47 Arena F et al. J Chem Soc Faraday Trans. 1992,88(22):3353
48 Gates B C et al. Chemistry of Catalytic Process. New York. McGraw-Hill. 1985