CN101891675B - Production method of 6-chloro-2-(trichloromethyl)pyridine - Google Patents
Production method of 6-chloro-2-(trichloromethyl)pyridine Download PDFInfo
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Abstract
The invention relates to a production method of a nitrogen fertilizer synergist-6-chloro-2-(trichloromethyl)pyridine, belonging to the crop production field. The production method comprises the following steps: taking 2-methylpyridine as a staring material; in the presence of solvents such as chlorobenzene, dichlorobenzene, chloro-trifluorotoluene, nitrobenzene and the like, introducing excessive chlorine at the temperature of 130-205 DEG C for chlorination to obtain a crude product of the 6-chloro-2-(trichloromethyl)pyridine; and purifying the crude product through rectification to obtain the high-purity product of the 6-chloro-2-(trichloromethyl)pyridine. The production method can overcome the defects of low yield, easy generation of a tar polymer, pipe blockage caused by materials and the like of the existing production method, thus achieving the purpose of improving reaction selectivity and product yield, reducing waste discharge and being easy to be industrialized.
Description
Technical field
The invention belongs to the farm crop production field, be specifically related to a kind of big production method of mass-producing of nitrogen fertilizer potentiating agent 6-chloro-2-nitrapyrin.
Background technology
6-chloro-2-nitrapyrin is a kind of nitrogen fertilizer potentiating agent that can suppress nitrification in the soil or denitrification, raising utilization rate of nitrogen fertilizer selectively, and code name is CP, and is nitrogenous 6%, white crystalline solid, and now external widespread usage, effect are best.China also makes overtesting on various crop, proof has certain effect of increasing production, and its amount of application is about 1% of the pure nitrogen level of executing, when its concentration in soil is l～10 mg/kg, soil nitrification there is the obvious suppression effect, about 30 days of validity period.To crops such as paddy rice, corn, wheat, Chinese sorghum, cotton, rapes, generally can increase production about 10%, and can reduce amount of application of nitrogen fertilizer 1/3～1/2, improve utilization rate of nitrogen fertilizer, reduce widespread pollution from the overuse of fertilizers and pesticides in rural area.
Have the preparation method's of some synthetic 6-chloro-2-nitrapyrins report at present both at home and abroad, as U.S. Pat 3424754, the preparation method that name is called " preparation of 6-chloro-2-nitrapyrin " report is by 2-picoline hydrochloride is fed chlorine, reaction obtains 75% volatile-type mixture under 200 ℃ of conditions, contain 90% 6-chloro-2-nitrapyrin, wherein 6-chloro-2-nitrapyrin yield is 68%, total recovery 50%, the shortcoming of this method is easily to produce tar polymer, intractable in the chlorination process; The patent No. is the United States Patent (USP) of US3420833, the method that name is called " vapor phase process is produced many chloro-pyridines compound " be with 2-picoline steam with chlorine under 400 ℃, after reaction in the presence of the thinner, obtain the mixture of 6-chloro-2-nitrapyrin enrichment, because this method is a gas-phase reaction, reaction mass must gasify, so its shortcoming is the energy consumption height; The patent No. is the United States Patent (USP) of US3418323, the method that name is called " N-serve compound " be by chlorine and 2-nitrapyrin under 120 ℃ ~ 135 ℃, liquid phase is carried out prepared in reaction 6-chloro-2-nitrapyrin under UV illumination is penetrated, and the shortcoming of this method is that the selectivity of reaction is not high; The patent No. is the United States Patent (USP) of US4577027, name is called " the direct liquid phase chlorination method of 2-picoline is produced many pyridinium chlorides mixture " and publication number is CN101314588A, the method that name is called " preparation method of N-serve " Chinese patent application is that the many chlorinated mixtures with the 2-picoline are the start material material, under 100 ℃～250 ℃, add chlorine and 2-picoline Synthetic 2-chloro-6-nitrapyrin continuously, the shortcoming first of the method that these two inventions provide, many chlorinated mixtures of used 2-picoline are to make by chlorination 2-picoline hydrochloride, preparation process easily produces tar polymer, total yield of products only is 49%, another shortcoming is, because the muriate majority of 2-picoline has volatility, production process easily causes material pipe to stop up, and operation control is had relatively high expectations.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of new 6-chloro-2-nitrapyrin, with solve the product yield that exists in the existing production method low, easily generate problems such as tar polymer, material blocking pipe, thereby realize improving reaction preference and product yield, reduce waste discharge, be easier to the purpose of suitability for industrialized production.
The technical solution used in the present invention is:
The present invention is to be starting raw material with the 2-picoline, in the presence of chlorobenzene, dichlorobenzene, chloro phenylfluoroform, oil of mirbane equal solvent, under 130 ℃ of-205 ℃ of temperature, feed excessive chlorine and carry out chlorination reaction, one one-step chlorination directly obtains the 6-chloro-2-nitrapyrin crude product of content 〉=90%, pass through the rectificating method purifying raw again, obtain the 6-chloro-2-nitrapyrin product of purity 〉=99.0%.
Because the chlorination reaction of 2-picoline is heat release, if move the untimely local superheating phenomenon that very easily produces of heat, makes the 2-picoline generate tar polymer, thereby cause reaction preference and product yield not high in the reaction process; The muriate of 2-picoline has volatility simultaneously, and volatile matter is reacted the hydrogenchloride of generation and excessive chlorine is taken out of, deposits on duct wall, will cause line clogging, so production operation control is had relatively high expectations.The contriver finds through a large amount of research experiments, by in the chlorination reaction process of 2-picoline, adding appropriate solvent, one can in time shift out the heat that reaction produces, avoid the 2-picoline because local superheating generates tar polymer, hydrogenchloride that its two solvents partial gasification following response generates and excessive chlorine are discharged, meeting condensation and dissolve deposits on duct wall, therefore, it is low that the present invention has overcome the product yield that exists in the existing production method, easily generate tar polymer, shortcomings such as material blocking pipe, thereby raising reaction preference and product yield have been realized, reduce waste discharge, be easier to the purpose of suitability for industrialized production.
The production method of a kind of 6-chloro-2-nitrapyrin provided by the invention specifically, its production process may further comprise the steps:
(1) with partial solvent the 2-picoline is mixed with solution, add the solvent of surplus in the reactor and feed excessive chlorine, join 2-picoline solution in the reactor continuously then, under 130 ℃ ~ 205 ℃, carry out chlorination reaction, GC detects 6-chloro-2-dichloromethyl pyridine content≤0.5% o'clock, stopped reaction obtains 6-chloro-2-nitrapyrin crude product, and the reaction equation in this step is as follows:
Main reaction:
Side reaction:
(2) adopt rectificating method purification step (1) crude product, obtain 6-chloro-2-nitrapyrin product,
Wherein, above-mentioned solvent is selected from the aromatics of halo or nitration, and the weight ratio of solvent total amount and 2-picoline is 0.1-10: 1.The present invention's employing is mixed with solution with starting raw material 2-picoline and feeds intake, its objective is and avoid in reaction process, generating tar polymer, prevent the material blocking pipe, improve the condition that feeds intake simultaneously, make operation control convenient, production process is safety and environmental protection more.
As preferred version, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, the weight ratio of chlorine and 2-picoline is 3.5 ~ 10: 1 in the described step (1).Feed chlorine according to this ratio, can well carry out chlorination reaction on the one hand, production cost is reasonably controlled.
As preferred version,, wherein, be hybridly prepared into material solution with the solvent of solvent total amount 20 ~ 30% and 2-picoline in the described step (1) and feed intake according to the production method of 6-chloro-2-nitrapyrin of the present invention.Adopt 25% left and right sides dissolution with solvents raw material, its objective is and avoid in reaction process, generating tar polymer, prevent the material blocking pipe.
As preferred version, production method according to 6-chloro-2-nitrapyrin of the present invention, wherein, described solvent is selected from the following material a kind of: chlorobenzene, dichlorobenzene, phenylfluoroform, chloro phenylfluoroform, dichloro-phenylfluoroform, three chloro phenylfluoroform or oil of mirbane.Select the reason of these solvents to be, these solvents and 2-picoline have good mutual solubility, fusing point, boiling point and temperature of reaction coupling.
As more preferably scheme, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, described chloro phenylfluoroform comprises 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride or 4-chlorobenzotrifluoride; Described dichloro-phenylfluoroform comprises 2,3-two chlorobenzotrifluorides, 2,4-two chlorobenzotrifluorides, 2,5-two chlorobenzotrifluorides, 2,6-two chlorobenzotrifluorides, 3,4-two chlorobenzotrifluorides or 3,5-two chlorobenzotrifluorides; Described three chloro phenylfluoroforms comprise 2,3,4-trichlorobenzotrifluoride, 2,3,5-trichlorobenzotrifluoride, 2,3,6-trichlorobenzotrifluoride, 2,4,5-trichlorobenzotrifluoride, 2,4,6-trichlorobenzotrifluoride or 3,4,5-trichlorobenzotrifluoride.
As preferred version, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, the chlorination reaction of described step (1) is operated as follows:
After the reactor internal solvent reaches 135 ℃ ~ 165 ℃ of initial reaction temperatures, interim heating and heat preservation, every period following reaction times of temperature is 6 ~ 15 hours or presses per hour 1 ~ 2 ℃ frequency intensification, the adding speed of chlorine and 2-picoline solution improves with the temperature of reaction rising or remains unchanged, add up to 2-picoline solution, temperature of reaction reaches 190 ℃ ~ 205 ℃ at last, keep temperature and chlorine feeding speed at this moment, GC follows the tracks of the 6-chloro-2-dichloromethyl pyridine content detect in the reaction product≤0.5% o'clock, be reaction end, wherein, the feeding speed of chlorine is 9 ~ 60kg/h; The adding speed of 2-picoline solution is 2 ~ 35kg/h.The contriver discovers, take at the uniform velocity to heat up and 2-picoline material solution to add that speed at the uniform velocity improves be one of measure of generating of control tar polymer.
As preferred version, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, the rectificating method of described step (2) is pressed following operation:
At pressure is that 2kPa, rectifying temperature in the kettle are that 90 ℃ ~ 120 ℃, rectifying tower top temperature are that 50 ℃ ~ 80 ℃ and reflux ratio are under the condition of 4 ~ 8:1, reclaims solvent; At pressure is that 2 kPa, rectifying temperature in the kettle are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 4 ~ 8:1, collects 6-chloro-2-nitrapyrin product.The rectifying device that the present invention adopts is a packing tower, and filler is a Stainless Steel Cloth.
As more preferably scheme, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, the recovery solvent and the product front-end volatiles that obtain in the described rectificating method recycle; The product after cut that obtains is as the raw material of other products.
As scheme most preferably, according to the production method of 6-chloro-2-nitrapyrin of the present invention, wherein, described product front-end volatiles comprise 2-nitrapyrin, 6-chloro-2-dichloromethyl pyridine; The product after cut comprises 3,5-two chloro-2-nitrapyrins etc.
The present invention compared with prior art has the following advantages:
(1) reaction process of the present invention need not to use catalyzer and adopts illumination.
(2) the present invention adopts solvent liquid phase chlorination technology, and no tar polymer generates in the production process, and no material blocking pipe phenomenon takes place, and makes that production process control is more simple.
(3) 6-chloro-2-nitrapyrin product purity of the present invention 〉=99.0%, total recovery 〉=60%.
(4) the present invention adopts the method that rectifying separation is purified, and rectifying front-end volatiles solvent, 2-nitrapyrin, 6-chloro-2-dichloromethyl pyridine etc. can turn back to reactive system and recycle, thereby reduce production costs; After cut 3,5-two chloro-2-nitrapyrins etc. can be used for synthetic other products, accomplish the comprehensive utilization of resource.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1
Add 4-chlorobenzotrifluoride 96kg in the 300L glass lined reaction vessel, adding 2-picoline 160kg and 4-chlorobenzotrifluoride 20kg are made into 2-picoline solution in the elevated dosing vessel.Open to stir, after reactor is heated to 165 ℃, feed chlorine, keep 165 ℃ of temperature of reaction, add 2-picoline solution, reacted 8 hours with 2.25kg per hour with 9kg per hour; Temperature of reaction is brought up to 170 ℃, insulation, and per hour chlorine feeding amount is brought up to 12kg, and 2-picoline solution add-on is brought up to 3.375kg/h, reacts 8 hours; Temperature of reaction is brought up to 180 ℃, insulation, and per hour chlorine feeding amount is brought up to 15kg, and 2-picoline solution add-on is brought up to 4.5kg/h, reacts 8 hours; Temperature of reaction is brought up to 190 ℃, insulation, and per hour chlorine feeding amount is brought up to 27kg, and 2-picoline solution add-on is brought up to 5.625kg/h, reacts 8 hours; Temperature of reaction is brought up to 195 ℃, insulation, and per hour chlorine feeding amount is brought up to 33kg, 2-picoline solution add-on is brought up to 6.75kg/h, reacts after 8 hours, and 2-picoline solution accumulative total add-on reaches 180kg, stop 2-picoline solution and add, keep per hour chlorine feeding amount 33kg, 195 ℃ of temperature, reacted again 2 hours, sampling GC analyzes, and 6-chloro-2-dichloromethyl pyridine content≤0.5% o'clock stops chlorine and feeds, reaction has been carried out again 2 hours, and the chlorine consumption reaches 900kg.Feed N
2Or air is to tail gas neutrality, and temperature of reaction kettle is reduced to 80 ℃, and chlorizate is put into rectifying still.At pressure is that 2kPa, still temperature are that 100 ℃, rectifying tower top temperature are that 61 ℃ and reflux ratio are under the condition of 6:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 7:1, collects and obtains 6-chloro-2-nitrapyrin product 242.1 kg, analyzes through GC, and content is 99.3%, and fusing point is 61 ℃ ~ 63 ℃, and total recovery is 61%.
Embodiment 2
Add dichlorobenzene 1820kg in the 3000L glass lined reaction vessel, add 2-picoline 260kg and dichlorobenzene 780kg in the elevated dosing vessel, be made into 2-picoline solution.Open to stir, after reactor is heated to 135 ℃,, keep 135 ℃ of temperature of reaction, add 2-picoline solution, reacted 10 hours with 35kg per hour per hour to feed chlorine in 50 ~ 60kg hour; It is constant that chlorine and 2-picoline solution add speed, temperature of reaction is brought up to 150 ℃, insulation, react after 10 hours, temperature of reaction is brought up to 160 ℃, and insulation was reacted 10 hours again, when 2-picoline solution accumulative total add-on reaches 1040kg, stop to add 2-picoline solution, per hour to feed chlorine in 10 ~ 12kg hour, temperature is brought up to 190 ℃, after reacting 3 hours again, sampling GC analyzed in per 1 hour, and 6-chloro-2-dichloromethyl pyridine content≤0.5% o'clock stops chlorine and feeds, this moment, reaction was carried out 2 hours again, and the chlorine consumption reaches 1610kg.Feed N
2Or air is to tail gas neutrality, and temperature of reaction kettle is reduced to 80 ℃, and chlorizate is put into rectifying still.At pressure is that 2kPa, still temperature are that 105 ℃, rectifying tower top temperature are that 80 ℃ and reflux ratio are under the condition of 7:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 8:1, obtains 6-chloro-2-nitrapyrin 390 kg, analyzes content 99.4%, 60 ℃ ~ 63 ℃ of fusing points, total recovery 60.5% through GC.
Embodiment 3
Add chlorobenzene 20kg in the 300L glass lined reaction vessel, add 2-picoline 240kg and chlorobenzene 4kg in the elevated dosing vessel, be made into 2-picoline solution.Open and stir, after reactor was heated to 160 ℃, per hour 15 ~ 20kg feeding chlorine and per hour 2 ~ 3kg adding 2-picoline solution kept 160 ℃ of temperature of reaction, react 6 hours; Temperature of reaction is brought up to 175 ℃, insulation, and chlorine feeding speed is that 30 ~ 40kg/h and 2-picoline solution adding speed are 4 ~ 6kg/h, reacts 12 hours; Temperature of reaction is brought up to 190 ℃, insulation, and chlorine feeding speed is that 30 ~ 50kg/h and 2-picoline solution adding speed are 11 ~ 12kg/h, reacts 15 hours; When 2-picoline solution accumulative total add-on reaches 244kg, stop to add 2-picoline solution, per hour to feed chlorine in 20 ~ 22kg hour, 190 ℃ of temperature, react 2 hours again after, sampling GC analyzed in per 1 hour, 6-chloro-2-dichloromethyl pyridine content≤0.5% o'clock, stop chlorine and feed, this moment, reaction was carried out again 1 hour, and the chlorine consumption reaches 1520kg.Feed N
2To tail gas neutrality, temperature of reaction kettle is reduced to 80 ℃, and chlorizate is put into rectifying still.At pressure is that 2kPa, still temperature are that 90 ℃, rectifying tower top temperature are that 52 ℃ and reflux ratio are under the condition of 5:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 4:1, obtains 6-chloro-2-nitrapyrin 365kg, analyzes content 99.0%, 60 ℃ ~ 63 ℃ of fusing points, total recovery 61.3% through GC.
Embodiment 4
Replace the 4-chlorobenzotrifluoride with phenylfluoroform, chlorination reaction is with embodiment 1 operation.At pressure is that 2kPa, still temperature are that 90 ℃, rectifying tower top temperature are that 50 ℃ and reflux ratio are under the condition of 4:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 6:1,6-chloro-2-nitrapyrin 196.4 kg, analyze content 99.2%, 61 ℃ ~ 63 ℃ of fusing points, total recovery 60% through GC.
Embodiment 5
Replace the 4-chlorobenzotrifluoride with oil of mirbane, chlorination reaction is with embodiment 1 operation.At pressure is that 2kPa, still temperature are that 120 ℃, rectifying tower top temperature are that 80 ℃ and reflux ratio are under the condition of 8:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 5:1,6-chloro-2-nitrapyrin 199.1kg, analyze content 99.1%, 60 ℃ ~ 63 ℃ of fusing points, total recovery 60.8% through GC.
Embodiment 6
Add 3,4 in the 500L glass lined reaction vessel, 5-trichlorobenzotrifluoride 120kg adds 2-picoline 260kg and 3,4 in the elevated dosing vessel, and 5-trichlorobenzotrifluoride 40kg is made into 2-picoline solution.Open and stir, after reactor is heated to 130 ℃, per hour to feed chlorine in 50 ~ 60kg hour, temperature of reaction per hour promotes 1 ~ 2 ℃, add 2-picoline solution with 8 ~ 9kg per hour, when 2-picoline solution accumulative total add-on reaches 300kg, stop to add 2-picoline solution, keep original chlorine to feed speed, temperature is 190 ~ 205 ℃, after reacting 1 hour again, sampling GC analyzed in per 1 hour, and 6-chloro-2-dichloromethyl pyridine content in the reaction product≤0.5% o'clock stops chlorine and feeds, this moment, reaction was carried out again 2 hours, and the chlorine consumption reaches 1570kg.Feed N
2To tail gas neutrality, temperature of reaction kettle is reduced to 80 ℃, puts into rectifying still.At pressure is that 2kPa, still temperature are that 110 ℃, rectifying tower top temperature are that 64 ℃ and reflux ratio are under the condition of 7:1, reclaims solvent; At pressure is that 2kPa, still temperature are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 5:1, obtains 6-chloro-2-nitrapyrin 406 kg, analyzes content 99.0%, 60 ℃ ~ 63 ℃ of fusing points, total recovery 63% through GC.
The foregoing description only is the elaboration to the preferred implementation of technical solution of the present invention, studies show that, the announcement of summary of the invention part and the foregoing description according to the present invention, disclosed as solvent species and consumption, various process parameters range in or the like, those skilled in the art make reasonable adjustment can obtain technique effect as above-mentioned embodiment, therefore, the present invention gives unnecessary details no longer one by one.
Although the contriver has done comparatively detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, for the those skilled in the art in this area, the foregoing description is modified and/or flexible or to adopt the replacement scheme that is equal to be obvious, the essence that all can not break away from spirit of the present invention, the term that occurs among the present invention is used for can not being construed as limiting the invention the elaboration of technical solution of the present invention and understanding.
Claims (8)
1. the production method of a 6-chloro-2-nitrapyrin is characterized in that described production method comprises the steps:
(1) with partial solvent the 2-picoline is mixed with solution, add the solvent of surplus in the reactor and feed excessive chlorine, join 2-picoline solution in the reactor continuously then, under 130 ℃-205 ℃, carry out chlorination reaction, GC detects 6-chloro-2-dichloromethyl pyridine content≤0.5% o'clock, stopped reaction obtains 6-chloro-2-nitrapyrin crude product
(2) adopt rectificating method purification step (1) crude product, obtain 6-chloro-2-nitrapyrin product,
Wherein, above-mentioned solvent is selected from the aromatics of halo or nitration, and the weight ratio of solvent total amount and 2-picoline is 0.1-10:1.
2. production method according to claim 1 is characterized in that, the weight ratio of chlorine and 2-picoline is 3.5-10 in the described step (1): 1.
3. production method according to claim 1 is characterized in that, solvent and 2-picoline with solvent total amount 20% ~ 30% in the described step (1) are mixed and made into material solution.
4. production method according to claim 1 is characterized in that, described solvent is selected from the following material a kind of: chlorobenzene, dichlorobenzene, phenylfluoroform, chloro phenylfluoroform, dichloro-phenylfluoroform, three chloro phenylfluoroform or oil of mirbane.
5. production method according to claim 4 is characterized in that, described chloro phenylfluoroform comprises 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride or 4-chlorobenzotrifluoride; Described dichloro-phenylfluoroform comprises 2,3-two chlorobenzotrifluorides, 2,4-two chlorobenzotrifluorides, 2,5-two chlorobenzotrifluorides, 2,6-two chlorobenzotrifluorides, 3,4-two chlorobenzotrifluorides or 3,5-two chlorobenzotrifluorides; Described three chloro phenylfluoroforms comprise 2,3,4-trichlorobenzotrifluoride, 2,3,5-trichlorobenzotrifluoride, 2,3,6-trichlorobenzotrifluoride, 2,4,5-trichlorobenzotrifluoride, 2,4,6-trichlorobenzotrifluoride or 3,4,5-trichlorobenzotrifluoride.
6. according to the described production method of one of claim 1-5, it is characterized in that the chlorination reaction of described step (1) is operated as follows:
After the reactor internal solvent reaches 135 ℃ ~ 165 ℃ of initial reaction temperatures, interim heating and heat preservation, every period following reaction times of temperature is 6 ~ 15 hours or presses per hour 1 ℃ ~ 2 ℃ frequency intensification, the adding speed of chlorine and 2-picoline solution improves with the temperature of reaction rising or remains unchanged, add up to 2-picoline solution, temperature of reaction reaches 190 ℃ ~ 205 ℃ at last, keep temperature and chlorine feeding speed at this moment, GC follows the tracks of the 6-chloro-2-dichloromethyl pyridine content detect in the reaction product≤0.5% o'clock, be reaction end, wherein, the feeding speed of chlorine is 9 ~ 60kg/h; The adding speed of 2-picoline solution is 2 ~ 35kg/h.
7. production method according to claim 1 is characterized in that, the rectificating method of described step (2) is pressed following operation:
At pressure is that 2kPa, rectifying temperature in the kettle are that 90 ℃ ~ 120 ℃, rectifying tower top temperature are that 50 ℃ ~ 80 ℃ and reflux ratio are under the condition of 4 ~ 8:1, reclaims solvent; At pressure is that 2kPa, rectifying temperature in the kettle are that 145 ℃, rectifying tower top temperature are that 114 ℃ and reflux ratio are under the condition of 4 ~ 8:1, collects 6-chloro-2-nitrapyrin product.
8. production method according to claim 1 is characterized in that, the recovery solvent and the product front-end volatiles that obtain in the described rectificating method recycle; The product after cut that obtains is as the raw material of other products.
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| CN102304082B (en) * | 2011-09-30 | 2013-05-22 | 常州大学 | Synthesis method of 2-chloro-4-(piperidylmethyl)pyridine |
| CN109694346A (en) * | 2018-10-30 | 2019-04-30 | 浙江埃森化学有限公司 | The method that 2- picoline liquid phase Light chlorimation prepares N-serve |
| CN109516948B (en) * | 2018-10-30 | 2022-01-11 | 浙江埃森化学有限公司 | Method and production line for preparing 2, 6-dichloropyridine by gas-phase photochlorination of pyridine |
| CN109879803A (en) * | 2019-03-05 | 2019-06-14 | 浙江埃森化学有限公司 | A kind of method of purification of pyridinium chloride |
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