CN105732485A - 一种合成3-甲基吡啶的方法 - Google Patents

一种合成3-甲基吡啶的方法 Download PDF

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CN105732485A
CN105732485A CN201610296074.3A CN201610296074A CN105732485A CN 105732485 A CN105732485 A CN 105732485A CN 201610296074 A CN201610296074 A CN 201610296074A CN 105732485 A CN105732485 A CN 105732485A
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picoline
catalyst
zsm
tubular reactor
method synthesizing
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王柏军
时建刚
王运红
李秋菊
丁金囤
高海珺
赵彤彤
张昊
郑雪
赵云
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Handan Zhaodu Fine Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure
    • C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
    • C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Abstract

一种合成3?甲基吡啶的方法，其工艺步骤为：①首先预处理催化剂ZSM?5并将催化剂ZSM?5装入管式反应器中即装有分子筛的管式反应器，②再将丙烯醛、丙酮、水蒸气和氨分别加热至180—210℃以一定比例混合，经氮气稀释后加压到2.0—2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，③随后通过冷却塔分离，精馏得到3?甲基吡啶和吡啶。与现有技术相比，本发明原料易得、操作简单、收率高且催化剂ZSM?5重复使用次数高。

Description

一种合成3-甲基吡啶的方法
技术领域
本发明涉及一种合成3-甲基吡啶的方法。
背景技术
3-甲基吡啶主要应用于农药、医药、饲料添加剂、香料等领域，在医药上用于合成盐酸、烟酸铵等，具有广泛用途。目前常采用低碳醛和氨为主要原料缩合而得，如申请公布号为CN1506354的中国专利申请，以氨、甲醛、乙醛为原料，以处理过的分子筛为催化剂气相合成；JP8333343的日本专利，采用改性分子筛为催化剂，用丙烯醛、乙醛或（和）酮和氨为原料合成；文件GB1192255则采用环氧丙烷、丙烯醛为原料，固体酸为催化剂合成；US5395940以2-4碳的醛、3-5碳的酮、氨、MCM-49或MCM-22为催化剂合成；授权公告号为CN101979380B的中国发明专利采用离子液体制备。以上方法不是因反应选择性差（收率低）就是因催化剂重复使用次数少、反应条件高（高温高压）而难以实现工业化生产。因此，研究一种收率高、催化剂重复使用次数多、反应条件低的合成3-甲基吡啶的方法，是目前需要解决的技术问题。
发明内容
本发明所要解决的技术问题是提供一种收率高、催化剂重复使用次数多、反应条件低的合成3-甲基吡啶的方法。
本发明解决其技术方案的技术方案是：
一种合成3-甲基吡啶的方法，其工艺步骤为：①首先预处理催化剂ZSM-5并将催化剂ZSM-5装入管式反应器中即装有分子筛的管式反应器，②再将丙烯醛、丙酮、水蒸气和氨分别加热至180—210℃以一定比例混合，经过氮气稀释后加压到2.0—2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，③随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶。
作为本发明的一种优选方案，所述的预处理催化剂即将ZSM-5在温度为50—200℃、压力为0.1—3MPa的金属氟化物的三氟化硼/乙醚溶液中浸泡0.5—10小时。
作为本发明的一种优选方案，所述的金属氟化物为碱金属和碱土金属氟化物。
作为本发明的一种优选方案，所述的预处理催化剂即研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。
作为本发明的一种优选方案，丙烯醛、丙酮、水蒸气和氨的体积比为6%：1.6%：2%：15%。
所述的催化剂活化处理再利用为将使用后的催化剂ZSM-5经120℃水蒸气处理后，再将使用后的催化剂ZSM-5在温度为50—200℃、压力为0.1—3MPa的金属氟化物、三氟化硼/乙醚溶液中浸泡0.5—10小时，优选将研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。
与现有技术相比，本发明原料易得、操作简单、收率高且催化剂ZSM-5重复使用次数高。
具体实施方式
一种合成3-甲基吡啶的方法，其工艺步骤为：①首先预处理催化剂ZSM-5并将催化剂ZSM-5装入管式反应器中即装有分子筛的管式反应器，②再将丙烯醛、丙酮、水蒸气和氨分别加热至180—210℃以一定比例混合，氮气稀释后加压到2.0—2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，③随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶。
作为本发明的一种优选方案，所述的预处理催化剂即将ZSM-5在温度为50—200℃、压力为0.1—3MPa的金属氟化物、三氟化硼/乙醚溶液中浸泡0.5—10小时。
作为本发明的一种优选方案，所述的金属氟化物为碱金属和碱土金属氟化物。
作为本发明的一种优选方案，所述的预处理催化剂即研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。
作为本发明的一种优选方案，丙烯醛、丙酮、水蒸气和氨的体积比为6%：1.6%：2%：15%。
所述的催化剂活化处理再利用为将使用后的催化剂ZSM-5在温度为50—200℃、压力为0.1—3MPa的金属氟化物、三氟化硼/乙醚溶液中浸泡0.5—10小时优选将研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。
实施例1
把预处理过的丙烯醛、丙酮、水蒸气、氨气分别加热到180℃后，以体积比6%：1.6%：2%：15%的比例混合，氮气稀释后，加压到2.0MPa，以9L/min的速度通过装有分子筛的管式反应器，随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶，经气相色谱分析，丙烯醛转化率95.6%，以丙烯醛计，3-甲基吡啶收率52.3%，吡啶收率8.4%。
实施例2
把预处理过的丙烯醛、丙酮、水蒸气、氨气分别加热到200℃后，以体积比6%：1.6%：2%：15%的比例混合，氮气稀释后，加压到2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶，经气相色谱分析，丙烯醛转化率96.7%，以丙烯醛计，3-甲基吡啶收率55.6%，吡啶收率8.3%。
实施例3
把预处理过的丙烯醛、丙酮、水蒸气、氨气分别加热到220℃后，以体积比6%：1.6%：2%：15%的比例混合，氮气稀释后，加压到2.0MPa，以9L/min的速度通过装有分子筛的管式反应器，随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶，经气相色谱分析，丙烯醛转化率95.4%，以丙烯醛计，3-甲基吡啶收率53.8%，吡啶收率7.9%。
实施例4
把预处理过的丙烯醛、丙酮、水蒸气、氨气分别加热到210℃后，以体积比6%：1.6%：2%：15%的比例混合，氮气稀释后，加压到2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶，经气相色谱分析，丙烯醛转化率97.7%，以丙烯醛计，3-甲基吡啶收率60.3%，吡啶收率9.8%。
催化剂活化处理再利用为将使用后的催化剂ZSM-5经120℃水蒸气处理后，再将使用后的催化剂ZSM-5在温度为50—200℃、压力为0.1—3MPa的金属氟化物、三氟化硼/乙醚溶液中浸泡0.5—10小时，优选将研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。

Claims (5)

1.一种合成3-甲基吡啶的方法，其特征在于，其工艺步骤为：①首先预处理催化剂ZSM-5并将催化剂ZSM-5装入管式反应器中即装有分子筛的管式反应器，②再将丙烯醛、丙酮、水蒸气和氨分别加热至180—210℃以一定比例混合再与氮气稀释，加压到2.0—2.4MPa，以9L/min的速度通过装有分子筛的管式反应器，③随后通过冷却塔分离，精馏得到3-甲基吡啶和吡啶；④催化剂活化处理再利用。
2.根据权利要求1所述的一种合成3-甲基吡啶的方法，其特征在于，所述的催化剂预处理是将ZSM-5在温度为50—200℃、压力为0.1—3MPa金属氟化物的三氟化硼/乙醚溶液中浸泡0.5—10小时。
3.根据权利要求2所述的一种合成3-甲基吡啶的方法，其特征在于，所述的金属氟化物为碱金属和碱土金属氟化物。
4.根据权利要求2或3所述的一种合成3-甲基吡啶的方法，其特征在于，所述的预处理催化剂即将研磨后的金属氟化物、三氟化硼/乙醚及ZSM-5加入到高压反应釜中，油浴加热到120℃，保温6小时，过滤得到预处理催化剂ZSM-5。
5.根据权利要求1所述的一种合成3-甲基吡啶的方法，其特征在于，丙烯醛、丙酮、水蒸气和氨的体积比为6%：1.6%：2%：15%。
CN201610296074.3A 2016-05-08 2016-05-08 一种合成3-甲基吡啶的方法 Pending CN105732485A (zh)

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Cited By (1)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115403518A (zh) * 2022-09-19 2022-11-29 浙江伟锋药业有限公司 一种5-烷基吡啶-2,3-二羧酸酯的连续流合成工艺

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