CN107628988A - A kind of synthetic method of 2,3 dichloropyridine - Google Patents
A kind of synthetic method of 2,3 dichloropyridine Download PDFInfo
- Publication number
- CN107628988A CN107628988A CN201710892921.7A CN201710892921A CN107628988A CN 107628988 A CN107628988 A CN 107628988A CN 201710892921 A CN201710892921 A CN 201710892921A CN 107628988 A CN107628988 A CN 107628988A
- Authority
- CN
- China
- Prior art keywords
- reaction
- dichloropyridines
- mno
- iro
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of synthetic method of 2,3 dichloropyridines (III), step is：1) using pyridine (I) as predominant starting material, water or water vapour as reaction medium, under chlorination derivant existence condition, pyridine and chlorine reaction obtain pyridinium chloride (II) and are used as next step reaction raw materials to complete；2) pyridinium chloride (II) obtained using the first step is used as reaction raw materials, water or water vapour are as reaction medium, under acid binding agent, catalyst existence condition, pyridinium chloride (II) contacts with hydrogen, reacted through catalytic hydrogenating reduction, 2 of purity more than 99%, 3 dichloropyridines (III) are obtained, the catalyst is nanometer IrO2‑ZnO‑MnO2Composite catalyst.Reaction equation is：Wherein, n=2~5.Reaction conversion ratio of the present invention and selectivity height, product with stable quality, production operation simply, low cost and other advantages, overcome 2 obtained by existing synthetic method, 3 dichloropyridines (III) quality is unstable and must can just make 2,3 dichloropyridine (III) qualities deficiency up to standard through multiple rectifying.
Description
Technical field
The present invention relates to the preparation method of organic compound, more particularly to the synthetic method of one kind 2,3- dichloropyridines.
Background technology
Pyridinium chloride, as 2- chloropyridines, 2,3- dichloropyridines, 2,6- dichloropyridines, 2,3,5- trichloropyridines etc. are
Important fine chemistry industry synthetic intermediate, it is widely used in agricultural chemicals, the production field of medicine.Wherein 2,3- dichloropyridines are 6 kinds
A kind of purposes pyridinium chloride larger compared with wide, dosage, is novel pesticide Rynaxypyr in dichloropyridine isomers
Key intermediate, 2,3,5- trichloropyridines are that synthesis has excellent preventive effect function to rat-tail show wheat ma, oat, rye grass and green bristlegrass
Herbicide dislike careless ether, alkynes oxalic acid, the primary raw material of clodinafop-propargyl.
The method of open production 2,3- dichloropyridines mainly has two kinds at present.First, referred to as " diazonium-chloro method ", with ammonia
Yl pyridines, chloro aminopyridine or niacinamide etc. are predominant starting material, are chemically reacted through one or multi-step, synthesize 2,3- bis-
Chloropyridine.Hebei Yanao Chemical Co., Ltd.【CN101302190B】With Anhui Jixi County Huihuang Chemical Co., Ltd.
【CN104926715A】Using 3- aminopyridines as initiation material, synthesize 2- chlorine-3-aminopyridines through one-step chlorination reaction,
3- Amino-2-Chloropyridines synthesize 2,3- dichloropyridines through diazotising-chloro process again.Nanjing Guang Tong medication chemistries Co., Ltd
【CN102086174B】With Nanjing Tian Ze Chemical Co., Ltd.s【CN103570609B】Using 2- chloro-nicotinamides as predominant starting material,
Obtain 3- Amino-2-Chloropyridines through a step Hofmann degradation, 3- Amino-2-Chloropyridines in acid condition with natrium nitrosum, chlorine
Change cuprous mixing and synthesize 2,3- dichloropyridines through diazotising-chloro process.Du pont company【CN1910152B、
CN101959862B】Directly with 3- Amino-2-Chloropyridines, 2,3- dichloropyridines are synthesized through a step diazotising-chloro process.Shandong
Tian Xin Chemical Co., Ltd.s【CN105399663A】With 2,3- diamino-pyridines for initiation material, through diazotising-chloro process one
Step synthesis 2,3- dichloropyridines.The technique of diazonium-chloro method production 2,3- dichloropyridines is in eighties of last century and this century previous decade
Be widely used, but the production technology can produce the high nitrogen high-salt wastewater of significant amount, environmental pollution is very big, waste processing cost too
Height, diazotization process degree of safety is not high, does not meet wanting for energy-conservation, emission reduction, environmental protection, safety that currently country proposes to chemical enterprise
Ask.
For solve diazonium-chloro method present in environmental issue, researcher develop again chlorination-dechlorinating process for produce 2,
3- dichloropyridines.Hengshun Chemical Co., Ltd., Chuzhou【CN103145609B】With 2,3,6- trichloropyridines for raw material, C1-C4 is used
Alcohol be solvent, palladium carbon, using formic acid, sodium formate or ammonium formate as hydrogen donor, is selectively taken off 6- positions chlorine and closed as catalyst
Into 2,3- dichloropyridines.Lian Hua Science and Technology Co., Ltd.【CN102153507B】With 2,6- dichloropyridines for initiation material, with
Lewis acid carries out chlorination reaction as catalyst, chlorine as chlorine source, and reaction terminates, and cooling, rectification under vacuum obtain 2,3,6-
Trichloropyridine；2 isolated, 3,6 trichloropyridines mixed with acid binding agent, metallic catalyst, organic solvent with pressure vessel in, with
Hydrogen selectively takes off 6- positions chlorine as hydrogen source, obtains 2,3- dichloropyridines, 3- chloropyridines.Use chlorination disclosed above-de-
Although chlorine method solves the deficiencies of wastewater flow rate is big in diazonium-chloro method, but still suffer from that expensive raw material price, source be limited, easy quilt
Trade monopoly, technique one way feed back is more, conversion ratio is low, and needing Multistage rectifying tower, rectifying can just obtain qualified 2, the 3- bis- of quality repeatedly
Chloropyridine.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of technique of continuity method production pyridinium chloride.
The synthetic method of one kind 2,3- dichloropyridines, it is characterised in that concretely comprise the following steps：
The first step, using pyridine (I) as initiation material, water or water vapour as reaction medium, in the presence bar of chlorination derivant
Under part, pyridine and chlorine reaction, stratification obtains aqueous phase and pyridinium chloride (II) phase, pyridinium chloride (II) after reaction
It is mutually post-treated or not post-treated, as next step reaction raw materials；
Second step, the pyridinium chloride (II) obtained using the first step as reaction raw materials, water or water vapour as reaction medium,
Under derivant, acid binding agent, catalyst existence condition, pyridinium chloride (II) contacts with hydrogen, and it is anti-that catalytic hydrogenating reduction occurs
Should, post-processed after reaction, obtain 2,3- dichloropyridines (III), the catalyst is nanometer IrO2-ZnO-MnO2It is compound to urge
Agent；
Represent as follows with equation,
Wherein, n=2~5.
Further, the nanometer IrO2-ZnO-MnO2The synthetic method of composite catalyst is：
1) Ti/IrO2The preparation of pole plate：By the aqueous solution of the chloro-iridic acid of iridium weight/mass percentage composition >=35.0% and absolute ethyl alcohol with
Volume ratio 1:10~15 uniformly mixing, then mixed liquor is coated in into Ti plate surfaces, are dried after coating in the environment of≤150 DEG C,
10~20min of calcining under 400~500 DEG C of environment is placed in after drying, then takes out air cooling, then repeat to apply again in coating surface
Cover, dry and calcination process 3~5 times, last time calcination time is 1~2h, and Ti/IrO is made2Pole plate；
2) MnO2Preparation：With Ti/IrO obtained by step 1)2Pole plate is anode, and graphite cake is negative electrode, MnSO4、NaSO4And H2SO4
Mixed solution is electrolyte electrosynthesis glyoxal MnO2, wherein electrolytic current density is 10~15mA/cm2, electrolysis time >=5h, electrolysis
Temperature >=90 DEG C, MnSO in electrolyte4、NaSO4And H2SO4Concentration be respectively 150~200g/L, 50~80g/L and 1~
1.5mol/L；
3) prepared by precursor：By Ir：Zn mol ratios are 1:10~20 proportioning is by the chlorine iridium of iridium weight/mass percentage composition >=35.0%
Aqueous acid and ZnCl2Solid is hybridly prepared into solution, and ammoniacal liquor is added into solution and is existed until no longer producing precipitation, then by solution
Liquid phase is evaporated in the environment of≤200 DEG C, obtains solid mixture as precursor；
4) IrO2-ZnO-MnO2The preparation of composite catalyst：The MnO that step 2) is obtained2Powder is made, according to MnO2：Preceding body
Body mass ratio is 3~8:1 ratio is by MnO2It is well mixed with precursor, then mixture is calcined and obtains IrO2-ZnO-MnO2
Composite catalyst, the calcining heat are 500~600 DEG C, and calcination time is more than 1h；
5) nanoscale IrO2-ZnO-MnO2The preparation of composite catalyst：By obtained IrO in step 4)2-ZnO-MnO2It is compound to urge
Agent ball mill grinding, ball-milling technology are：Ball-milling Time >=7h, rotating speed are 400~450r/min, and ratio of grinding media to material is 3~5:1, ball milling
Powder afterwards crosses the screen cloth of 2000 mesh, and the powder for collecting net is nanometer IrO2-ZnO-MnO2Composite catalyst powder.
Further, in the first step reaction, pyridine（I）It is gaseous state or liquid, reaction medium and pyridine（I）Quality
Than for 5 ~ 10:1, reaction temperature is 120 ~ 280 DEG C.
Further, in first step reaction, chlorination reaction derivant be ultraviolet light, iron powder, iron chloride one kind or
Several is used in mixed way, and wherein iron powder and/or iron chloride is distributing or fixed, iron powder and/or iron chloride and pyridine（I）'s
Mass ratio is 0.05 ~ 0.1:1.
Further, the post-processing approach of the first step reaction is washing, stratification, and aqueous phase recovers lower batch chlorination
In course of reaction, wherein water scouring water and pyridinium chloride（II）Mass ratio is 1 ~ 2:1.
Further, in the second step reaction, pyridinium chloride（II）It is gaseous state or liquid, reaction medium and pyridine chlorine
Compound（II）Mass ratio be 0.05 ~ 5:1, reaction temperature is 50 ~ 80 DEG C, and reaction pressure is 0.3 ~ 1.0MPa.
Further, in second step reaction, catalyst be distributing or it is fixed be present in reaction system, be catalyzed
Agent and pyridinium chloride（II）Mass ratio be 0.005 ~ 0.05:1.
Further, in the reaction of described second step, acid binding agent used is pyridine, substituted pyridines, tertiary ammonia, the alkali of 6 ~ 12 carbon
One or more of mixing in metal carbonate, alkali metal hydrogencarbonate, alkaline-earth metal sodium carbonate, alkali metal bicarbonates,
Acid binding agent and pyridinium chloride（II）Mass ratio be 0.3 ~ 1:1.
Further, the post processing of described second step reaction, refer to catalyst is recovered by filtration and set is back to lower batch and urged
Change in hydrogenation reduction, stand, water-oil phase separation, after water-oil phase separation, aqueous phase recovers lower batch catalytic hydrogenating reduction
In reaction, oil phase obtains high-quality 2,3- dichloropyridines through washing, simple rectifying（III）.
Further, the operation is batch (-type) or continous way.
The present invention discloses a kind of advanced technologies of continuity method production pyridinium chloride, and its advance is presented as：
（1）Independent research nanometer IrO2-ZnO-MnO2Composite catalyst, experiment find that such catalyst is compared to traditional
Metal catalyst generates the reacting catalytic performance of 2,3- dichloropyridines more to pyridinium chloride (mixing of a variety of chloro-products)
Good, product 2, the purity of 3- dichloropyridines is considerably higher.
（2）Organic solvent is replaced to avoid the cost input of recovery organic solvent, reduction from being produced into as reaction medium using water
Originally the environmental sanitation of workshop, is improved；Using the immiscible feature of profit, reaction terminates, and passes through simple stratification
Smoothly realize the separation of reaction medium and material；
（3）The characteristics of being reduced using pyridine ring alkalescence with substitution chlorine atom number increase on ring, reaction terminates, pyridine chlorination
Thing（II）Or 2,3- dichloropyridines（III）It can remove by slightly acidic water washing and be mingled with pyridine therein, wash water returns to reaction
Process, reduce the wastewater flow rate of technique；
（4）The less frequency is related to distillation process and can greatly reduce organic matter coking, equipment corrosion and pyrrole caused by high temperature
Pyridine chloride（II）Or 2,3- dichloropyridines（III）The phenomenon of outward appearance jaundice, beneficial to 2,3- dichloropyridines（III）The stabilization of quality
And improve；
（5）Using coal chemical industry product pyridine cheap and easy to get as raw material, solve the problems, such as that primary raw material is not easy to obtain, reduce technique
Cost.
Brief description of the drawings
Fig. 1 is four kinds of catalyst pyridinium chlorides（II）2,3- dichloropyridines is pure in hydrogenation reduction product
Degree.
Embodiment
The following examples further illustrate some features of the present invention, but the present invention applies for the content of protection
Do not limited with scope by following embodiments.
Embodiment 1
790 kilograms of pyridines, 3950 kg of water are mixed with 80 kilograms of iron powders, 120 ~ 230 DEG C, are continually fed into 3000 kilograms of chlorine,
Stirring terminates to reaction, stratification, obtains 1500 kilograms of pyridinium chlorides（II）；
By 1500 kilograms of pyridinium chlorides（II）Mixed with 1500 kg of water, stratification, obtain 1440 kilograms of pyridinium chlorides
（II）；
By 1440 kilograms of pyridinium chlorides（II）With 5000 kg of water, 7.2 kilograms of nanometer IrO2-ZnO-MnO2Composite catalyst,
420 kilograms of pyridine mixing, at 40 ~ 60 DEG C, under the conditions of Hydrogen Vapor Pressure is 0.3 ~ 0.5MPa, reaction is complete, and palladium carbon is recovered by filtration, and filters
Liquid 200 kilograms of washings of oil reservoir, obtains 2, the 3- dichloropyridines of 1035.9 kilograms of purity 98.3% through stratification；
The 2,3- dichloropyridines of 1035.9 kilograms of purity 98.3% obtain the colourless of 916.5 kilograms of purity 99.7% through rectification and purification
Bright shape 2,3- dichloropyridines, yield 86.6%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Wherein, nanometer IrO2-ZnO-MnO2The synthetic method of composite catalyst is：
1) Ti/IrO2The preparation of pole plate：By iridium weight/mass percentage composition be 35.0% chloro-iridic acid the aqueous solution and absolute ethyl alcohol with
Volume ratio 1:10 uniformly mixing, then mixed liquor is coated in into Ti plate surfaces, are dried after coating in the environment of 150 DEG C, after drying
It is placed under 400 DEG C of environment and calcines 10min, then takes out air cooling, then in coating surface repetitive coatings, drying and calcination process again
3 times, last time calcination time is 1h, and Ti/IrO is made2Pole plate；
2) MnO2Preparation：With Ti/IrO obtained by step 1)2Pole plate is anode, and graphite cake is negative electrode, MnSO4、NaSO4And H2SO4
Mixed solution is electrolyte electrosynthesis glyoxal MnO2, wherein electrolytic current density is 10mA/cm2, electrolysis time 5h, electrolysis temperature
>=90 DEG C, MnSO in electrolyte4、NaSO4And H2SO4Concentration be respectively 150g/L, 50g/L and 1mol/L；
3) prepared by precursor：By Ir：Zn mol ratios are 1:10 proportioning by iridium weight/mass percentage composition be 35.0% chloro-iridic acid water
Solution and ZnCl2Solid is hybridly prepared into solution, and ammoniacal liquor is added into solution until no longer producing precipitation, then by solution 200
Liquid phase is evaporated in the environment of DEG C, obtains solid mixture as precursor；
4) IrO2-ZnO-MnO2The preparation of composite catalyst：The MnO that step 2) is obtained2Powder is made, according to MnO2：Preceding body
Body mass ratio is 3:1 ratio is by MnO2It is well mixed with precursor, then mixture is calcined and obtains IrO2-ZnO-MnO2It is multiple
Catalyst is closed, the calcining heat is 500 DEG C, and calcination time is more than 1h；
5) nanoscale IrO2-ZnO-MnO2The preparation of composite catalyst：By obtained IrO in step 4)2-ZnO-MnO2It is compound to urge
Agent ball mill grinding, ball-milling technology are：Ball-milling Time is 7h, and rotating speed is 400~450r/min, ratio of grinding media to material 3:1, after ball milling
Powder crosses the screen cloth of 2000 mesh, collects the nanometer IrO of net2-ZnO-MnO2Composite catalyst powder.
Embodiment 2
It is under the conditions of 180 ~ 220 DEG C, ultraviolet light, 790 kilograms of pyridines and the mixed vapour of 7900 kg of water and 3000 is public
Jin chlorine contact, reaction；Produced mixed gas, into being fixed with the reactor of iron powder, chlorizate is collected, cools down, is quiet
Layering is put, obtains 1560 kilograms of pyridinium chlorides（II）；
By 1560 kilograms of pyridinium chlorides（II）With 7800 kg of water, 10 kilograms of nanometer IrO2-ZnO-MnO2Composite catalyst,
700 kilograms of sodium carbonate mixing, under the conditions of 30 ~ 40 DEG C, Hydrogen Vapor Pressure are 0.3 ~ 0.5MPa, reaction is complete, and platinum carbon is recovered by filtration,
Filtrate obtains 2, the 3- dichloropyridines of 1050 kilograms of purity 97.6% through stratification；
The 2,3- dichloropyridines of 1050 kilograms of purity 97.6% are obtained into the water white transparency of 903 kilograms of purity 99.5% through rectification and purification
Shape 2,3- dichloropyridines, yield 84.3%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Wherein, nanometer IrO2-ZnO-MnO2The synthetic method of composite catalyst is：
1) Ti/IrO2The preparation of pole plate：By the aqueous solution of the chloro-iridic acid of iridium weight/mass percentage composition 35.0% and absolute ethyl alcohol with body
Product ratio 1:12 uniformly mixing, then mixed liquor is coated in into Ti plate surfaces, are dried after coating in the environment of 100 DEG C, and drying is rearmounted
10min is calcined under 450 DEG C of environment, then takes out air cooling, then in coating surface repetitive coatings, drying and calcination process 3 again
Secondary, last time calcination time is 1h, and Ti/IrO is made2Pole plate；
2) MnO2Preparation：With Ti/IrO obtained by step 1)2Pole plate is anode, and graphite cake is negative electrode, MnSO4、NaSO4And H2SO4
Mixed solution is electrolyte electrosynthesis glyoxal MnO2, wherein electrolytic current density is 12mA/cm2, electrolysis time 6h, electrolysis temperature >=
90 DEG C, MnSO in electrolyte4、NaSO4And H2SO4Concentration be respectively 180g/L, 70g/L and 1.2mol/L；
3) prepared by precursor：By Ir：Zn mol ratios are 1:18 proportioning by iridium weight/mass percentage composition be 35.0% chloro-iridic acid water
Solution and ZnCl2Solid is hybridly prepared into solution, and ammoniacal liquor is added into solution until no longer producing precipitation, then by solution 200
Liquid phase is evaporated in the environment of DEG C, obtains solid mixture as precursor；
4) IrO2-ZnO-MnO2The preparation of composite catalyst：The MnO that step 2) is obtained2Powder is made, according to MnO2：Preceding body
Body mass ratio is 5:1 ratio is by MnO2It is well mixed with precursor, then mixture is calcined and obtains IrO2-ZnO-MnO2It is multiple
Catalyst is closed, the calcining heat is 550 DEG C, and calcination time is more than 1h；
5) nanoscale IrO2-ZnO-MnO2The preparation of composite catalyst：By obtained IrO in step 4)2-ZnO-MnO2It is compound to urge
Agent ball mill grinding, ball-milling technology are：Ball-milling Time is 7h, and rotating speed is 400~450r/min, ratio of grinding media to material 5:1, after ball milling
Powder crosses the screen cloth of 2000 mesh, collects the nanometer IrO of net2-ZnO-MnO2Composite catalyst powder.
Embodiment 3
It is under the conditions of 200 ~ 280 DEG C, ultraviolet light, 790 kilograms of pyridines and the mixed vapour of 7900 kg of water and 3000 is public
Jin chlorine contact, reaction；Produced mixed gas, into being fixed with the reactor of iron powder, chlorizate is collected, cools down, is quiet
Layering is put, obtains 1430 kilograms of pyridinium chlorides（II）；
By 1430 kilograms of pyridinium chlorides（II）Mixed with 2860 kg of water, stratification, obtain 1380 kilograms of pyridinium chlorides
（II）；
By 1380 kilograms of pyridinium chlorides（II）With 6900 kg of water, 69 kilograms of nanometer IrO2-ZnO-MnO2Composite catalyst,
1380 kilograms of calcium carbonate mixing, under the conditions of 60 ~ 80 DEG C, Hydrogen Vapor Pressure are 0.8 ~ 1.0MPa, reaction is complete, and platinum is recovered by filtration
Carbon, filtrate obtain 2, the 3- dichloropyridines of 750 kilograms of purity 93.3% through stratification；
The 2,3- dichloropyridines of 750 kilograms of purity 93.3% are obtained into the water white transparency of 580 kilograms of purity 99.1% through rectification and purification
Shape 2,3- dichloropyridines, yield 77.9%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Wherein, nanometer IrO2-ZnO-MnO2The synthetic method of composite catalyst is：
1) Ti/IrO2The preparation of pole plate：By iridium weight/mass percentage composition be 35.0% chloro-iridic acid the aqueous solution and absolute ethyl alcohol with
Volume ratio 1:15 uniformly mixing, then mixed liquor is coated in into Ti plate surfaces, are dried after coating in the environment of 150 DEG C, after drying
It is placed under 500 DEG C of environment and calcines 20min, then takes out air cooling, then in coating surface repetitive coatings, drying and calcination process again
5 times, last time calcination time is 2h, and Ti/IrO is made2Pole plate；
2) MnO2Preparation：With Ti/IrO obtained by step 1)2Pole plate is anode, and graphite cake is negative electrode, MnSO4、NaSO4And H2SO4
Mixed solution is electrolyte electrosynthesis glyoxal MnO2, wherein electrolytic current density is 15mA/cm2, electrolysis time 5h, electrolysis temperature
>=90 DEG C, MnSO in electrolyte4、NaSO4And H2SO4Concentration be respectively 200g/L, 80g/L and 1.5mol/L；
3) prepared by precursor：By Ir：Zn mol ratios are 1:20 proportioning by iridium weight/mass percentage composition be 35.0% chloro-iridic acid water
Solution and ZnCl2Solid is hybridly prepared into solution, and ammoniacal liquor is added into solution until no longer producing precipitation, then by solution 200
Liquid phase is evaporated in the environment of DEG C, obtains solid mixture as precursor；
4) IrO2-ZnO-MnO2The preparation of composite catalyst：The MnO that step 2) is obtained2Powder is made, according to MnO2：Preceding body
Body mass ratio is 8:1 ratio is by MnO2It is well mixed with precursor, then mixture is calcined and obtains IrO2-ZnO-MnO2It is multiple
Catalyst is closed, the calcining heat is 600 DEG C, and calcination time is more than 1h；
5) nanoscale IrO2-ZnO-MnO2The preparation of composite catalyst：By obtained IrO in step 4)2-ZnO-MnO2It is compound to urge
Agent ball mill grinding, ball-milling technology are：Ball-milling Time is 7h, rotating speed 450r/min, ratio of grinding media to material 5:1, the powder after ball milling
The screen cloth of 2000 mesh is crossed, collected the nanometer IrO of net2-ZnO-MnO2Composite catalyst powder.
Embodiment 4
120 ~ 130 DEG C, by 790 kilograms of pyridines and 3950 kg of water, 39.5 kilograms of iron chloride, stirring, it is continually fed into 2000 kilograms
Chlorine, stirring to reaction are completed；Stratification, obtain 1000 kilograms of pyridinium chlorides（II）；
By 1000 kilograms of pyridinium chlorides（II）With 200 kg of water, 30 kilograms of nanometer IrO2-ZnO-MnO2Composite catalyst, 300
The mixing of kilogram pyridine, under the conditions of 40 ~ 50 DEG C, Hydrogen Vapor Pressure are 0.5 ~ 0.6MPa, reaction is complete, and platinum carbon, filtrate is recovered by filtration
Through stratification, 2, the 3- dichloropyridines of 790 kilograms of purity 94.3%, the nanometer IrO are obtained2-ZnO-MnO2Composite catalyst
Synthetic method it is in the same manner as in Example 2；
The 2,3- dichloropyridines of 790 kilograms of purity 94.3% are obtained into the water white transparency of 605 kilograms of purity 99.2% through rectification and purification
Shape 2,3- dichloropyridines, yield 75.5%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Embodiment 5
120 ~ 130 DEG C, by 790 kilograms of pyridines and 3950 kg of water, 39.5 kilograms of iron chloride, stirring, it is continually fed into 2000 kilograms
Chlorine, stirring to reaction are completed；Stratification, obtain 1000 kilograms of pyridinium chlorides（II）；
By 1000 kilograms of pyridinium chlorides（II）With 2000 kg of water, 30 kilograms of nanometer IrO2-ZnO-MnO2Composite catalyst,
500 kilograms of sodium acid carbonate mixing, under the conditions of 40 ~ 50 DEG C, Hydrogen Vapor Pressure are 0.5 ~ 0.6MPa, reaction is complete, and platinum is recovered by filtration
Carbon, filtrate obtain 2, the 3- dichloropyridines of 810 kilograms of purity 94.6%, the nanometer IrO through stratification2-ZnO-MnO2It is compound
The synthetic method of catalyst is in the same manner as in Example 2；
The 2,3- dichloropyridines of 810 kilograms of purity 94.6% are obtained into the colourless of 653.4 kilograms of purity 99.5% through rectification and purification
Bright shape 2,3- dichloropyridines, yield 85.4%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Embodiment 6
120 ~ 130 DEG C, by 790 kilograms of pyridines and 3950 kg of water, 39.5 kilograms of iron chloride, stirring, it is continually fed into 2000 kilograms
Chlorine, stirring to reaction are completed；Stratification, obtain 1000 kilograms of pyridinium chlorides（II）；
With the overheat mixed gas being made up of 5000 kilograms of water vapours and 400 kilograms of pyridine vapors 1000 kilograms of pyridinium chlorides
（II）Bring into and be fixed with a nanometer IrO2-ZnO-MnO2The reactor of composite catalyst simultaneously mixes with hydrogen, in 40 ~ 50 DEG C, hydrogen pressure
Under the conditions of power is 0.5 ~ 0.6MPa, reaction is complete, collects reaction solution, stratification, obtains the 2,3- of 603 kilograms of purity 94.6%
Dichloropyridine, the nanometer IrO2-ZnO-MnO2The synthetic method of composite catalyst is in the same manner as in Example 2；
The 2,3- dichloropyridines of 603 kilograms of purity 94.6% are obtained into the colourless of 540.4 kilograms of purity 99.5% through rectification and purification
Bright shape 2,3- dichloropyridines, yield 85.5%, evaporate head and evaporate tail sleeve to lower batch distillation process.
Comparative example 1
The synthetic method of one kind 2,3- dichloropyridines, the addition of its reactive component, addition manner, response parameter, reactions steps
Deng identical with embodiment, it is differed only in：Second step pyridinium chloride（II）In catalytic hydrogenating reduction reaction, use
Catalyst be and IrO in embodiment 22-ZnO-MnO2The palladium carbon of equivalent.After second step reaction completely, reaction solution is collected, is stood
Layering, 2, the 3- dichloropyridines that 943 kilograms of purity are 74.6% are obtained, as shown in Figure 1.
Comparative example 2
The synthetic method of one kind 2,3- dichloropyridines, the addition of its reactive component, addition manner, response parameter, reactions steps
Deng identical with embodiment, it is differed only in：Second step pyridinium chloride（II）In catalytic hydrogenating reduction reaction, use
Catalyst be and IrO in embodiment 22-ZnO-MnO2The platinum carbon of equivalent.After second step reaction completely, reaction solution is collected, is stood
Layering, 2, the 3- dichloropyridines that 1017 kilograms of purity are 70.9% are obtained, as shown in Figure 1.
Comparative example 3
The synthetic method of one kind 2,3- dichloropyridines, the addition of its reactive component, addition manner, response parameter, reactions steps
Deng identical with embodiment, it is differed only in：Second step pyridinium chloride（II）In catalytic hydrogenating reduction reaction, use
Catalyst be and IrO in embodiment 22-ZnO-MnO2The Raney's nickel of equivalent.After second step reaction completely, reaction solution is collected, it is quiet
Layering is put, obtains 2, the 3- dichloropyridines that 966 kilograms of purity are 71.2%, as shown in Figure 1.
As shown in Figure 1, compared to traditional metal catalyst, to pyridinium chloride (mixing of a variety of chloro-products)
In the reaction for generating 2,3- dichloropyridines, nanometer IrO2-ZnO-MnO2Composite catalyst shows more preferably excellent effect, can
A variety of chloro-pyridine chlorides are catalyzed into very high 2, the 3- dichloropyridines of purity, this is conventional metals catalyst (palladium carbon, platinum carbon
Or Raney's nickel) do not accomplished.
Claims (10)
1. one kind 2, the synthetic method of 3- dichloropyridines, it is characterised in that concretely comprise the following steps：
The first step, using pyridine (I) as initiation material, water or water vapour as reaction medium, in the presence bar of chlorination derivant
Under part, pyridine and chlorine reaction, stratification obtains aqueous phase and pyridinium chloride (II) phase, pyridinium chloride (II) phase after reaction
It is post-treated or not post-treated, as next step reaction raw materials；
Second step, the pyridinium chloride (II) obtained using the first step as reaction raw materials, water or water vapour as reaction medium,
Under derivant, acid binding agent, catalyst existence condition, pyridinium chloride (II) contacts with hydrogen, and catalytic hydrogenating reduction reaction occurs,
Post-processed after reaction, obtain 2,3- dichloropyridines (III), the catalyst is nanometer IrO2-ZnO-MnO2Composite catalyzing
Agent；
Represent as follows with equation,
Wherein, n=2~5.
A kind of 2. synthetic method of 2,3- dichloropyridines according to claim 1, it is characterised in that the nanometer IrO2-
ZnO-MnO2The synthetic method of composite catalyst is：
1)Ti/IrO2The preparation of pole plate：By the aqueous solution of the chloro-iridic acid of iridium weight/mass percentage composition >=35.0% and absolute ethyl alcohol with body
Product ratio 1:10~15 uniformly mixing, then mixed liquor is coated in into Ti plate surfaces, are dried after coating in the environment of≤150 DEG C, are dried
10~20min of calcining under 400~500 DEG C of environment is placed in after dry, then takes out air cooling, then coating surface again repetitive coatings,
Drying and calcination process 3~5 times, last time calcination time be 1~2h, obtained Ti/IrO2Pole plate；
2)MnO2Preparation：With Ti/IrO obtained by step 1)2Pole plate is anode, and graphite cake is negative electrode, MnSO4、NaSO4And H2SO4
Mixed solution is electrolyte electrosynthesis glyoxal MnO2, wherein electrolytic current density is 10~15mA/cm2, electrolysis time >=5h, electrolysis
Temperature >=90 DEG C, MnSO in electrolyte4、NaSO4And H2SO4Concentration be respectively 150~200g/L, 50~80g/L and 1~
1.5mol/L；
3) prepared by precursor：By Ir：Zn mol ratios are 1:10~20 proportioning is by the chlorine iridium of iridium weight/mass percentage composition >=35.0%
Aqueous acid and ZnCl2Solid is hybridly prepared into solution, and ammoniacal liquor is added into solution and is existed until no longer producing precipitation, then by solution
Liquid phase is evaporated in the environment of≤200 DEG C, obtains solid mixture as precursor；
4)IrO2-ZnO-MnO2The preparation of composite catalyst：The MnO that step 2) is obtained2Powder, according to MnO2：Precursor quality
Than for 3~8:1 ratio is by MnO2It is well mixed with precursor, then mixture is calcined and obtains IrO2-ZnO-MnO2It is compound to urge
Agent, the calcining heat are 500~600 DEG C, and calcination time is more than 1h；
5) nanoscale IrO2-ZnO-MnO2The preparation of composite catalyst：By obtained IrO in step 4)2-ZnO-MnO2Composite catalyzing
Agent ball mill grinding, ball-milling technology are：Ball-milling Time >=7h, rotating speed are 400~450r/min, and ratio of grinding media to material is 3~5:1, after ball milling
Powder cross the screen clothes of 2000 mesh, the powder for collecting net is nanometer IrO2-ZnO-MnO2Composite catalyst powder.
3. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the first step is anti-
Ying Zhong, pyridine (I) are gaseous state or liquid, and the mass ratio of reaction medium and pyridine (I) is 5~10:1, reaction temperature be 120~
280℃。
4. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the first step is anti-
Ying Zhong, chlorination derivant are one or more of mixing of ultraviolet light, iron powder, iron chloride, and wherein iron powder and/or iron chloride is point
The mass ratio for dissipating formula or fixed, iron powder and/or iron chloride and pyridine (I) is 0.05~0.1:1.
5. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the first step is anti-
The post-processing approach answered is washing, stratification, and aqueous phase is recovered in lower batch chlorination reaction process, wherein water scouring water and pyridine
Chloride (II) mass ratio is 1~2:1.
6. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the second step is anti-
Ying Zhong, pyridinium chloride (II) are gaseous state or liquid, and the mass ratio of reaction medium and pyridinium chloride (II) is 0.05~5:1,
Reaction temperature is 50~80 DEG C, and reaction pressure is 0.3~1.0MPa.
7. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the second step is anti-
Ying Zhong, catalyst be distributing or it is fixed be present in reaction system, the mass ratio of catalyst and pyridinium chloride (II) is
0.005~0.05:1.
8. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that the second step is anti-
Ying Zhong, acid binding agent used are pyridine, substituted pyridines, tertiary ammonia, alkali carbonate, alkali metal hydrogencarbonate, the alkaline earth of 6~12 carbon
One or more of mixing in metal carbonate sodium, alkali metal bicarbonates, acid binding agent and the mass ratio of pyridinium chloride (II)
For 0.3~1:1.
9. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1 or 2, it is characterised in that described second step
The post processing of reaction, refer to catalyst is recovered by filtration and covers to be back in lower batch catalytic hydrogenating reduction reaction, stand, water-oil phase
Separation, after water-oil phase separation, aqueous phase is recovered in lower batch catalytic hydrogenating reduction reaction, and oil phase produces through washing, simple rectifying
To high-quality 2,3- dichloropyridines (III).
10. the synthetic method of one kind 2,3- dichloropyridines as claimed in claim 1, it is characterised in that the operation is batch (-type)
Or continous way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892921.7A CN107628988A (en) | 2017-09-27 | 2017-09-27 | A kind of synthetic method of 2,3 dichloropyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892921.7A CN107628988A (en) | 2017-09-27 | 2017-09-27 | A kind of synthetic method of 2,3 dichloropyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107628988A true CN107628988A (en) | 2018-01-26 |
Family
ID=61104185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710892921.7A Withdrawn CN107628988A (en) | 2017-09-27 | 2017-09-27 | A kind of synthetic method of 2,3 dichloropyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107628988A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433803A (en) * | 2019-08-12 | 2019-11-12 | 华南理工大学 | It is a kind of for dielectric film electrolysis water or the loaded catalyst of vapor and preparation method thereof |
| CN111620812A (en) * | 2020-05-27 | 2020-09-04 | 石家庄万业化工科技有限公司 | Synthetic method of 2, 3-dichloropyridine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432528A (en) * | 2011-12-01 | 2012-05-02 | 武汉市祥德科技发展有限公司 | Synthesis process of 2, 3-dichloropyridine |
| WO2014202626A1 (en) * | 2013-06-18 | 2014-12-24 | Saltigo Gmbh | Method for producing 2, 3-dichlorpyridine |
| CN106866647A (en) * | 2017-03-31 | 2017-06-20 | 九江善水科技股份有限公司 | The synthetic method of Yi Zhong Evil grass ethers and its trichloropyridine of intermediate 2,3,5 |
| CN107266357A (en) * | 2017-08-08 | 2017-10-20 | 九江善水科技股份有限公司 | A kind of synthetic method of 2,3 dichloropyridine |
-
2017
- 2017-09-27 CN CN201710892921.7A patent/CN107628988A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432528A (en) * | 2011-12-01 | 2012-05-02 | 武汉市祥德科技发展有限公司 | Synthesis process of 2, 3-dichloropyridine |
| WO2014202626A1 (en) * | 2013-06-18 | 2014-12-24 | Saltigo Gmbh | Method for producing 2, 3-dichlorpyridine |
| CN106866647A (en) * | 2017-03-31 | 2017-06-20 | 九江善水科技股份有限公司 | The synthetic method of Yi Zhong Evil grass ethers and its trichloropyridine of intermediate 2,3,5 |
| CN107266357A (en) * | 2017-08-08 | 2017-10-20 | 九江善水科技股份有限公司 | A kind of synthetic method of 2,3 dichloropyridine |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110433803A (en) * | 2019-08-12 | 2019-11-12 | 华南理工大学 | It is a kind of for dielectric film electrolysis water or the loaded catalyst of vapor and preparation method thereof |
| CN111620812A (en) * | 2020-05-27 | 2020-09-04 | 石家庄万业化工科技有限公司 | Synthetic method of 2, 3-dichloropyridine |
| CN111620812B (en) * | 2020-05-27 | 2022-05-24 | 石家庄万业化工科技有限公司 | Synthetic method of 2, 3-dichloropyridine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107266357B (en) | A kind of synthetic method of 2,3- dichloropyridines | |
| US9957623B2 (en) | Systems and methods for preparation and separation of products | |
| Li et al. | Facile synthesis of porous CuO polyhedron from Cu-based metal organic framework (MOF-199) for electrocatalytic water oxidation | |
| CN102755897B (en) | Method for preparing catalyst for methanol dehydrogenation to methyl formate through step coprecipitation-spray process | |
| JP2017075398A (en) | Electrochemical hydroxide systems and methods using metal oxidation | |
| WO2015184388A1 (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CA2950294A1 (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| CN103603008B (en) | A Nano TiO2 Electrode Doped with Rare Earth Lanthanum and Its Electrocatalytic Reduction of Furfural | |
| CN103804242B (en) | A kind of shortening prepares the method for m-sulfanilic acid | |
| CN104001516A (en) | Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile | |
| CN106588758A (en) | Synthetic process for 2-hydrazinylpyridine derivative | |
| CN103539699B (en) | A kind of synthesis technique of 3,4 difluorobenzonilyiles | |
| CN104387340A (en) | Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine | |
| CN113680355B (en) | Preparation method and application of copper-containing catalyst for alkyne hydrochlorination | |
| CN113388851B (en) | Electrochemical method for synthesizing 1,10-decanediol | |
| CN107628988A (en) | A kind of synthetic method of 2,3 dichloropyridine | |
| CN101603179B (en) | Electrolytic synthesis method of 3,5,6-trichloropyridine carboxylic acid | |
| CN104603329B (en) | The method for preparing vanillic aldehyde | |
| CN106478406B (en) | A kind of preparation method of nano-grade metal-organic framework materials | |
| CN101671296A (en) | New method for obtaining 2-chloro-3-methylpyridine from mixture of 2-chloro-5-methylpyridine and 2-chloro-3-methylpyridine | |
| CN105271208B (en) | A kind of graphene and preparation method thereof | |
| Vanhoof et al. | A comparative overview of the electrochemical valorization and incorporation of CO 2 in industrially relevant compounds | |
| CN102732911A (en) | Electrode, electrolytic device and method used for electrolytic synthesis of 3,6-dichloropicolinic acid | |
| CN104325154A (en) | Preparation technology of ultrafine copper powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180126 |