吡啶衍生物的合成及其催化剂的研究
摘要
吡啶衍生物的用途十分广泛，除用作溶剂外，还广泛应用于医药、农药、橡胶和染料等作为中间体。近年来，随着化学工业的发展，对吡啶及其衍生物的需求日益增长，而从煤焦油提取的方法，由于产量有限，已不适应市场的需求，改由合成法替代。但国内目前仅有的吡啶衍生物的生产装置及催化剂技术是从国外引进的，因此开发此项技术显得非常重要。
在目前的工业化生产中，这条合成路线主要是以甲醛、乙醛和氨气为原料，经缩合反应后实现的。可通过改变原料醛的种类或不同反应物摩尔比来调整产物的种类及分布，所使用的催化剂主要为ZSM-5分子筛。
本课题的主要研究内容为：(1)选择H-ZSM-5作为合成吡啶及其衍生物的催化剂，以甲醛、乙醛和氨气为原料进行了反应工艺的实验研究，确定了较佳的反应条件，并研究了加入第三种醛类丙醛作为反应物对提高3—甲基吡啶选择性的作用；(2)开展了吡啶衍生物合成催化剂的改性研究，用Zn~(2+)对H-ZSM-5分子筛进行改性；(3)研究了吡啶的甲基化反应，使用的催化剂为分子筛H-ZSM-5与共沉淀法制备的尖晶石。
通过实验，得到了以下的一些结果：(1)用H-ZSM-5作化剂、以甲醛、乙醛和氨气为原料合成吡啶及其衍生物，较佳的反应条件为：反应温度450～475℃，空速1000h~(-1)左右，甲醛：乙醛为1：1～2为较佳，有机物(甲醛、乙醛)：氨气为1：4左右，再生温度在550℃是合适的。加入第三种醛组分丙醛能显著地提高3—甲基吡啶的收率，而对吡啶总收率影响不大；(2)以甲醛、乙醛和氨气为原料，使用改性分子筛为催化剂能较大幅度地提高吡啶的总收率，提高的幅度在10％以上；(3)以尖晶石和H-ZSM-5为催化剂进行吡啶的甲基化反应，反应能在一定程度上进行，但存在收率低等问题，需作进一步探索。
Pyridine bases are widely used as intermediates in the formation of medicine, insecticide, rubber and dyestuff besides as solvents. With the rapid development of chemical industry , the demand for the pyridine bases increases quickly. But the way of refining from the coal tar hasn't satisfied the market needs, therefore replaced by the synthesis means. Several producing devices are imported from foreign countries, so it is important to study the pyridine bases' synthesis means, including the catalysts applied in the synthesis means.
This way mainly is completed through the condensation of formaldehyde, acetaldehyde and ammonia in the latest producing device. By changing original components and the mol ratio, different products and different distributions can be obtained, the catalyst is ZSM-5 zeolite.
The main contents of this task are:(1)choose the H-ZSM-5 zeolite as better catalyst for the pyridine bases' synthesis , carry out the research of technical conditions of synthesis which formaldehyde, acetaldehyde and ammonia are used and better synthesis conditions are selected. Besides these procedures, the addition of propionaldehyde as the third aldehyde for improving of the 3-picoline was studied.(2)carry out the ion-exchange of the H-ZSM-5 zeolite for the synthesis of pyridine bases;(3) research the reaction of pyridine methylation with H-ZSM-5 zeolite and the spinel through co-precipitation .
We obtained better reaction condition of pyridine bases with formaldehyde, acetaldehyde and ammonia, i.e. space velocity about 1000h-1, formaldehyde : acetaldehyde =1 : 1, organic compound : ammonia=1 : 4, reaction temperature =450℃-475℃.The addition of the propionaldehyde can improve the yield of 3-picoline rather than effect the total yield of pyridine bases. By using the ion-exchange zeolite Zn-ZSM-5 can improve the total yield of pyridine bases by 10% than ordinary H-ZSM-5 zeolite; The methylation reaction with the spinel and the H-ZSM-5 zeolite indicates that catalysts have some effects on the pyridine's methylation, but the yield is too low (<= 5%) ,so it is necessary to further the study.
在目前的工业化生产中，这条合成路线主要是以甲醛、乙醛和氨气为原料，经缩合反应后实现的。可通过改变原料醛的种类或不同反应物摩尔比来调整产物的种类及分布，所使用的催化剂主要为ZSM-5分子筛。
本课题的主要研究内容为：(1)选择H-ZSM-5作为合成吡啶及其衍生物的催化剂，以甲醛、乙醛和氨气为原料进行了反应工艺的实验研究，确定了较佳的反应条件，并研究了加入第三种醛类丙醛作为反应物对提高3—甲基吡啶选择性的作用；(2)开展了吡啶衍生物合成催化剂的改性研究，用Zn~(2+)对H-ZSM-5分子筛进行改性；(3)研究了吡啶的甲基化反应，使用的催化剂为分子筛H-ZSM-5与共沉淀法制备的尖晶石。
通过实验，得到了以下的一些结果：(1)用H-ZSM-5作化剂、以甲醛、乙醛和氨气为原料合成吡啶及其衍生物，较佳的反应条件为：反应温度450～475℃，空速1000h~(-1)左右，甲醛：乙醛为1：1～2为较佳，有机物(甲醛、乙醛)：氨气为1：4左右，再生温度在550℃是合适的。加入第三种醛组分丙醛能显著地提高3—甲基吡啶的收率，而对吡啶总收率影响不大；(2)以甲醛、乙醛和氨气为原料，使用改性分子筛为催化剂能较大幅度地提高吡啶的总收率，提高的幅度在10％以上；(3)以尖晶石和H-ZSM-5为催化剂进行吡啶的甲基化反应，反应能在一定程度上进行，但存在收率低等问题，需作进一步探索。
Pyridine bases are widely used as intermediates in the formation of medicine, insecticide, rubber and dyestuff besides as solvents. With the rapid development of chemical industry , the demand for the pyridine bases increases quickly. But the way of refining from the coal tar hasn't satisfied the market needs, therefore replaced by the synthesis means. Several producing devices are imported from foreign countries, so it is important to study the pyridine bases' synthesis means, including the catalysts applied in the synthesis means.
This way mainly is completed through the condensation of formaldehyde, acetaldehyde and ammonia in the latest producing device. By changing original components and the mol ratio, different products and different distributions can be obtained, the catalyst is ZSM-5 zeolite.
The main contents of this task are:(1)choose the H-ZSM-5 zeolite as better catalyst for the pyridine bases' synthesis , carry out the research of technical conditions of synthesis which formaldehyde, acetaldehyde and ammonia are used and better synthesis conditions are selected. Besides these procedures, the addition of propionaldehyde as the third aldehyde for improving of the 3-picoline was studied.(2)carry out the ion-exchange of the H-ZSM-5 zeolite for the synthesis of pyridine bases;(3) research the reaction of pyridine methylation with H-ZSM-5 zeolite and the spinel through co-precipitation .
We obtained better reaction condition of pyridine bases with formaldehyde, acetaldehyde and ammonia, i.e. space velocity about 1000h-1, formaldehyde : acetaldehyde =1 : 1, organic compound : ammonia=1 : 4, reaction temperature =450℃-475℃.The addition of the propionaldehyde can improve the yield of 3-picoline rather than effect the total yield of pyridine bases. By using the ion-exchange zeolite Zn-ZSM-5 can improve the total yield of pyridine bases by 10% than ordinary H-ZSM-5 zeolite; The methylation reaction with the spinel and the H-ZSM-5 zeolite indicates that catalysts have some effects on the pyridine's methylation, but the yield is too low (<= 5%) ,so it is necessary to further the study.
引文
1刘长令，汪灿明，于春睿等，农药，1999，38(5)：1～3
2王之德，天然气化工，1994(1)：33～37
3魏宝荣，梁娅，薛其峰等，陕西化工，1994(4)：26～28
4肖国民，钱杰生，化工时刊，1997(2)，3～5
5W09700861
6H. Sato, S. Shimizu, N. Abe and K. Hirose. Chemistry. Letters 1994,59～62
7US5013843
8US5395940
9US6187963
10Rama Rao A V ,Kulkarni S J,R, Subrahmanyam M, et al. Appl Catal A[J],1994,113:1～7
11王彩彬，李玉润，医药工业，1984(6)：1～6
12Kulkarni S J, Ramachandra Rao R。Subrahmanyam M, et al. Appl Catal A[J],1994.,113:1～7
13Van Der Gaag F J, Louter F, Oudejans J C, et al. Appl Catal[J],1986,26:191～201
14Prins R. Catal Today [J],1997,37,:103～120
15Kameswari, U.;Swamz, C.S.;Pillai, C.N. Stud. Surf. Catal. 1994,84:1959～64
16Sreekumar, k. ; Mathew, Thomas; Rajgopal, R. et al; Catal. Lett. 2000,65(1～3):99～105.
17K. Sreekumar, Thomas Mathew, Biju M. Devass Y, et al; Appl. Catal. A. 205(2001),11～18.
18JP2002,30070
19US 5,066,809
20S. Lanini, R. Prins. Appl. Cata1.A.1996,137(2) :287～306.
21WO 9000,546
22WO 9000,547
23US 5, 708, 176
24Stanislaw E. GOLUNSKI St. Appl Catal [J], 23 (1986): 1～14
25顾伯锷，吴震霄著．工业催化导论．北京：高等教育出版社．1990，119～194
26A.V. Rama Rao, S.J. Kulkarni. Appl. Catal. A general 111(1994): 104～108
27Ramachandra Rao, Kulkarni S J, Subrahmanzam M, et al. React Kinet Catal Lett[J],1995,56(2):301～309
28WO 9802286
29WO 9003366
30Sato, hiroshi; Shimiyu, shinnkichi; Abe, Nobuzuki; et al. Stud. Surf. Sci. Catal 1994(84): 1951～8
31Baidev Singh, Sisir Kr. Poz, Krishnadeo P. Sharma, tarun Kr. Goswami. J. Chem. Technol. 1998,71(3),246～252
32US5395940
33王桂茹，王祥生编著．催化剂与催化作用．-大连：大连理工大学出版社，2000．8
34于甦生，赵静，杨冰等．华东理工大学学报，2000，26(6)：326～328
35Sung-Jeng Jong, Ajit R. Pradhan. Jin-Fu Wu. et al.J Catal. 1998,174(2),210～218
36US5780635
37EP388070
38Shinkichi Shimiyu, Nobuzuki Abe, akira Iguchi, et al. Micropirous and Mesoporous Materials[J],1998,21:447～451
39v.v. Antonova, T.I. Ovchinnikova, B.F Ustavshchikov and V 。K. Promonenkov, Zh. Org. Khim。,1980,16,547
40韩念和，刘兴云，李宣文，余励勤，庞礼燃料化学学报，1987，5(4)：289～297
41黄曜，李全芝，殷行知，周佩玲，石油化工，1992，2l(10)：641～645
42程谟杰，王江迈，杨亚书，李灿物理化学学报，1995，11(8)：724～729
程谟杰，杨亚书，王江迈，李灿石油化工，1996，25(7)：458～461
2王之德，天然气化工，1994(1)：33～37
3魏宝荣，梁娅，薛其峰等，陕西化工，1994(4)：26～28
4肖国民，钱杰生，化工时刊，1997(2)，3～5
5W09700861
6H. Sato, S. Shimizu, N. Abe and K. Hirose. Chemistry. Letters 1994,59～62
7US5013843
8US5395940
9US6187963
10Rama Rao A V ,Kulkarni S J,R, Subrahmanyam M, et al. Appl Catal A[J],1994,113:1～7
11王彩彬，李玉润，医药工业，1984(6)：1～6
12Kulkarni S J, Ramachandra Rao R。Subrahmanyam M, et al. Appl Catal A[J],1994.,113:1～7
13Van Der Gaag F J, Louter F, Oudejans J C, et al. Appl Catal[J],1986,26:191～201
14Prins R. Catal Today [J],1997,37,:103～120
15Kameswari, U.;Swamz, C.S.;Pillai, C.N. Stud. Surf. Catal. 1994,84:1959～64
16Sreekumar, k. ; Mathew, Thomas; Rajgopal, R. et al; Catal. Lett. 2000,65(1～3):99～105.
17K. Sreekumar, Thomas Mathew, Biju M. Devass Y, et al; Appl. Catal. A. 205(2001),11～18.
18JP2002,30070
19US 5,066,809
20S. Lanini, R. Prins. Appl. Cata1.A.1996,137(2) :287～306.
21WO 9000,546
22WO 9000,547
23US 5, 708, 176
24Stanislaw E. GOLUNSKI St. Appl Catal [J], 23 (1986): 1～14
25顾伯锷，吴震霄著．工业催化导论．北京：高等教育出版社．1990，119～194
26A.V. Rama Rao, S.J. Kulkarni. Appl. Catal. A general 111(1994): 104～108
27Ramachandra Rao, Kulkarni S J, Subrahmanzam M, et al. React Kinet Catal Lett[J],1995,56(2):301～309
28WO 9802286
29WO 9003366
30Sato, hiroshi; Shimiyu, shinnkichi; Abe, Nobuzuki; et al. Stud. Surf. Sci. Catal 1994(84): 1951～8
31Baidev Singh, Sisir Kr. Poz, Krishnadeo P. Sharma, tarun Kr. Goswami. J. Chem. Technol. 1998,71(3),246～252
32US5395940
33王桂茹，王祥生编著．催化剂与催化作用．-大连：大连理工大学出版社，2000．8
34于甦生，赵静，杨冰等．华东理工大学学报，2000，26(6)：326～328
35Sung-Jeng Jong, Ajit R. Pradhan. Jin-Fu Wu. et al.J Catal. 1998,174(2),210～218
36US5780635
37EP388070
38Shinkichi Shimiyu, Nobuzuki Abe, akira Iguchi, et al. Micropirous and Mesoporous Materials[J],1998,21:447～451
39v.v. Antonova, T.I. Ovchinnikova, B.F Ustavshchikov and V 。K. Promonenkov, Zh. Org. Khim。,1980,16,547
40韩念和，刘兴云，李宣文，余励勤，庞礼燃料化学学报，1987，5(4)：289～297
41黄曜，李全芝，殷行知，周佩玲，石油化工，1992，2l(10)：641～645
42程谟杰，王江迈，杨亚书，李灿物理化学学报，1995，11(8)：724～729
程谟杰，杨亚书，王江迈，李灿石油化工，1996，25(7)：458～461