吡啶氯化工艺研究
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摘要
吡啶氯化物都是重要的化工原料,以吡啶直接氯化生产吡啶氯化物尤其是深度氯化物的研究多年来一直是化工行业的一个热点,也一度被誉为世界性难题。
本文在调研了大量文献的基础上,设计了吡啶氯化反应系统,筛选了不同的催化剂载体和催化剂活性组分,并且优化了反应的工艺条件,获得了比较好的结果,为以后工业化生产奠定了基础。
根据实际情况,计算了氯气、氮气和吡啶所需要的预热器换热面积,设计并加工了切实可行的蛇管式沙浴预热装置,设计并加工了固定床直管式吡啶反应器、撞击流气体混合器。经过调试能够正常运转。
结果表明催化剂(20%CoCl2、80%LaCl3/C)是一种催化活性比较高的吡啶氯化催化剂,对于该催化剂,最优的反应条件是原料配比值为nCl2:nPyridine = 8:1左右,适宜的反应温度为330～340℃,最佳的吡啶流量为280ml/h左右。
并且在此条件下,吡啶的转化率可以达到90%以上,目的产物五氯吡啶收率可以达到80%左右(纯度95%)。该催化剂在最优条件下经过系统正常运转42h后仍然有较好的活性和选择性,证明此反应系统设计合理,经济上可行,能够为以后的中试和工业化生产提供参考。进行了合理的工业化概念设计——年产1000吨五氯吡啶工业装置设计,经过经济性核算,五氯吡啶成本(不计算固定资产和能耗)为1.912万元/吨,远低于市场价格。
Pyridine and chloro-pyridines are very useful chemical materials,chemical intermediate, medical and pesticide intermediates. In recent years, it has been a hotspot in chemical field that chloro-pyridines are produced directly from pyridine, especially the poly-chloro-pyridine. So, it has been considered as a hard question world widely.
In this paper, according to a great deal of references, the system of pyridine-chlorination was built. Several catalyst carrier and active component were tested. The optimal technologic conditions were found, which reached in a better result. A foundation was built for industrialization latter.
According to the practical instance, the warm-up areas of nitrogen, chlorine, and pyridine warm-uppers were calculated. Three spiral-piping warm-uppers warmed by sand and upright fixed bed reactor for pyridine chlorination were designed and machined. They worked naturally after debugged.
The result showed the catalyst (20%CoCl280%LaCl3) was a high active one for pyridine chlorination. About this catalyst the optimum react conditions are the ratio of material: nCl2:nPyridine = 8:1, the fitting react temperature: 330～340℃, the optimal flux of pyridine: 280ml/h or so.
Under this condition, the conversation of pyridine reached over 90%, the yield of pentachloropyridine reached about 80%(95% pure). The catalyst has good activity and selectivity after continuous working naturally. A notional industrial design of pentachloropyridine with annual production 1000 tons was built. After economical calculation, the cost of pentachloropyridine (except fixed capital and energy sources) is far below the price on the market. It proved that this reaction system is reasonably designed and feasible economically and could be used for the magnified test and industrialization.
本文在调研了大量文献的基础上,设计了吡啶氯化反应系统,筛选了不同的催化剂载体和催化剂活性组分,并且优化了反应的工艺条件,获得了比较好的结果,为以后工业化生产奠定了基础。
根据实际情况,计算了氯气、氮气和吡啶所需要的预热器换热面积,设计并加工了切实可行的蛇管式沙浴预热装置,设计并加工了固定床直管式吡啶反应器、撞击流气体混合器。经过调试能够正常运转。
结果表明催化剂(20%CoCl2、80%LaCl3/C)是一种催化活性比较高的吡啶氯化催化剂,对于该催化剂,最优的反应条件是原料配比值为nCl2:nPyridine = 8:1左右,适宜的反应温度为330～340℃,最佳的吡啶流量为280ml/h左右。
并且在此条件下,吡啶的转化率可以达到90%以上,目的产物五氯吡啶收率可以达到80%左右(纯度95%)。该催化剂在最优条件下经过系统正常运转42h后仍然有较好的活性和选择性,证明此反应系统设计合理,经济上可行,能够为以后的中试和工业化生产提供参考。进行了合理的工业化概念设计——年产1000吨五氯吡啶工业装置设计,经过经济性核算,五氯吡啶成本(不计算固定资产和能耗)为1.912万元/吨,远低于市场价格。
Pyridine and chloro-pyridines are very useful chemical materials,chemical intermediate, medical and pesticide intermediates. In recent years, it has been a hotspot in chemical field that chloro-pyridines are produced directly from pyridine, especially the poly-chloro-pyridine. So, it has been considered as a hard question world widely.
In this paper, according to a great deal of references, the system of pyridine-chlorination was built. Several catalyst carrier and active component were tested. The optimal technologic conditions were found, which reached in a better result. A foundation was built for industrialization latter.
According to the practical instance, the warm-up areas of nitrogen, chlorine, and pyridine warm-uppers were calculated. Three spiral-piping warm-uppers warmed by sand and upright fixed bed reactor for pyridine chlorination were designed and machined. They worked naturally after debugged.
The result showed the catalyst (20%CoCl280%LaCl3) was a high active one for pyridine chlorination. About this catalyst the optimum react conditions are the ratio of material: nCl2:nPyridine = 8:1, the fitting react temperature: 330～340℃, the optimal flux of pyridine: 280ml/h or so.
Under this condition, the conversation of pyridine reached over 90%, the yield of pentachloropyridine reached about 80%(95% pure). The catalyst has good activity and selectivity after continuous working naturally. A notional industrial design of pentachloropyridine with annual production 1000 tons was built. After economical calculation, the cost of pentachloropyridine (except fixed capital and energy sources) is far below the price on the market. It proved that this reaction system is reasonably designed and feasible economically and could be used for the magnified test and industrialization.
引文
旺灿明,程春生,王凤宇等,2-氯代吡啶的合成研究,农药,1997,36(8):15～16
肖良,2-氯代吡啶和2,6-氯吡啶发展前景广阔,农药快讯,2002(13):13
陈煦,李永强,张和等,2,3,6-三氯吡啶的合成,精细石油化工,2002(3):38～40
金炼铁,余红杰,三氯吡啶酚及其钠盐的合成,精细化工,2002,19(8):474～476
许振元,许丹倩,毒死蜱的合成研究,农药,1998,37(1):15～17
张柏青,周曙光,胡军等,毒死蜱的合成研究,PESTICIDES,1999,38(7):4～5
孙致远,卢建华,赵风革等,毒死蜱的合成,农药,1998,37(4):13～14
石磊,含氯有机中间体,精细化工原料及中间体,2003,3:28～29
张智峰 ,农药知识简介,中学化学教学参考, 1999,187(3):49
岳永德,王如意等,毒死蜱在土壤中的光催化降解,安徽农业大学学报,2002,29(1):1～3
Russell M, Bimber, Painesville, Ohio Polychloro derivatives of mono-and-dicyano pyridine and a method for their prepartion . US: 3,325,503,1965-02-18
许丹倩,许振元,3,5,6-三氯吡啶-2-酚的合成,浙江工业大学学报,1996,24(1):16～23
Pew R G,Mich M. Process for producing 3,5,6-trichloropyridin-2-ol[P]. US:4,996,323,1989-05- 12
Pierre Rartin, Rheinfelden Switzerland Process for producing 2,3,5,6-tetrachloropyridine and 3,5,6-trichloropyridin-2-ol. US: 4,327,216 ,1980-11-24
Frank H, Murphy, Alvin, Tex.Process for producing 2,3,5,6-tetrachloropyridine .US: 4,703,123,1986-09-19
Becker Ylgal Production of 3,5,6-trichloropyridin-2-ol and novel intermediate thereof.EP:0,341,585,89-05-05
Eric Smith, Madison, Conn Process for preparing highly chloinated pyridines. US: 3,538,100 1968-03-15
Lorraine M K, Walnut C. Process for preparing phosphorothioates and phenylphosphorothioates [P].US:3,907,815,1973-05-21
陈甘棠,化学反应工程,化学工业出版社,205～253
陈甘棠,化学反应工程,化学工业出版社,147～151
刁玉伟,化工设备机械基础,大连理工大学出版社:45
高建,廖传华,管式反应器的数学模拟设计,粮食加工与食品机械,2002(11):35～37
唐军,钱旭红,陈卫东等,农药中间体五氯吡啶极其衍生物的制备和反应理论探析,农药译丛,1994,16(5):32～37
唐淑萍,管壳式换热器的结构设计,化学工业与工程技术,2002,23(5):39
王万得,杨恩翠等,吡啶气相光氯化反应机理研究,高等学校化学学报,2002,23(12):2256～2257
郝金库,赵增国等,吡啶光氯化反应的量子化学研究,1999,19(4):1～2
尹春华,罗和安等,间笨二甲腈气相催化氯化反应动力学模型,湖南化工,2000,30(1):20～22
王尚弟,孙俊全编,催化剂工程导论,北京:化学工业出版社,2001.4:81
赵九生等,催化剂生产原理. 北京:科学出版社,1986:72
29.A. B. Stiles. Catalyst Manufacture: Laboratory and Commercial Preparations. Marcel Dekker Co.1988
梁娟等,催化剂新材料,北京:化学工业出版社,1996:86
朱洪法,催化剂载体,北京:化学工业出版社,1993:95
朱洪法,催化剂成型,北京:化学工业出版社,1994:62
[日]白琦高保等编,王家寰等译,催化剂制造,北京:石油工业出版社,1991:53
[日]尾琦萃主编,催化手册翻译小组译,催化剂手册—按元素分类,北京:化学工业出版社,1982:74
刘希尧,催化剂宏观物性的测定(上),石油化工,1999(12)2000(1):106
刘希尧,催化剂宏观物性的测定(下),石油化工,2000(2):135
刘维桥,孙桂大,固体催化剂实用研究方法,北京:中国石化出版社,2000:236
吴越,催化化学,北京:科学出版社,1998:128
卢章焕,石油化工基础数据手册,北京,化学工业出版社,1982:166
(美)乔佩(Chopey,N.P.),(美)希克思(Hicks,T.G.)著,化工计算手册北京化学工业出版社1988.12:237
陈松茂编,有机合成工艺设计及反应装置,上海,上海交通大学出版社,1988:115
国家医药管理局上海医药设计院编,化工工艺设计手册 /北京-化学工业出版社 1986:38
肖良,2-氯代吡啶和2,6-氯吡啶发展前景广阔,农药快讯,2002(13):13
陈煦,李永强,张和等,2,3,6-三氯吡啶的合成,精细石油化工,2002(3):38～40
金炼铁,余红杰,三氯吡啶酚及其钠盐的合成,精细化工,2002,19(8):474～476
许振元,许丹倩,毒死蜱的合成研究,农药,1998,37(1):15～17
张柏青,周曙光,胡军等,毒死蜱的合成研究,PESTICIDES,1999,38(7):4～5
孙致远,卢建华,赵风革等,毒死蜱的合成,农药,1998,37(4):13～14
石磊,含氯有机中间体,精细化工原料及中间体,2003,3:28～29
张智峰 ,农药知识简介,中学化学教学参考, 1999,187(3):49
岳永德,王如意等,毒死蜱在土壤中的光催化降解,安徽农业大学学报,2002,29(1):1～3
Russell M, Bimber, Painesville, Ohio Polychloro derivatives of mono-and-dicyano pyridine and a method for their prepartion . US: 3,325,503,1965-02-18
许丹倩,许振元,3,5,6-三氯吡啶-2-酚的合成,浙江工业大学学报,1996,24(1):16～23
Pew R G,Mich M. Process for producing 3,5,6-trichloropyridin-2-ol[P]. US:4,996,323,1989-05- 12
Pierre Rartin, Rheinfelden Switzerland Process for producing 2,3,5,6-tetrachloropyridine and 3,5,6-trichloropyridin-2-ol. US: 4,327,216 ,1980-11-24
Frank H, Murphy, Alvin, Tex.Process for producing 2,3,5,6-tetrachloropyridine .US: 4,703,123,1986-09-19
Becker Ylgal Production of 3,5,6-trichloropyridin-2-ol and novel intermediate thereof.EP:0,341,585,89-05-05
Eric Smith, Madison, Conn Process for preparing highly chloinated pyridines. US: 3,538,100 1968-03-15
Lorraine M K, Walnut C. Process for preparing phosphorothioates and phenylphosphorothioates [P].US:3,907,815,1973-05-21
陈甘棠,化学反应工程,化学工业出版社,205～253
陈甘棠,化学反应工程,化学工业出版社,147～151
刁玉伟,化工设备机械基础,大连理工大学出版社:45
高建,廖传华,管式反应器的数学模拟设计,粮食加工与食品机械,2002(11):35～37
唐军,钱旭红,陈卫东等,农药中间体五氯吡啶极其衍生物的制备和反应理论探析,农药译丛,1994,16(5):32～37
唐淑萍,管壳式换热器的结构设计,化学工业与工程技术,2002,23(5):39
王万得,杨恩翠等,吡啶气相光氯化反应机理研究,高等学校化学学报,2002,23(12):2256～2257
郝金库,赵增国等,吡啶光氯化反应的量子化学研究,1999,19(4):1～2
尹春华,罗和安等,间笨二甲腈气相催化氯化反应动力学模型,湖南化工,2000,30(1):20～22
王尚弟,孙俊全编,催化剂工程导论,北京:化学工业出版社,2001.4:81
赵九生等,催化剂生产原理. 北京:科学出版社,1986:72
29.A. B. Stiles. Catalyst Manufacture: Laboratory and Commercial Preparations. Marcel Dekker Co.1988
梁娟等,催化剂新材料,北京:化学工业出版社,1996:86
朱洪法,催化剂载体,北京:化学工业出版社,1993:95
朱洪法,催化剂成型,北京:化学工业出版社,1994:62
[日]白琦高保等编,王家寰等译,催化剂制造,北京:石油工业出版社,1991:53
[日]尾琦萃主编,催化手册翻译小组译,催化剂手册—按元素分类,北京:化学工业出版社,1982:74
刘希尧,催化剂宏观物性的测定(上),石油化工,1999(12)2000(1):106
刘希尧,催化剂宏观物性的测定(下),石油化工,2000(2):135
刘维桥,孙桂大,固体催化剂实用研究方法,北京:中国石化出版社,2000:236
吴越,催化化学,北京:科学出版社,1998:128
卢章焕,石油化工基础数据手册,北京,化学工业出版社,1982:166
(美)乔佩(Chopey,N.P.),(美)希克思(Hicks,T.G.)著,化工计算手册北京化学工业出版社1988.12:237
陈松茂编,有机合成工艺设计及反应装置,上海,上海交通大学出版社,1988:115
国家医药管理局上海医药设计院编,化工工艺设计手册 /北京-化学工业出版社 1986:38