CN105712924A - 以改性分子筛催化生产吡啶及甲基吡啶的方法 - Google Patents
以改性分子筛催化生产吡啶及甲基吡啶的方法 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 7
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 carboxyl compound Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229960003350 isoniazid Drugs 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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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
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- 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
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- Chemical & Material Sciences (AREA)
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- Pyridine Compounds (AREA)
Abstract
本发明涉及吡啶及其衍生物合成领域，具体地说是一种以改性分子筛催化生产吡啶及甲基吡啶的方法。制备过程按照原料氨、甲醛和乙醛的摩尔比例为0.5~1:1~1.5:2~8，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为180~350℃、压力为0.2~0.5Mpa条件下反应4~15h，气相空速为200~280/h，得到吡啶及甲基吡啶。本发明制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产，产品收率达82.5%以上。
Description
技术领域
本发明属于吡啶及其衍生物合成领域，具体地说是一种以改性分子筛催化生产吡啶及甲基吡啶的方法。
背景技术
吡啶是农药和药物生产中的一种重要中间体，而且还是聚合物和纺织工业中的一种重要溶剂。吡啶的重要衍生物包括烟酸和烟酰胺（人体健康所需的基本维生素）、氯苯朴尔敏、十六基吡啶盐、异烟肼、以及百草枯等。在环状结构上连接一个甲基的吡啶成为甲基吡啶或者皮考林，并且包括2-甲基吡啶、3-甲基吡啶，以及4-甲基吡啶。吡啶和甲基吡啶可作为煤焦油工业或焦炭工业生产的副产品而获得。然后，在焦油中人们仅仅发现少量吡啶，而获得吡啶的优选方法是进行催化合成。催化合成一般通过氨与羧基化合物例如醛或酮的催化气相反应。然后，这些催化合成反应历来具有收率低、选择性差，以及操作周期和催化剂寿命短的缺点。
目前国内大多数生产单位使用催化剂崔化合成吡啶及其衍生物的工艺，催化合成法适应工业化大规模生产，技术含量高、一次性投资大、原料消耗低、产品质量稳定、环境污染轻，国内企业普遍使用，很多企业和科研单位也正在积极开发。但是目前催化合成法制备吡啶及其衍生物的产品的工艺中仍普遍存在制备时间长、反应不充分、工序复杂、生产效率低、生产转化率低、催化剂寿命短、催化选择性差等问题，研发一种高效并且高转化率的催化合成法制备吡啶及其衍生物成为趋势。
发明内容
本发明的目的是克服目前催化合成法制备吡啶及其衍生物的产品的工艺中仍普遍存在制备时间长、反应不充分、工序复杂、生产效率低、生产转化率低、催化剂寿命短、催化选择性差等问题，提供一种高效并且高转化率的催化合成法制备吡啶及其衍生物成为趋势。。
本发明的方案是通过这样实现的：一种以改性分子筛催化生产吡啶及甲基吡啶的方法，按照原料氨、甲醛和乙醛的摩尔比例为0.5~1:1~1.5:2~8，在合成催化剂和改性分子筛存在的条件下，进行催化合成反应得到吡啶及甲基吡啶。
作为本发明的进一步限定，所述的合成催化剂为4A沸石Na12Al12Si12O48·27H2O、层状硅酸钠、聚丙烯酸、偏硅酸钠中的任一种或是它们的混合。
作为本发明的进一步限定，所述的改性分子筛为MCM-41、MCM-22、HY以及HZSM-5，优选MCM-41、MCM-22分子筛中的任一种，经过300~500℃高温活化3h，冷却后于45℃～60℃的硅烷化试剂中隔氧搅拌反应12~16h得到。
作为本发明的进一步限定，所述的催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为0.5~3%和3~15%。
作为本发明的进一步限定，所述的催化合成反应是在温度为180~350℃、压力为0.2~0.5Mpa条件下反应4~15h，气相空速为200~280/h。
本发明具备以下良好效果：利用氧化催化剂和改性分子筛促进吡啶的合成反应的发生，在催化剂存在的情况下降低生产的能耗和缩短反应的时间，并减少了多烷基吡啶和较高分子量的芳族化合物等的形成，实现生产成本的降低，提高产品的质量，减小环境污染。本发明使用的改性分子筛具有结构稳定、催化活性和选择性高的特点，使得水解反应过程温和，制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产，产品收率达82.5%以上。
具体实施方式
以下结合实施例描述本发明制备吡啶及甲基吡啶的合成方法，这些描述并不是对本发明内容作进一步的限定。
实施例1
本实施例用到合成催化剂为4A沸石Na12Al12Si12O48·27H2O。改性分子筛为MCM-22，经过500℃高温活化3h，冷却后于45℃℃的硅烷化试剂中隔氧搅拌反应12h得到。
本实施例按照原料氨、甲醛和乙醛的摩尔比例为0.5~1:1~1.5:2~8，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为200℃、压力为0.4Mpa条件下反应15h，气相空速为230/h，得到吡啶及甲基吡啶。催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为3%和15%。
本实施例得到的产品收率达86%，其中吡啶及甲基吡啶的含量分别为64%和22%。
实施例2
本实施例用到合成催化剂为层状硅酸钠。改性分子筛为HZSM-5，经过300℃高温活化3h，冷却后于60℃的硅烷化试剂中隔氧搅拌反应16h得到。
本实施例按照原料氨、甲醛和乙醛的摩尔比例为0.6:1:5，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为350℃、压力为0.35Mpa条件下反应4h，气相空速为220/h，得到吡啶及甲基吡啶。催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为0.5%和6%。
本实施例得到的产品收率达86%，其中吡啶及甲基吡啶的含量分别为60.5%和25.5%。
实施例3
本实施例用到合成催化剂为聚丙烯酸。改性分子筛为HY，经过450℃高温活化3h，冷却后于50℃的硅烷化试剂中隔氧搅拌反应12~16h得到。
本实施例按照原料氨、甲醛和乙醛的摩尔比例为0.81:1.2:8，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为180℃、压力为0.4Mpa条件下反应8h，气相空速为250/h，得到吡啶及甲基吡啶。催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为1%和3%。
本实施例得到的产品收率达88%，其中吡啶及甲基吡啶的含量分别为58%和30%。
实施例4
本实施例用到合成催化剂为偏硅酸钠。改性分子筛为MCM-22，经过500℃高温活化3h，冷却后于60℃的硅烷化试剂中隔氧搅拌反应14h得到。
本实施例按照原料氨、甲醛和乙醛的摩尔比例为1:1.5:6，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为300℃、压力为0.5Mpa条件下反应12h，气相空速为200/h，得到吡啶及甲基吡啶。催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为2.5%和10%。
本实施例得到的产品收率达88%，其中吡啶及甲基吡啶的含量分别为64%和24%。
实施例5
本实施例用到合成催化剂为层状硅酸钠和偏硅酸钠质量比1:1的混合物。改性分子筛为MCM-41，经过400℃高温活化3h，冷却后于55℃的硅烷化试剂中隔氧搅拌反应14h得到。
本实施例按照原料氨、甲醛和乙醛的摩尔比例为0.5:1:2，在合成催化剂和改性分子筛存在的条件下，催化合成反应是在温度为250℃、压力为0.2Mpa条件下反应10h，气相空速为280/h，得到吡啶及甲基吡啶。催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为1%和9%。
本实施例得到的产品收率达82.5%，其中吡啶及甲基吡啶的含量分别为62%和22.5%。
本发明上述实施例方案仅是对本发明的说明而不能限制本发明，权利要求中指出了本发明产品组成成分、成分比例、制备方法参数的范围，而上述的说明并未指出本发明参数的范围，因此，在与本发明的权利要求书相当的含义和范围内的任何改变，都应当认为是包括在权利要求书的范围内。
本发明是经过多位吡啶合成反应研发人员长期工作经验积累，并通过创造性劳动创作而出，本发明使用的改性分子筛具有结构稳定、催化活性和选择性高的特点，使得水解反应过程温和，制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产。产品收率达82.5%以上。
Claims (5)
1.一种以改性分子筛催化生产吡啶及甲基吡啶的方法，其特征在于，按照原料氨、甲醛和乙醛的摩尔比例为0.5~1:1~1.5:2~8，在合成催化剂和改性分子筛存在的条件下，进行催化合成反应得到吡啶及甲基吡啶。
2.根据权利要求1所述的以改性分子筛催化生产吡啶及甲基吡啶的方法，其特征在于，所述的合成催化剂为4A沸石Na12Al12Si12O48·27H2O、层状硅酸钠、聚丙烯酸、偏硅酸钠中的任一种或是它们的混合物。
3.根据权利要求1所述的以改性分子筛催化生产吡啶及甲基吡啶的方法，其特征在于，所述的改性分子筛为MCM-41、MCM-22、HY以及HZSM-5，优选MCM-41、MCM-22分子筛中的任一种，经过300~500℃高温活化3h，冷却后于45℃～60℃的硅烷化试剂中隔氧搅拌反应12~16h得到。
4.根据权利要求1所述的以改性分子筛催化生产吡啶及甲基吡啶的方法，其特征在于，所述的催化合成反应过程中合成催化剂和改性分子筛在催化反应体系中的含量或体积分数分别为0.5~3%和3~15%。
5.根据权利要求1所述的以改性分子筛催化生产吡啶及甲基吡啶的方法，其特征在于，所述的催化合成反应是在温度为180~350℃、压力为0.2~0.5Mpa条件下反应4~15h，气相空速为200~280/h。
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