乙醇催化氨化合成2-甲基吡啶和4-甲基吡啶.pdf

石油化工
2010年第39卷第7期
PETROCHEMICAL TECHNOLOGY
775
8精细化工
乙醇催化氨化合成2-甲基吡啶和4-甲基呲啶
冯成,张月成,文彦珑,赵继全
(河北工业大学化工学院,天津300130)
摘要]通过对HZSM-5分子筛进行金属修饰制得一系列催化剂,考察了该系列催化剂对乙醇催化氨化合成2~甲基吡啶和4
甲基吡啶的性能,其中Pb。-Feas-Cos/ZSM-5(n(Si):n(Al)=200)催化剂的活性最高。同时考察了反应温度、n(氨气)
n(乙醇)和停留时间对合成反应的影响。实验结果表明,在P。-Feos-Co、/ZSM-5(n(Si):n(AI)=200)催化剂作用下,乙
醇催化氨化反应的适宜条件为:催化剂用量30mL、0.1MPa、450℃、n(氨气):(乙醇)=6:1、停留时间19.28;在此条件下,乙
醇转化率达100.0%,2-甲基吡啶和4-甲基吡啶的总收率达到29.0%。催化剂稳定性实验结果表明,反应进行16b后,2-甲基
吡啶和4-甲基吡啶的总收率仍可达23.6%。采用空气氧化法再生催化剂可部分快复催化剂的活性,反应过程中部分催化剂活
性组分被还原和生成积碳是导致催化剂活性下降的原因。
[关键词]乙醇;2-甲基呲啶;4-甲基呲啶;氨气;氨化;HESM-5分子筛俳化剂
[文章编号]1000-8144(2010)07-0775-07「中图分类号]TQ203.2[文献标识码」A
Syntheses of 2-picoline and 4-picoline by Catalytic Ammoniation of Ethanol
Feng Cheng, Zhang Yuecheng, Wen Yanlong, Zhao Jiguan
School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
I Abstract] A series of catalysts were prepared through modification of HZSM-5 molecular sieves
with several metals and used in ammoniation of ethanol to 2-picoline and 4-picoline. Pbs-feos-cos
ZSM-5(n(Si): n (Al)is 200 catalyst showed good catalytic activity in a fixed-bed reactor. Effects
of reaction temperature, mole ratio of ammonia to ethanol and residence time on the catalyst activity
were investigated. Under the optimized reaction conditions: catalyst dosage 30 ML, reaction pressure
0. 1 Mpa, reaction temperature 450 t, mole ratio of ammonia to ethanol 6: 1 and residence time
9.2 s, conversion of ethanol and total yield of both 2-picoline and 4-picoline were 100. 0g and
29.0%, respectively. The tota yield could still reach 23.6% after the catalyst running for 16 h. The
catalyst activity could be recovered partially through air oxidation. The fresh and used catalysts were
characterized by means of XRD and XPS. The results showed that the main reasons for the catalyst
deactivation were formation of Pb"by reduction of the active species and carbon deposition on the
catalyst during the catalyst running
I Keywords]ethanol; 2-picoline; 4-picoline; ammonia; ammoniation HZSM-5 molecular sieve catalyst
吡啶及其衍生物是一类重要的有机含氮化合料合成吡啶及其衍生物的方法。1956年美国
物,广泛应用于医药、农药、饲料、合成橡胶和染料 Indianapolis公司叩实现了吡啶破合成的工业化。
等领域“。吡啶类化合物最初由煤焦油分离制
得?,但由于煤焦油中吡啶衍生物的含量低,组分[收稿日期]2010-01-22:[修改稿日期」200-04-07。
复杂,因此分离提纯的难度较大,产品成本较高。
[作者简介]冯成(1981ー),男,河北省石家庄市人,博士生,电话
随着吡啶碱类化合物需求的不断增加,以煤焦油为
022-60204726,电邮fengchengcctv@163.com。联系人:张月成,电
话022-60204726,电邮yizhang@hebut.cdu.cn。
原料制取此啶及其行生物的方法已不能满足市场【基金项目」河比省青年科学基金项目(B20000E省科学
需求。1924年, Chichibabin提出了以醛和氨为原技术研究与发展指导计划项目(072156136)。