甲基萘甲醇烷基化合成2，6-二甲基萘的研究
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摘要
研究了HY、Hβ和HZSM-5沸石分子筛对甲基萘择型甲基化反应的催化性能。结果发现，这些沸石分子筛的活性顺序为HY＞Hβ＞HZSM-5，对DMN的选择性顺序为HZSM-5＞Hβ＞HY。在常压条件下，三种不同类型沸石分子筛(HY、Hβ、HZSM-5)中，Hβ用于甲基萘甲醇烷基化反应时，2,6-DMN的产率最高，操作条件在：反应温度400℃左右，甲醇含量(甲醇:甲基萘:均三甲苯)控制在0.25:1:3(重量比)，载气N_2流量2-4ml／min时表现出较高的催化活性。但反应的稳定性需要进一步提高。由于超临界流体具有良好的溶解性能、扩散性能，在超临界条件下反应时，催化剂的失活状况得到明显改善。三种不同类型分子筛的催化活性随反应时间变化的研究表明，HZSM-5分子筛保持活性时间最长。进一步研究了在HZSM-5催化下，甲基萘甲醇烷基化反应的条件，压力75MPa，温度450℃时得到较好的转化率，较高的选择性和较长的催化剂寿命。
Naphthalene alkylation with MeOH was studied over HZSM-5,H P and HY Zeolites.lt was found that the catalytic performance of the catalysts for naphthalene conversion decreased in the order of HY>H >HZSM-5,but for the selectivity to DMN in the order of HZSM-5> H P >HY.When the
reaction is carried out in gas phase,obvious catalyst deactivation is observed.This paper aims at slowing down the rate of catalyst deactivation of naphthalene alkylation with MeOH reaction based on some special properties of supercritical fluid(higher solubility than gases and higher diffusibility
than lipuids).The night conversion of MN and selectivity of DMN in the methylation on H b zeolite in the following conditions:at the reaction temperature 400C;the prepared weight rato of MN to methanol is in the range of 4 : 1; the flux of carrier gas NI in the range of 2 to 4ml/min.The higst conversion
of MN,selectiviry of DMN and slowing down the rate of catalyst deactivation in the methylation on HZSM-5 under supercritical condition. in the following conditionsrat the reaction temperature 440-460C pressure 65-75 MPa.
Naphthalene alkylation with MeOH was studied over HZSM-5,H P and HY Zeolites.lt was found that the catalytic performance of the catalysts for naphthalene conversion decreased in the order of HY>H >HZSM-5,but for the selectivity to DMN in the order of HZSM-5> H P >HY.When the
reaction is carried out in gas phase,obvious catalyst deactivation is observed.This paper aims at slowing down the rate of catalyst deactivation of naphthalene alkylation with MeOH reaction based on some special properties of supercritical fluid(higher solubility than gases and higher diffusibility
than lipuids).The night conversion of MN and selectivity of DMN in the methylation on H b zeolite in the following conditions:at the reaction temperature 400C;the prepared weight rato of MN to methanol is in the range of 4 : 1; the flux of carrier gas NI in the range of 2 to 4ml/min.The higst conversion
of MN,selectiviry of DMN and slowing down the rate of catalyst deactivation in the methylation on HZSM-5 under supercritical condition. in the following conditionsrat the reaction temperature 440-460C pressure 65-75 MPa.
引文
1 何志荣，朱凌皓．2，6-萘二甲酸及其酯开发生产[J]．中国化工信息，1999，(39)：11
2 R. F. McMahon, J. D. Greene Jr, D. A. Peterson. Process for Preparing 2, 6-Naphthalenedicarboxylic Acid[P]. US: 61145575。2000-09-05
3 杨彦文，王新，张文会．焦油洗油资源综合利用的工艺研究[J]．河北化工，1997，(1)：26-29
4 孙绪江，张军，齐彦伟．分子筛吸附分离2，6-二甲基萘[J]．精细石油化I，1999，(5)：4-6
5 Eldib Enginerring Co. [J]. Chemicalweek, p27, 1992-06-24
6 Yang K, Aizawa S. Process for Production of Dimethylnaphthalenes[P]. US: 4963248, 1990—10—16
7 Rex Clark N. Crowther J D, Galdwin K, et al. Preparation of Dimethylnaphthalenes[P]. GB: 2133032, 1983-01-07
8 Weitkamp J. Neuber M, Wilhelm D, et al. Preparation of 2, 6-dialkyl-naphthalenes[P]. US: 4795847, 1989-01-03
9 Weitkamp J, Neuber M. Lewis Acid Catalysts and Solvents Effects on the Alkylation of Naphthalene, J.of Ind. & Eng. Chem [J]. Stud. Surf. Sci. Catal. 1991, 60: 291-301
10 Fraenkel D, Cherniavsky M, Ittah B, et al. Ittah B,et al. Shape-Selective Alkylation of Naphthalene and Methylnaphthalene with Methanol over H-ZSM-5 Zeolite Catalyts [J]. J. of Catal, 1986, 101: 273-83
11 Komatsu I, Araki Y, Namba S, et al. [J]. Stud. Surf. Sci. Catal, 1994, 84:1821-1828
12 Tomoyuki I, Pu S B, Jun-ichiro K. [J]. Appl. Catal. A: General, 1996, 146: 285-296
13 Pu S B, Tomoyuki. [J]. Appl. Catal. A: General, 1996, 146: 305-316
14 徐海升，宋成盈，赵建宏等．[J]．石油学报(石油加工)，1999，15(1)：52—55
15 Angevine P J, Degnan T F, Marler D O. Process for Preparing Dialkylnapthalenet[P]. US: 5001295, 1991—03—19
16 Motoyuki M, Yamamoto K, Mcwilliams J P, et al. Process for Preparing Dialkylnapthalene[P]. US: 5744670. 1998-04-28
17 Motoyuki M, Yamamoto K, Mcwilliams J P, et al. Process for Preparing Dialkylnaphthalene[P]. US: 5844064. 1998-12-01
18 Motoyuki M, Yamamoto K, Ajit V, et al. Process for Preparing Dialkylnaphthalene[P]. US: 6011190, 2000-01-04
19 Motoyuki M, Yamamoto K, Sapre A V et al. Process for Preparing 2,
6-DialkyInaphthalene[P]. US: 6018080-2000-01-25
20 金田究弘．二甲基萘的制造方法[P]日本公开特许公报：JP4-120029[P]，1992-04-21
21 G.P. Hagen,D.T. Hung. Selective production of 2,6-dimethylnaphthalene[P].US :5670704,1997-09-23
22 D. K. Yong, H. K. Ju, J. S. Jun, et al. Lewis Acid Catalysts and Solvents Effects on the Alkylation of Naphthalene, J.of Ind. & Eng. Chem [J]. J. of Ind.& Eng. Chem. 1998, 4(4): 329-333
23 阿部正澍，清水俊夫．2，6—二甲基萘的制造方法[P]．日本公开特许公报：JP6-287152，1994—10—11
24 阿部正澍，清水俊夫．2，6—二甲基萘的制造方法[P]．日本公开特许公报：JP7—126194，1995—05—25
25 简井俊雄．二甲基萘的制造方法[P]．日本公开特许公报：JP11-139998[P]，1999-05-25
26 户井田努．二甲基萘的制造方法[P]．日本公开特许公报：JP63-14737，1988-01-21
27 Matsuda T, Katsunoro Y, Yaashuhiro M, et al. Shape Selective Catalysis by ZSM-5 in Disproportionation of 2-Methylnaphthalene [J]. Chem.Lett, 1990(7): 1085-1088
28 沈剑平，姜延顺，马骏，等．β-甲基萘歧化反应中HZSM-5择形性[J]．高等学校化学学报，1993，14(6)：845-848
29 沈剑平，姜延顺，马骏，等．层柱材料在β-甲基萘歧化反应中的催化行为[J]．高等学校化学学报，1993，14(8)：1135-1139
30 栗同林，刘希尧，王祥生．β沸石对甲基萘歧化反应的择形性[J]．催化学报，1997，18(3)：221-224
31 Angevine P J, Degnan T F, Marler D O. Process for the Catalytic Dispr oportionation of Methylllaphthalener[P]. us: 4982040, 1991-01-01
32 Abe T, Uchiyama S, Ojima T, et al. Process for Porduction of 2, 6-Dimethylnaphthalene[P]. US: 5008479, 199t-04-16
33 Takagawa M, Yamagishi K, Yoshihara J, et al. Process for Producing 2, 6-Dimethylnaphthalene[P]. yS: 5068480。1991。11-26
34 Inamasa K, Fushimi N, Takagawa M. Process for Prodyucing 2, 6-Dimethylnaphthalene[P]. US: 5321178, 1994-06-14
35 Bergstroem C, Niemelae M. Process for Preparaing 2, 6-Dimethylnaphthalene[P]. WO: 0034212, 2000-06-14
36 Jakkula J, Niemi V,Vahterlsto K, et al. Process of Producing 2, 6-Dimethylnaphthalene by dehydrocyclizing 1-(p-Tolyl)-2-methlbutane and / or 1-(p-Toly)-2-methylbutene using a Reduced Vanadium Catalyst[P]. US: 6127589。
2000-10． 03
37 Del Rossi K J, Green L A, Huss Jr A, et al . Process for Preparing Dimethylnaphthalene[P]. US: 5043501, 1991-08-27
38 ChenCY,SchinskiW, O Rear D,et al .Method of Making Dimethylnaphthalenes[P].US:5955641, 1999-09-21
39 Sikkenga;D.L.Monoalkenylation of alkylbenzenes in a fixed catalyst bed[P].US :4990717,1991-02-05
40 G.P.Hussmann G P,McMazhon P E.Cyclization Catalyst[P].US:4740647,1988-04-26
41 Sikkenga D L,Lamb J D,Zaenger I C, et al.Preparation of Dimethylnaphthalene[P] US:4950825,. 1990-08-21
42 Sikkenga D L,Lamb J D,Zaenger I C, et al.Preparation of Dimethyltetralin [P].US:5073670,1991-12-17
43 Sikkenga D L,Zaenger I C, Williams G S. Preparation of Dimethyltetralin in a Distillation Reactoi[P]. US:5284987,1994-02-08
44 Ozawa S, Takagawa M,Dnamasa K.Process for Production of Dimethyltetralin[P]. US:5396008,1995-03-07
45 Sikkenga D L, Zaenger I C, Lamb J D,et al .preparation of a Dimethylteralin by Cyclizing an Orthotolylpentene Phenylhexene Uising an Ultra-stable Crystalline Aluminosilicate Molecular Sieve y-Zeolite[P]. US:5401892,1995-03-28
46 Sikkenga D L,Zaenger I C,Williams G S.Preparation of Dimethylnaphthalene [P].US:5012024,1991-04-30
47 Amelse J A.Selective Dehyrogenation Processes and Catalysts[P]. US :5189234,1993-02-23
48 Kyuko Y, Ozawa S,Takagawa M,et al.Process for Production of Dimethylnaphthalene[P].US:53960 07,19 95-03-07
49 Ozawa S,Takagawa M,Fujimori T.Process for Production of Dimethylnaphthalene[P].US:5446226,1995-08-29
50 Vahteristo K, Halme;E,Koskimies S,et al.Manufacturing of 2,6-dimethylnaphthalene [P].US:5952534,199 9-09-14
51 Abe T, Ebata S,Machida H,et al.Process for Production of 2,6-Dimethylnaphth alene [P].US:5023390,1991-06-11
52 Meshram,N.R.,Negde,S.G.and Knlkarni,S.B.Zeolite, 1986(6):434
53 Dan Fraenkel,Margaret Chemiavsky, Baruch Ittah Shape-Sele ctive Alkylation of Naphthalene and Methy lnaphthalene with Methanol over HZSM-5 Zeolite Catalysts[J],Journal of Catalyst 1986(101),273-283
54 曾昭槐．择形催化．北京：中国石化出版社，1994：4-6，468-469，475，483，91-93
55 沈忠耀．超临界流体．化工百科全书(第二卷)，北京：化学工业出版社，1991．325-339
56 郭继志 袁渭康 初议超临界条件下的化学反应．化工进展，2000 (3)，8-13
57 王涛 艾大刚 李成岳．超临界化学反应的研究现状和趋势．化工进展，(3)，17-20
58 Tiltscer H,Woif H,Schelchshom J.Utilization of SCF Solvent-EFFects in Heterogeneous Catalysis. Ber Bunsenges Phy Chem, 1984,88:897-900
59 Georgios M,Hofmann H.Coke Removal from a Zeolite Catalyst by Supercritical Fluids. Chem Eng Tech nol,1991,14:73-78
60 Tohnston K P, Kim S.New Direction in Supercritical Fluid and Technologu. Acs Symp Series, 1989,406: 37-43
61 闫世润等．超临界相F-T合成的研究概况．天然气化工，1996 (21)，47-51
62 Eckert C A et, al.,Fluid Phase Epuilib.,Phg. Chem., 1991,95:7795
2 R. F. McMahon, J. D. Greene Jr, D. A. Peterson. Process for Preparing 2, 6-Naphthalenedicarboxylic Acid[P]. US: 61145575。2000-09-05
3 杨彦文，王新，张文会．焦油洗油资源综合利用的工艺研究[J]．河北化工，1997，(1)：26-29
4 孙绪江，张军，齐彦伟．分子筛吸附分离2，6-二甲基萘[J]．精细石油化I，1999，(5)：4-6
5 Eldib Enginerring Co. [J]. Chemicalweek, p27, 1992-06-24
6 Yang K, Aizawa S. Process for Production of Dimethylnaphthalenes[P]. US: 4963248, 1990—10—16
7 Rex Clark N. Crowther J D, Galdwin K, et al. Preparation of Dimethylnaphthalenes[P]. GB: 2133032, 1983-01-07
8 Weitkamp J. Neuber M, Wilhelm D, et al. Preparation of 2, 6-dialkyl-naphthalenes[P]. US: 4795847, 1989-01-03
9 Weitkamp J, Neuber M. Lewis Acid Catalysts and Solvents Effects on the Alkylation of Naphthalene, J.of Ind. & Eng. Chem [J]. Stud. Surf. Sci. Catal. 1991, 60: 291-301
10 Fraenkel D, Cherniavsky M, Ittah B, et al. Ittah B,et al. Shape-Selective Alkylation of Naphthalene and Methylnaphthalene with Methanol over H-ZSM-5 Zeolite Catalyts [J]. J. of Catal, 1986, 101: 273-83
11 Komatsu I, Araki Y, Namba S, et al. [J]. Stud. Surf. Sci. Catal, 1994, 84:1821-1828
12 Tomoyuki I, Pu S B, Jun-ichiro K. [J]. Appl. Catal. A: General, 1996, 146: 285-296
13 Pu S B, Tomoyuki. [J]. Appl. Catal. A: General, 1996, 146: 305-316
14 徐海升，宋成盈，赵建宏等．[J]．石油学报(石油加工)，1999，15(1)：52—55
15 Angevine P J, Degnan T F, Marler D O. Process for Preparing Dialkylnapthalenet[P]. US: 5001295, 1991—03—19
16 Motoyuki M, Yamamoto K, Mcwilliams J P, et al. Process for Preparing Dialkylnapthalene[P]. US: 5744670. 1998-04-28
17 Motoyuki M, Yamamoto K, Mcwilliams J P, et al. Process for Preparing Dialkylnaphthalene[P]. US: 5844064. 1998-12-01
18 Motoyuki M, Yamamoto K, Ajit V, et al. Process for Preparing Dialkylnaphthalene[P]. US: 6011190, 2000-01-04
19 Motoyuki M, Yamamoto K, Sapre A V et al. Process for Preparing 2,
6-DialkyInaphthalene[P]. US: 6018080-2000-01-25
20 金田究弘．二甲基萘的制造方法[P]日本公开特许公报：JP4-120029[P]，1992-04-21
21 G.P. Hagen,D.T. Hung. Selective production of 2,6-dimethylnaphthalene[P].US :5670704,1997-09-23
22 D. K. Yong, H. K. Ju, J. S. Jun, et al. Lewis Acid Catalysts and Solvents Effects on the Alkylation of Naphthalene, J.of Ind. & Eng. Chem [J]. J. of Ind.& Eng. Chem. 1998, 4(4): 329-333
23 阿部正澍，清水俊夫．2，6—二甲基萘的制造方法[P]．日本公开特许公报：JP6-287152，1994—10—11
24 阿部正澍，清水俊夫．2，6—二甲基萘的制造方法[P]．日本公开特许公报：JP7—126194，1995—05—25
25 简井俊雄．二甲基萘的制造方法[P]．日本公开特许公报：JP11-139998[P]，1999-05-25
26 户井田努．二甲基萘的制造方法[P]．日本公开特许公报：JP63-14737，1988-01-21
27 Matsuda T, Katsunoro Y, Yaashuhiro M, et al. Shape Selective Catalysis by ZSM-5 in Disproportionation of 2-Methylnaphthalene [J]. Chem.Lett, 1990(7): 1085-1088
28 沈剑平，姜延顺，马骏，等．β-甲基萘歧化反应中HZSM-5择形性[J]．高等学校化学学报，1993，14(6)：845-848
29 沈剑平，姜延顺，马骏，等．层柱材料在β-甲基萘歧化反应中的催化行为[J]．高等学校化学学报，1993，14(8)：1135-1139
30 栗同林，刘希尧，王祥生．β沸石对甲基萘歧化反应的择形性[J]．催化学报，1997，18(3)：221-224
31 Angevine P J, Degnan T F, Marler D O. Process for the Catalytic Dispr oportionation of Methylllaphthalener[P]. us: 4982040, 1991-01-01
32 Abe T, Uchiyama S, Ojima T, et al. Process for Porduction of 2, 6-Dimethylnaphthalene[P]. US: 5008479, 199t-04-16
33 Takagawa M, Yamagishi K, Yoshihara J, et al. Process for Producing 2, 6-Dimethylnaphthalene[P]. yS: 5068480。1991。11-26
34 Inamasa K, Fushimi N, Takagawa M. Process for Prodyucing 2, 6-Dimethylnaphthalene[P]. US: 5321178, 1994-06-14
35 Bergstroem C, Niemelae M. Process for Preparaing 2, 6-Dimethylnaphthalene[P]. WO: 0034212, 2000-06-14
36 Jakkula J, Niemi V,Vahterlsto K, et al. Process of Producing 2, 6-Dimethylnaphthalene by dehydrocyclizing 1-(p-Tolyl)-2-methlbutane and / or 1-(p-Toly)-2-methylbutene using a Reduced Vanadium Catalyst[P]. US: 6127589。
2000-10． 03
37 Del Rossi K J, Green L A, Huss Jr A, et al . Process for Preparing Dimethylnaphthalene[P]. US: 5043501, 1991-08-27
38 ChenCY,SchinskiW, O Rear D,et al .Method of Making Dimethylnaphthalenes[P].US:5955641, 1999-09-21
39 Sikkenga;D.L.Monoalkenylation of alkylbenzenes in a fixed catalyst bed[P].US :4990717,1991-02-05
40 G.P.Hussmann G P,McMazhon P E.Cyclization Catalyst[P].US:4740647,1988-04-26
41 Sikkenga D L,Lamb J D,Zaenger I C, et al.Preparation of Dimethylnaphthalene[P] US:4950825,. 1990-08-21
42 Sikkenga D L,Lamb J D,Zaenger I C, et al.Preparation of Dimethyltetralin [P].US:5073670,1991-12-17
43 Sikkenga D L,Zaenger I C, Williams G S. Preparation of Dimethyltetralin in a Distillation Reactoi[P]. US:5284987,1994-02-08
44 Ozawa S, Takagawa M,Dnamasa K.Process for Production of Dimethyltetralin[P]. US:5396008,1995-03-07
45 Sikkenga D L, Zaenger I C, Lamb J D,et al .preparation of a Dimethylteralin by Cyclizing an Orthotolylpentene Phenylhexene Uising an Ultra-stable Crystalline Aluminosilicate Molecular Sieve y-Zeolite[P]. US:5401892,1995-03-28
46 Sikkenga D L,Zaenger I C,Williams G S.Preparation of Dimethylnaphthalene [P].US:5012024,1991-04-30
47 Amelse J A.Selective Dehyrogenation Processes and Catalysts[P]. US :5189234,1993-02-23
48 Kyuko Y, Ozawa S,Takagawa M,et al.Process for Production of Dimethylnaphthalene[P].US:53960 07,19 95-03-07
49 Ozawa S,Takagawa M,Fujimori T.Process for Production of Dimethylnaphthalene[P].US:5446226,1995-08-29
50 Vahteristo K, Halme;E,Koskimies S,et al.Manufacturing of 2,6-dimethylnaphthalene [P].US:5952534,199 9-09-14
51 Abe T, Ebata S,Machida H,et al.Process for Production of 2,6-Dimethylnaphth alene [P].US:5023390,1991-06-11
52 Meshram,N.R.,Negde,S.G.and Knlkarni,S.B.Zeolite, 1986(6):434
53 Dan Fraenkel,Margaret Chemiavsky, Baruch Ittah Shape-Sele ctive Alkylation of Naphthalene and Methy lnaphthalene with Methanol over HZSM-5 Zeolite Catalysts[J],Journal of Catalyst 1986(101),273-283
54 曾昭槐．择形催化．北京：中国石化出版社，1994：4-6，468-469，475，483，91-93
55 沈忠耀．超临界流体．化工百科全书(第二卷)，北京：化学工业出版社，1991．325-339
56 郭继志 袁渭康 初议超临界条件下的化学反应．化工进展，2000 (3)，8-13
57 王涛 艾大刚 李成岳．超临界化学反应的研究现状和趋势．化工进展，(3)，17-20
58 Tiltscer H,Woif H,Schelchshom J.Utilization of SCF Solvent-EFFects in Heterogeneous Catalysis. Ber Bunsenges Phy Chem, 1984,88:897-900
59 Georgios M,Hofmann H.Coke Removal from a Zeolite Catalyst by Supercritical Fluids. Chem Eng Tech nol,1991,14:73-78
60 Tohnston K P, Kim S.New Direction in Supercritical Fluid and Technologu. Acs Symp Series, 1989,406: 37-43
61 闫世润等．超临界相F-T合成的研究概况．天然气化工，1996 (21)，47-51
62 Eckert C A et, al.,Fluid Phase Epuilib.,Phg. Chem., 1991,95:7795