CN102875461A - Production method of 4-chloro-2-cyanopyridine - Google Patents
Production method of 4-chloro-2-cyanopyridine Download PDFInfo
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- CN102875461A CN102875461A CN2012104382260A CN201210438226A CN102875461A CN 102875461 A CN102875461 A CN 102875461A CN 2012104382260 A CN2012104382260 A CN 2012104382260A CN 201210438226 A CN201210438226 A CN 201210438226A CN 102875461 A CN102875461 A CN 102875461A
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Abstract
The invention relates to a production method of 4-chloro-2-cyanopyridine. The method comprises the following steps: taking 2-cyanopyridine and chlorine gas as raw materials, evaporating 2-cyanopyridine and preheated chlorine gas through an evapourizer, mixing evaporated 2-cyanopyridine and preheated chlorine gas to obtain a mixture, causing the mixture to sequentially pass through a fluidized bed reactor and a fixed bed reactor, which are filled with modified cocoanut active charcoal catalysts and connected in series to generate gas-phase catalytic chlorination to prepare 4-chloro-2-cyanopyridine, and achieving the production of 4-chloro-2-cyanopyridine. The modified cocoanut active charcoal catalysts are used in the reaction process, the reaction temperature is lowered, the activities of the catalysts is improved, the problem that the catalysts are liable to coking is solved, the service lives of the catalysts are prolonged, and meanwhile, the yield and the content of 4-chloro-2-cyanopyridine are increased.
Description
Technical field
The present invention relates to a kind of production method of tetrachloro cyanopyridines, especially relate to the production method of a kind of tetrachloro-2-cyanopyridine.Belong to field of chemical technology.
Technical background
The tetrachloro cyanopyridines has higher biological activity, can be used as agricultural chemicals, medicine and dyestuff synthetic intermediate.With the synthetic a series of agricultural chemicals of tetrachloro-2-cyanopyridine exploitation especially weedicide have that consumption is few, selectivity is high, toxicity is low, characteristics that residual quantity is little and residual period is short in the soil and plant body, agricultural development and ecological protection are had great importance.In recent years, along with continually developing of its derived product, range of application and demand obtain rapid growth.
The production method of tetrachloro-2-cyanopyridine mainly is take 2-cyanopyridine and chlorine as raw material, makes by the gas phase chlorination reaction under the effect of catalyzer.European patent EP 182111 has been introduced with 2-cyanopyridine and chlorine and has been made tetrachloro-2-cyanopyridine at the fluidized-bed reactor that gac is housed in 500 ℃ of reactions, the method major defect is, because temperature of reaction is too high, fluidized-bed reaction is wayward, the high temperature polymerization phenomenon easily occurs, and the polymkeric substance of generation adheres to catalyst layer, causes the catalyst surface coking, reduce catalyst activity, reduced catalyzer work-ing life.Chinese patent CN100579964C also is as raw material take 2-cyanopyridine and chlorine, the gac that adopts iron trichloride and salt acid dipping is that Primary Catalysts is by the synthetic tetrachloro of gas phase chlorination reaction-2-cyanopyridine, present method exists the chlorination reaction yield low, the problem of poor product quality.
Summary of the invention
The object of the present invention is to provide a kind of above-mentioned shortcoming that overcomes, the one, can reduce temperature of reaction, improve catalyst activity, solve the easy coking problem of catalyzer, improve catalyzer work-ing life; The 2nd, the production method of a kind of tetrachloro of raising product yield and content-2-cyanopyridine.
The object of the present invention is achieved like this: take 2-cyanopyridine and chlorine as raw material, at first the nitrogen after 2-cyanopyridine and the preheating is vaporized by vaporizer, then with the 2-cyanopyridine after vaporization with after the chlorine of preheating mixes successively in the fluidized-bed of the two-stage series connection of the cocoanut active charcoal catalyzer by modification of the present invention is housed, the fixed-bed reactor generation gas phase catalysis chlorination reaction prepare tetrachloro-2-cyanopyridine, the production of realization tetrachloro-2-cyanopyridine.
Selected catalyzer is the cocoanut active charcoal catalyzer in tetrachloro involved in the present invention-2-cyanopyridine production method, and the average pore diameter of employed cocoanut active charcoal is not less than
, preferably exist
Between, specific surface area is not less than 1000m
2/ g is preferably at 1200-1800m
2Between/the g.It is large that cocoanut active charcoal has specific surface area than common gac, high adsorption capacity, rate of adsorption is fast, foreign matter content is few, and the intensity advantages of higher relatively is suitable as the gas phase chlorination catalyzer, consider simultaneously the difference of fluidized-bed reactor and fixed-bed reactor equipment, select varigrained cocoanut active charcoal, it is 6-30 purpose cocoanut active charcoal catalyzer that the catalyzer of fluidized-bed is selected granularity, is preferably the 8-24 order; It is 12-20 order, 20-30 order, 30-40 purpose cocoanut active charcoal catalyzer that at least two kinds of the catalyzer of fixed bed are selected from granularity, when the fixed-bed reactor activated-carbon catalyst is the cocoanut active charcoal catalyzer of 12-20 order, 20-30 order, three kinds of different grain size scopes of 30-40 order when forming by granularity, the weight ratio of each component is 1: 2-3: 4-6.
Adopt the cocoanut active charcoal catalyzer of modification among the present invention, namely take the above-mentioned common cocoanut active charcoal of choosing as carrier, in common cocoanut active charcoal, add one or more compositions of rare-earth metal chloride Lanthanum trichloride, praseodymium chloride, Cerium II Chloride, the interpolation total amount of metal chloride is the 0.3%-3% of gac gross weight, is preferably 0.6%-2%; Metal chloride is preferably Lanthanum trichloride, Cerium II Chloride, the Lanthanum trichloride addition is the 0.4%-1.5% of gac gross weight, the Cerium II Chloride addition is the 0.2%-0.5% of gac gross weight, the preparation method of the cocoanut active charcoal catalyzer of modification of the present invention is: rare-earth metal chloride is obtained finely dispersed pressed powder after with the ball mill ball milling, then join stirring and dissolving in 50-80 ℃ the salpeter solution after both being mixed, dissolve rear adding cocoanut active charcoal fully until metal chloride and make a mixture, heating is concentrated, and the spray-dried microspheroidal that is shaped to, the spraying drying temperature is 125-150 ℃, time is 8-12 hour, at last roasting and get final product in air, maturing temperature is 250-350 ℃, and the time is 1.5-3 hour.
The step of the tetrachloro that the present invention relates to-2-cyanopyridine production method is as follows:
A, preactivating catalysts step: reactor is fluidized-bed and fixed bed, the cocoanut active charcoal catalyzer that in fluidized-bed and fixed bed, adds above-mentioned modification, dehydration heats up, dewater complete after, pass into excessive chlorine activation, activation temperature is 200-250 ℃, 3 hours time, when two reactor each point temperature-stables, inspection does not measure HCl in the tail gas, is considered as activation and finishes;
B, the pre-pervaporation step of 2-cyanopyridine: with the melting vaporization in vaporizer of 2-cyanopyridine, take vaporizer out of by nitrogen subsequently, 2-cyanopyridine inlet amount is 1 with the ratio of nitrogen flow: 4-6;
C, reactions steps: will carry out the first step chlorination reaction with first fluidized-bed reactor at the step a that adds catalyzer after chlorine mixes through the 2-cyanopyridine of step b vaporization, the volume mol ratio that feeds intake of 2-cyanopyridine and chlorine is 1: 3-4, the fluidized-bed reaction temperature is controlled at 200-300 ℃, and reaction pressure is controlled at 0.008-0.1Mpa; Reaction time is 3-8 second; The fixed-bed reactor that enter the step a that adds catalyzer from fluidized-bed gas are out proceeded chlorination reaction, and temperature of reaction is controlled at 240-320 ℃, and reaction pressure is controlled at 0.008-0.1Mpa; Reaction time is 3-8 second;
D, separating step: will by out gas in the fixed-bed reactor through trap cooling, separate, the product tetrachloro of solid state-2-cyanopyridine is enriched in the trap bottom.
Cocoanut active charcoal used in the present invention is available from Jiangxi chemical industry company limited everyday, and its model comprises the multiple cocoanut active charcoal of 5-60 purpose.
The present invention has following characteristics:
1, activated-carbon catalyst is optimized
The present invention selects the cocoanut active charcoal catalyzer, and the average pore diameter of employed cocoanut active charcoal is not less than
, be preferably in
Between.When its mean diameter less than
, catalyzer will be degraded and shorten work-ing life, because by product is attached on the inside in hole, stop up at last the duct.On the contrary, if mean diameter surpasses
, the duct just is not easy to block.If what mean pore size was too much is higher than
, the quantity of required gac will increase in the chlorination reaction, because the superfluous minimizing that will cause chlorination specific surface area and active site.If the aperture is excessive, with the unfavorable factor that grain pattern occurs and become fragile.The cocoanut active charcoal specific surface area that the present invention uses is not less than 1000m
2/ g is preferably in 1200-1800m
2Between/the g.If specific surface area is less than 1000m
2/ g, the chlorization activity of the activated carbon surface minimizing of naming a person for a particular job, on the contrary, if the gac specific surface area of using surpasses 1000m
2During/g, chlorination reaction can be finished at low temperatures, can effectively prevent the generation of by product under the hot conditions, has reduced the precipitation of polymkeric substance at catalyst surface, and catalyst life will prolong.
2, the cocoanut active charcoal catalyzer is fully activated
Cocoanut active charcoal provides a strong chlorization activity to main chlorination reaction, but has simultaneously some shortcomings, and 1. catalyzer is easy to produce the local superheating phenomenon, and reaction is easy to surpass tetrachloro, forms the Perchloropyridine by product.2. polymerization reaction take place, the polymerization enriched material of generation adheres to catalyst surface.These side reactions have not only reduced the transformation efficiency of 2-cyanopyridine, and the caking of catalyst surface polymerization enriched material easily causes catalyst activity to reduce, and shorten catalyzer work-ing life.The present invention carries out abundant activation treatment to it before using catalyzer, namely use excessive chlorine pre-treatment certain hour in 200-300 ℃ of temperature, makes in its tail gas and can't detect hydrogen chloride gas.After treatment, largely upper inhibition side reaction occurs.
3, catalyzer is carried out modification
The present invention has added an amount of rare-earth metal chloride in the gas phase chlorination gac, they not only play the generation that suppresses harmful side reaction such as superchlorination reaction and some high-boiling-point impurities in chlorination reaction, and improved activity, selectivity and the stability of catalyzer, the chlorine atom is connected to has stronger specificity on the pyridine ring.
Improve by above-mentioned catalyzer, reduced the chlorination temperature of 2-cyanopyridine, improved product yield, product content 〉=98.5%, total recovery reaches 90%, and extend to about 100 days the work-ing life of catalyzer.
Embodiment:
The technical process of tetrachloro-2-cyanopyridine is:
Raw material 2-cyanopyridine beaten by volume pump (the new bright engineering machinery in Jiangyin City company limited makes to vaporizer, nonstandard, upper end φ 1600 * 4000 lower end φ 800 * 8000) in, simultaneously the nitrogen after the preheating is passed in the vaporizer together and vaporize, after mixing, chlorine after 2-cyanopyridine after the vaporization and the preheating enters successively the fluidized-bed of the cocoanut active charcoal catalyzer that the specific modification of the present invention is housed in mixing tank, fixed bed generation chlorination substitution reaction, product captures through trap after the reaction, and unnecessary chlorinated exhaust enters tail gas absorbing system and generates the byproduct sale.
Cocoanut active charcoal used in the present invention comprises the cocoanut active charcoal of 5-60 purpose Multiple Type available from Jiangxi chemical industry company limited everyday.
Embodiment 1: fluidized-bed and fixed bed all do not add the cocoanut active charcoal catalyzer of modification
In fluidized-bed, add the common cocoanut active charcoal catalyzer of 1000kg24 purpose, in fixed bed, add 3 kinds of common cocoanut active charcoal catalyzer 1200kg that different grain size mixes, granularity 16 purpose 150kg wherein, 25 purpose 450kg, 38 purpose 600kg.The resistance to air loss of check reactor and whole system pipeline, guarantee the air tight rising temperature that begins to heat afterwards, when temperature reaches 200 ℃, begin to pass into chlorine, until two reactor each point temperature-stables, inspection does not measure HCl in the tail gas, and activation finishes, soak time is generally 3 hours, and activation temperature is controlled in the 200-250 ℃ of scope.
After catalyst activation finishes, with nitrogen as carrier gas, to mix with the chlorine of preheating after the vaporization of 2-cyanopyridine, fluidized-bed, the fixed-bed reactor of the two-stage series connection of mixed gas by common cocoanut active charcoal catalyzer is housed carry out chlorination reaction, the fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.Obtain the product tetrachloro-2-cyanopyridine content is 98%, the Perchloropyridine foreign matter content is 2.8%, catalyzer work-ing life is 30 days.
Embodiment 2:(only adds the cocoanut active charcoal catalyzer of modification in the fluidized-bed)
Embodiment 2 primary processes are as described in the example 1, catalyzer that fluidized-bed adds is modification cocoanut active charcoal catalyzer, it is to have added 0.8% Lanthanum trichloride in the common cocoanut active charcoal catalyzer of 1000kg24 purpose, 0.2% Cerium II Chloride, and fixed bed still uses the common cocoanut active charcoal catalyzer by three kinds of different grain sizes mixing, 16 purpose 150kg wherein, 25 purpose 450kg, 38 purpose 600kg.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.Obtain the product tetrachloro-2-cyanopyridine content is 98.8%, the Perchloropyridine foreign matter content is 2.5%, catalyzer work-ing life is 50 days.
Embodiment 3:(only adds the cocoanut active charcoal catalyzer of modification in the fixed bed)
Embodiment 3 primary processes are as described in the example 1, fluidized-bed still is 1000kg24 purpose cocoanut active charcoal catalyzer, and catalyzer that fixed bed adds is modified catalyst, is to have added 1% Lanthanum trichloride and 0.2% Cerium II Chloride in the cocoanut active charcoal catalyzer that mixed by 1: 3: 4 of 16 orders, 25 orders, three kinds of granularities of 38 orders at 1200kg.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 98.5%, the Perchloropyridine foreign matter content is 2.6%, catalyzer work-ing life is 46 days.
Embodiment 4:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 3 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 1% Lanthanum trichloride and 0.2% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 0.8% Lanthanum trichloride and 0.2% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is the 12-20 order: the 20-30 order: 30-40 order=1: 3: 6.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99.2%, the Perchloropyridine foreign matter content is 1.6%, catalyzer work-ing life is 90 days.
Embodiment 5:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 5 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 1.5% Lanthanum trichloride and 0.5% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 1% Lanthanum trichloride and 0.2% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 3: 6.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99.5%, the Perchloropyridine foreign matter content is 1.4%, catalyzer work-ing life is 95 days.
Embodiment 6:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 6 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 1.5% Lanthanum trichloride and 0.5% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 1.2% Lanthanum trichloride and 0.3% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 2: 5.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99.5%, the Perchloropyridine foreign matter content is 1.4%, catalyzer work-ing life is 100 days.
Embodiment 7:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 7 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 1% Lanthanum trichloride and 0.2% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 1.5% Lanthanum trichloride and 0.5% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 2: 4.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99.2%, the Perchloropyridine foreign matter content is 1.5%, catalyzer work-ing life is 93 days.
Embodiment 8:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 8 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 0.4% Lanthanum trichloride and 0.2% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 0.4% Lanthanum trichloride and 0.2% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 3: 5.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99.1%, the Perchloropyridine foreign matter content is 1.6%, catalyzer work-ing life is 80 days.
Embodiment 9:(fluidized-bed and fixed bed add the cocoanut active charcoal catalyzer of modification simultaneously)
Embodiment 9 primary processes are as described in the example 1, fluidized-bed and fixed bed are modified catalyst, modified catalyst in the fluidized-bed is to have added 1.5% Lanthanum trichloride and 0.2% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, added 1% Lanthanum trichloride and 0.5% Cerium II Chloride in the fixed bed in cocoanut active charcoal, the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 2: 6.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product tetrachloro that the product that obtains obtains-2-cyanopyridine content 〉=99.2%, Perchloropyridine foreign matter content≤1.5%, catalyzer work-ing life is 98 days.
Embodiment 10:(is the cocoanut active charcoal catalyzer of fluidized-bed interpolation modification only)
Embodiment 10 primary processes are as described in the example 1, modified catalyst in the fluidized-bed is to have added 1.5% Lanthanum trichloride and 0.2% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, fixed bed still uses common cocoanut active charcoal, and the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 2: 5.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99%, the Perchloropyridine foreign matter content is 2.5%, catalyzer work-ing life is 55 days.
Embodiment 11:(is the cocoanut active charcoal catalyzer of fluidized-bed interpolation modification only)
Embodiment 11 primary processes are as described in the example 1, modified catalyst in the fluidized-bed is to have added 1.5% Lanthanum trichloride and 0.5% Cerium II Chloride in 24 order cocoanut active charcoal catalyzer, fixed bed still uses common cocoanut active charcoal, and the particle diameter proportioning is 16 orders: 25 orders: 38 orders=1: 2: 5.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 99%, the Perchloropyridine foreign matter content is 2.5%, catalyzer work-ing life is 62 days.
Embodiment 12:(only adds the cocoanut active charcoal catalyzer of modification in the fixed bed)
Embodiment 12 primary processes are as described in the example 1, fluidized-bed still is the common cocoanut active charcoal catalyzer of 1000kg24 purpose, and catalyzer that fixed bed adds is modified catalyst, particle diameter ratio is 16 orders, 25 orders, 38=1: 3: 5, added 0.4% Lanthanum trichloride and 0.2% Cerium II Chloride in common cocoanut active charcoal catalyzer.The fluidized-bed reaction temperature is controlled at
200-300 ℃, the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 98.5%, the Perchloropyridine foreign matter content is 2.5%, catalyzer work-ing life is 40 days.
Embodiment 13:(only adds the cocoanut active charcoal catalyzer of modification in the fixed bed)
Embodiment 13 primary processes are as described in the example 1, fluidized-bed still is the common cocoanut active charcoal catalyzer of 1000kg24 purpose, and catalyzer that fixed bed adds is modified catalyst, particle diameter ratio is 16 orders, 25 orders, 38=1: 2: 6, added 1.5% Lanthanum trichloride and 0.5% Cerium II Chloride in common cocoanut active charcoal catalyzer.The fluidized-bed reaction temperature is controlled at 200-300 ℃, and the control of fixed bed reaction temperature is at 240-320 ℃.The product that obtains obtain the product tetrachloro-2-cyanopyridine content is 98.5%, the Perchloropyridine foreign matter content is 3.5%, catalyzer work-ing life is 50 days.
By the embodiment interpretation of result, adopt the cocoanut active charcoal of modification that following advantage is arranged in the reaction process: the one, reduce temperature of reaction, improve catalyst activity, solve the easy coking problem of catalyzer, improve catalyzer work-ing life; The 2nd, improve product yield and content.
The production method of a kind of tetrachloro of the present invention-2-cyanopyridine is described by concrete example, those skilled in the art can use for reference content of the present invention, the links such as appropriate change raw material, processing condition realize corresponding other purpose, its relevant change does not all break away from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and all be deemed to be included within the scope of the present invention.
Claims (7)
1. the production method of tetrachloro-2-cyanopyridine, described method comprises the steps:
A, preactivating catalysts step: reactor is fluidized-bed and fixed bed, the cocoanut active charcoal catalyzer that in fluidized-bed and fixed bed, adds modification, dehydration heats up, dewater complete after, pass into excessive chlorine activation, activation temperature is 200-250 ℃, 3 hours time, when two reactor each point temperature-stables, inspection does not measure HCl in the tail gas, is considered as activation and finishes;
It is 6-30 purpose cocoanut active charcoal catalyzer that the catalyzer of fluidized-bed is selected granularity, and it is 12-20 order, 20-30 order, 30-40 purpose cocoanut active charcoal catalyzer that at least two kinds of the catalyzer of fixed bed are selected from granularity; The cocoanut active charcoal catalyzer of described modification is to make by one or more of adding rare-earth metal chloride Lanthanum trichloride, praseodymium chloride, Cerium II Chloride in cocoanut active charcoal, and the interpolation total amount of rare-earth metal chloride is the 0.3%-3% of cocoanut active charcoal gross weight;
B, the pre-pervaporation step of 2-cyanopyridine: the 2-cyanopyridine is vaporized in vaporizer, take vaporizer out of by nitrogen subsequently, 2-cyanopyridine inlet amount is 1 with the ratio of nitrogen flow: 4-6;
C, reactions steps: will carry out the first step chlorination reaction with first fluidized-bed reactor at the step a that adds catalyzer after chlorine mixes through the 2-cyanopyridine of step b vaporization, the volume mol ratio that feeds intake of 2-cyanopyridine and chlorine is 1: 3-4, the fluidized-bed reaction temperature is controlled at 200-300 ℃, and reaction pressure is controlled at 0.008-0.1Mpa; Reaction time is 3-8 second; The fixed-bed reactor that enter the step a that adds catalyzer from fluidized-bed gas are out proceeded chlorination reaction, and temperature of reaction is controlled at 240-320 ℃, and reaction pressure is controlled at 0.008-0.1Mpa; Reaction time is 3-8 second;
D, separating step: will by out gas in the fixed-bed reactor through trap cooling, separate, the product tetrachloro of solid state-2-cyanopyridine is enriched in the trap bottom.
2. according to claim 1 the production method of tetrachloro-2-cyanopyridine, it is characterized in that: the average pore diameter of cocoanut active charcoal is not less than
Specific surface area is not less than 1000m
2/ g.
3. according to claim 2 the production method of tetrachloro-2-cyanopyridine, it is characterized in that: the average pore diameter of cocoanut active charcoal exists
Between, specific surface area is at 1200-1800m
2Between/the g.
4. according to claim 1 the production method of tetrachloro-2-cyanopyridine, it is characterized in that: it is 8-24 purpose cocoanut active charcoal catalyzer that the catalyzer of fluidized-bed is selected granularity.
5. according to claim 1 the production method of tetrachloro-2-cyanopyridine, it is characterized in that: the fixed-bed reactor activated-carbon catalyst is that the cocoanut active charcoal catalyzer of 12-20 order, 20-30 order, three kinds of different grain size scopes of 30-40 order forms by granularity, and the weight ratio of each component is 1: 2-3: 4-6.
6. the production method of arbitrary described tetrachloro-2-cyanopyridine according to claim 1-5, it is characterized in that: the interpolation total amount of rare-earth metal chloride is the 0.6%-2% of gac gross weight.
7. the production method of arbitrary described tetrachloro-2-cyanopyridine according to claim 1-5, it is characterized in that: metal chloride is Lanthanum trichloride, Cerium II Chloride, wherein the Lanthanum trichloride addition is the 0.4%-1.5% of gac gross weight, and the Cerium II Chloride addition is the 0.2%-0.5% of gac gross weight.
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| CN104610141A (en) * | 2015-01-23 | 2015-05-13 | 江苏苏利精细化工股份有限公司 | Method for reducing content of pentachloropyridine in synthetic tetrachloro-2-cyanopyridine |
| CN104707662A (en) * | 2015-02-13 | 2015-06-17 | 南京航空航天大学 | Phenolic organic aerogel-doped catalyst and preparation method thereof |
| CN108339555A (en) * | 2017-01-24 | 2018-07-31 | 盐城恒盛化工有限公司 | A kind of method of support type chlorination catalyst and preparation method thereof and synthesis 4 chloro pyridine |
| CN109092091A (en) * | 2018-11-13 | 2018-12-28 | 湖南比德生化科技股份有限公司 | It is a kind of for producing the mixer of the chloro- 2- cyanopyridine of 3,4,5,6- tetra- |
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| CN104610141A (en) * | 2015-01-23 | 2015-05-13 | 江苏苏利精细化工股份有限公司 | Method for reducing content of pentachloropyridine in synthetic tetrachloro-2-cyanopyridine |
| CN104610141B (en) * | 2015-01-23 | 2017-01-04 | 江苏苏利精细化工股份有限公司 | A kind of reduce the method for Pentachloropyridine content in synthesized four chloro-2-cyanopyridine |
| CN104707662A (en) * | 2015-02-13 | 2015-06-17 | 南京航空航天大学 | Phenolic organic aerogel-doped catalyst and preparation method thereof |
| CN108339555A (en) * | 2017-01-24 | 2018-07-31 | 盐城恒盛化工有限公司 | A kind of method of support type chlorination catalyst and preparation method thereof and synthesis 4 chloro pyridine |
| CN108339555B (en) * | 2017-01-24 | 2021-10-29 | 盐城恒盛化工有限公司 | Supported chlorination catalyst, preparation method thereof and method for synthesizing tetrachloropyridine |
| CN109092091A (en) * | 2018-11-13 | 2018-12-28 | 湖南比德生化科技股份有限公司 | It is a kind of for producing the mixer of the chloro- 2- cyanopyridine of 3,4,5,6- tetra- |
| CN109092091B (en) * | 2018-11-13 | 2024-03-08 | 湖南比德生化科技股份有限公司 | Mixer for producing 3,4,5, 6-tetrachloro-2-cyanopyridine |
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