CN101648905A - Preparation method of 2- chloro-6-trichloromethyl pyridine - Google Patents
Preparation method of 2- chloro-6-trichloromethyl pyridine Download PDFInfo
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- CN101648905A CN101648905A CN200910092553A CN200910092553A CN101648905A CN 101648905 A CN101648905 A CN 101648905A CN 200910092553 A CN200910092553 A CN 200910092553A CN 200910092553 A CN200910092553 A CN 200910092553A CN 101648905 A CN101648905 A CN 101648905A
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Abstract
The invention provides a preparation method of 2-chloro-6-trichloromethyl pyridine. The method comprises the following steps: carrying out water gasification by taking 2-trichlormethyl as initial material, then taking activated carbon with metal ion oxides, such as Fe, Zn and the like as catalyst, taking nitrogen as carrier gas, reacting with chlorine and then generating 2-chloro-6-trichloromethylpyridine, and rectifying to obtain the finished product with the overall yield being more than 75 percent. In the preparation method, continuous reactions are adopted, and the operation is very safeand convenient; and meanwhile, hydrogen chloride generated by reaction is prepared into hydrochloric acid by water absorption as the used materials are less, excess chlorine and sodium hydroxide reactto prepare sodium hypochlorite, therefore, the emission amount of three wastes is less, which is environmental-friendly; and the production cost of the product is greatly reduced.
Description
Technical field
The present invention relates to a kind of preparation method of N-serve, specifically, relate to a kind of chemical preparation process of N-serve.
Background technology
The chlorine pyridine is a kind of nitrification inhibitor, claims nitrogen fertilizer potentiating agent again, and a class is to the deleterious organic compound of nitrobacteria.Goring reported first chlorine in 1962 pyridine has the inhibiting nitrification characteristic, and U.S. DOW chemical company just utilized the inhibiting nitrification feature development of chlorine pyridine to produce a kind of nitrification inhibitor product in 1974, and applied on agricultural.They can optionally suppress the activity of nitrobacteria in the soil, thereby the slow soil ammonium-state of resistance is converted into the speed of response of nitric nitrogen.Ammonium nitrogen can be difficult for running off by the soil colloid sorption, but under the ventilative condition of soil, ammonium nitrogen can be converted into nitric nitrogen under microbial process, and this process claims nitrated.The speed of reaction depends on soil humidity and temperature.When being lower than 10 ℃, nitration reaction speed is very slow; In the time of more than 20 ℃, speed of response is very fast.Except that some crop such as paddy rice can directly absorb the ammonium nitrogen under irrigation condition, most crops absorb nitric nitrogen.But nitric nitrogen runs off in soil easily, rationally uses nitrification inhibitor with control nitration reaction speed, can reduce the loss of nitrogen, improves the utilization ratio of nitrogenous fertilizer, thereby have very strong practical value in agriculture production.Document has reported that respectively with 2-picoline (US3420883/US4483993/US4487935/US4564681/JP2005255560/EP0 557967) and 2-picoline hydrochloride (US3424754) and 2-Pyridinecarboxylic Acid (US4419514) be raw material synthetic method, makes N-serve.Above method is not that raw material is not easy to obtain, and such as 2-Pyridinecarboxylic Acid, is exactly that reaction yield is undesirable, and what also have has used the disagreeableness tetracol phenixin of environment, thereby causes raw materials cost very high, does not have the market competitiveness; Therefore from aspects such as environment protection and production cost, all be necessary to improve.
Summary of the invention
The present invention is intended to overcome the defective of aforesaid method.A kind of yield height is provided, operational safety, production cost is lower, and three wastes discharge amount is few, the preparation method of environment amenable N-serve.
The objective of the invention is to adopt following technical scheme to realize: a kind of preparation method of N-serve, react under catalyst action by 2-picoline after aqueous vaporization and chlorine, make product.
Purpose of the present invention can also adopt following technical scheme further to realize.
Aforesaid preparation method, with the 2-picoline is starting raw material, under catalyst action, make product through chlorination reaction, comprise step: the 2-picoline mixes with the chlorine and the carrier gas of process preheating after aqueous vaporization, under the effect of catalyzer, react at a certain temperature, reaction product obtains N-serve after condensation, rectifying.
Aforesaid preparation method, wherein said carrier gas is nitrogen, helium or argon gas.
Aforesaid preparation method, the gasification of wherein said 2-picoline comprises and earlier the 2-picoline being mixed by a certain percentage with water, carries out the moment gasification then.
Aforesaid preparation method, wherein said water is distilled water or deionized water.
Aforesaid preparation method, wherein said catalyzer is the gac of loaded metal ion compound.
Aforesaid preparation method, wherein said metal ion compound comprises iron(ic) chloride, zinc chloride, cobalt chloride, bariumchloride, cupric chloride or rare earth chloride.
Aforesaid preparation method, the weight percent that wherein said metal ion compound accounts for gac is 1%-30%.
Aforesaid preparation method, the mol ratio of wherein said 2-picoline and water is 1: 5-20, preferred 1: 10.
Aforesaid preparation method, the mol ratio of wherein said 2-picoline and chlorine is 1: 10-30, preferred 1: 20.
Aforesaid preparation method, wherein said temperature of reaction are 180～320 ℃, preferred 220～260 ℃.
Chemical reaction process:
By technique scheme, the present invention has following advantage and beneficial effect at least:
1, the present invention adopts 2-picoline and chlorine to react under catalyst action, obtains product by rectifying then, the reaction conditions gentleness, and operation meets requirement of safe production easily.
2, the present invention adopts the gac of loaded metal ion to make catalyzer, makes the selectivity of reaction improve greatly, so the yield height, and cost is low.
3, the present invention adopt water vapour that the 2-picoline is gasified and with nitrogen as carrier gas, make a small amount of tar that reaction produces in reaction by wash-out, prolong the work-ing life of catalyzer.
4, the hydrogenchloride of the present invention's generation and excessive chlorine all recycle, and emit no waste water, and have accomplished cleaner production, and is energy-saving and cost-reducing.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The method of present embodiment Synthetic 2-chloro-6-nitrapyrin mainly is that the mixed gas of employing gasiform 2-picoline and water is a raw material, is carrier gas with nitrogen, carries out continuous reaction with chlorine by the fixed bed unit that is loaded with catalyzer.The operation step at first is the activation to catalyzer.Iron(ic) chloride mixed according to weight ratio with gac at 1: 99 be placed on the fixed bed, the unlatching heating system is with catalyzer temperature-elevating and be incubated 290 ℃, speed with per second 0.6L fed the nitrogen activation after 30 minutes, stop nitrogen and change feeding chlorine, speed with per second 0.9L activates 1 hour, after catalyst activation finishes, fixed bed unit is cooled to 250 ℃, prepare to carry out chlorination reaction.Adding 200 gram 2-picolines (2.13mol, content 99%), deionized water 383 grams (21.3mol) mix in order to reacting in mixing tank.Open fixed bed tail gas absorption system, when keeping nitrogen to reach more than 150 ℃ with the speed of per second 0.9L by the preheater temperature, insert fixed bed reaction equipment with the speed of per second 0.6L, chlorine.Mode with vaporization fully enters fixed bed reaction equipment to the 2-picoline aqueous solution that mixes through vaporizer heating back, keeps with the reacting of the speed uniform and stable of per minute 5.0 grams, and the 2-picoline aqueous solution dropwised in about 2.5 hours, the reaction end.Close heating system and chlorine, wait the fixed bed temperature to reduce to room temperature after, close nitrogen system again.The product that reaction obtains is prepared to make with extra care, separate after the receiving vessel condensation.Chlorine excessive in the reaction process absorbs back generation clorox with alkali.The hydrogen chloride gas that generates in the reaction process is made technical hydrochloric acid through the tail gas absorption system.
The qualitative analysis of fixed bed reaction products obtained therefrom contains N-serve 84.2% under this condition, and remaining is unreacted is lower boiling three chloroformate mixtures and react excessive high boiling material completely.With the rectifying column that is equivalent to 35 blocks of theoretical trays, add Stainless Steel Helices, under the 7mmHg vacuum condition, 170 ℃ of liquid temperature, isolate a small amount of lower boiling 2-nitrapyrin earlier, receive the about 145 ℃ main fraction of top temperature then, remaining is some high boiling heavy constituent products 3,6-two chloro-2-nitrapyrins can be used as the intermediate of pesticide herbicide.Obtain product 388 grams after the separation, content is more than 95%, and yield is greater than 75%.
Embodiment 2
Present embodiment Synthetic 2-the method for chloro-6-nitrapyrin is the same substantially with the method for embodiment 1 and reactions steps, adopts the fixed bed continuous reaction.Catalyzer changes zinc chloride into to be mixed according to weight ratio with gac at 3: 17, the import volume of 2-picoline and water changes 15 in the reaction ratio: 1mol, the fixed bed reaction temperature also is adjusted into 280 ℃, adding 200 gram 2-picolines (2.13mol, content 99%), deionized water 575 grams (31.95mol) mix in order to reacting in mixing tank.Open fixed bed tail gas absorption system, when keeping nitrogen to reach more than 150 ℃ with the speed of per second 0.8L by the preheater temperature, insert fixed bed reaction equipment with the speed of per second 0.5L, chlorine.Mode with vaporization fully enters fixed bed reaction equipment to the 2-picoline aqueous solution that mixes through vaporizer heating back, keeps with the reacting of the speed uniform and stable of per minute 4.0 grams, and the 2-picoline aqueous solution dropwised in about 2 hours, the reaction end.The qualitative analysis of fixed bed reaction products obtained therefrom contains N-serve 88.4% under this condition, and remaining is unreacted is lower boiling three chloroformate mixtures and react excessive high boiling material completely.Obtain product 381 grams after rectifying separation, content is more than 95%, and yield is greater than 73%.
Embodiment 3
Present embodiment Synthetic 2-the method for chloro-6-nitrapyrin is the same substantially with the method for embodiment 1 and reactions steps, adopts the fixed bed continuous reaction.Catalyzer changes cupric chloride into to be mixed according to weight ratio with gac at 3: 7, the import volume of 2-picoline and water changes 15 in the reaction ratio: 1mol, the fixed bed reaction temperature also is adjusted into 300 ℃, adding 200 gram 2-picolines (2.13mol, content 99%), deionized water 575 grams (31.95mol) mix in order to reacting in mixing tank.Open fixed bed tail gas absorption system, when keeping nitrogen to reach more than 150 ℃ with the speed of per second 1.0L by the preheater temperature, insert fixed bed reaction equipment with the speed of per second 0.55L, chlorine.Mode with vaporization fully enters fixed bed reaction equipment to the 2-picoline aqueous solution that mixes through vaporizer heating back, keeps with the reacting of the speed uniform and stable of per minute 6.0 grams, and the 2-picoline aqueous solution dropwised in about 3 hours, the reaction end.The qualitative analysis of fixed bed reaction products obtained therefrom contains N-serve 88.4% under this condition, and remaining is unreacted is lower boiling three chloroformate mixtures and react excessive high boiling material completely.Obtain product 381 grams after rectifying separation, content is more than 95%, and yield is greater than 73%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of a N-serve is characterized in that, is reacted under catalyst action by 2-picoline after aqueous vaporization and chlorine, makes product.
2. preparation method as claimed in claim 1 is characterized in that it comprises step:
The 2-picoline mixes with the chlorine and the carrier gas of process preheating after aqueous vaporization, under the effect of catalyzer, reacts under 180-320 ℃, and reaction product obtains N-serve after condensation, rectifying.
3. preparation method as claimed in claim 2 is characterized in that, wherein said carrier gas is nitrogen, helium or argon gas.
4. preparation method as claimed in claim 1 or 2 is characterized in that, the gasification of wherein said 2-picoline comprise earlier with 2-picoline and hydromassage you than being 1: the mixed of 5-20, carrying out moment then gasifies.
5. preparation method as claimed in claim 4 is characterized in that, wherein said water is distilled water or deionized water.
6. preparation method as claimed in claim 1 or 2 is characterized in that, wherein said catalyzer is the gac of loaded metal ion compound.
7. preparation method as claimed in claim 6 is characterized in that wherein said metal ion compound comprises iron(ic) chloride, zinc chloride, cobalt chloride, bariumchloride, cupric chloride or rare earth chloride.
8. preparation method as claimed in claim 6 is characterized in that, the weight percent that wherein said metal ion compound accounts for gac is 1%-30%.
9. as claim 4 or 5 described preparation methods, it is characterized in that the mol ratio of wherein said 2-picoline and water is 1: 10.
10. preparation method as claimed in claim 1 or 2 is characterized in that, the mol ratio of wherein said 2-picoline and chlorine is 1: 10-30.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891675A (en) * | 2010-06-09 | 2010-11-24 | 横店集团东阳英洛华绿色电化学有限公司 | Production method of 6-chloro-2-(trichloromethyl)pyridine |
| CN102875454A (en) * | 2012-10-17 | 2013-01-16 | 山东绿霸化工股份有限公司 | 2-chloro-5-tirfluoromethylpyridine and synthetic method thereof |
| CN106316933A (en) * | 2016-08-20 | 2017-01-11 | 大连九信精细化工有限公司 | Continuous preparation method for 2-fluoro-6-trifluoromethyl pyridine |
| CN107501168A (en) * | 2017-08-09 | 2017-12-22 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of 2 trichloromethyl pyridine |
| CN108530346A (en) * | 2018-05-07 | 2018-09-14 | 盐城工学院 | A kind of preparation method of N-serve and its preparation method of catalyst and catalyst |
| CN108658847A (en) * | 2018-05-07 | 2018-10-16 | 盐城工学院 | A kind of iron content pyridine chloride salt ions liquid and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483993A (en) * | 1983-04-08 | 1984-11-20 | Kalama Chemical, Inc. | Production of polychlorinated pyridine mixtures by liquid phase chlorination of beta-picoline or beta-picoline hydrochloride |
| CN101314588B (en) * | 2008-07-04 | 2010-12-01 | 浙江奥复托化工有限公司 | Preparation for 6-chlorine-2-trichloromethyl pyridine |
-
2009
- 2009-09-10 CN CN2009100925533A patent/CN101648905B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891675A (en) * | 2010-06-09 | 2010-11-24 | 横店集团东阳英洛华绿色电化学有限公司 | Production method of 6-chloro-2-(trichloromethyl)pyridine |
| CN101891675B (en) * | 2010-06-09 | 2011-12-14 | 横店集团东阳英洛华绿色电化学有限公司 | Production method of 6-chloro-2-(trichloromethyl)pyridine |
| CN102875454A (en) * | 2012-10-17 | 2013-01-16 | 山东绿霸化工股份有限公司 | 2-chloro-5-tirfluoromethylpyridine and synthetic method thereof |
| CN102875454B (en) * | 2012-10-17 | 2014-10-22 | 山东绿霸化工股份有限公司 | 2-chloro-5-tirfluoromethylpyridine and synthetic method thereof |
| CN106316933A (en) * | 2016-08-20 | 2017-01-11 | 大连九信精细化工有限公司 | Continuous preparation method for 2-fluoro-6-trifluoromethyl pyridine |
| CN107501168A (en) * | 2017-08-09 | 2017-12-22 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of 2 trichloromethyl pyridine |
| CN108530346A (en) * | 2018-05-07 | 2018-09-14 | 盐城工学院 | A kind of preparation method of N-serve and its preparation method of catalyst and catalyst |
| CN108658847A (en) * | 2018-05-07 | 2018-10-16 | 盐城工学院 | A kind of iron content pyridine chloride salt ions liquid and its preparation method and application |
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| CN101648905B (en) | 2011-03-16 |
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Address after: 100192, D-1 building, North Territory, Dongsheng Science Park, No. 66 Xiao Dong Road, Beijing, Haidian District, Zhongguancun Patentee after: BEIJING NUTRICHEM COMPANY LIMITED Address before: 100192, D-1 building, North Territory, Dongsheng Science Park, No. 66 Xiao Dong Road, Beijing, Haidian District, Zhongguancun Patentee before: Nutrichem Co., Ltd. |