CN109529891A - A kind of preparation method of supported catalyst and preparation method thereof and 2,3,6- trichloropyridine - Google Patents
A kind of preparation method of supported catalyst and preparation method thereof and 2,3,6- trichloropyridine Download PDFInfo
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- CN109529891A CN109529891A CN201811561307.3A CN201811561307A CN109529891A CN 109529891 A CN109529891 A CN 109529891A CN 201811561307 A CN201811561307 A CN 201811561307A CN 109529891 A CN109529891 A CN 109529891A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
A kind of supported catalyst and preparation method thereof, is related to chemical catalyst field, which is made of carrier material and lewis acid catalyst.Wherein, carrier material is active carbon；Lewis acid catalyst is the mixture of iron chloride, stannous chloride and aluminium chloride.The supported catalyst has preferable catalytic effect for the chlorination reaction of 2,6- dichloropyridine, efficiently can obtain 2,3,6- trichloropyridines by high productivity.A kind of preparation method of above-mentioned supported catalyst, it is easy to operate, it is not high to equipment requirement, it can conveniently and efficiently produce above-mentioned supported catalyst.The preparation method of one kind 2,3,6- trichloropyridine comprising under the catalysis of above-mentioned supported catalyst, by 2,6- dichloropyridine and chlorine hybrid reaction.It has high conversion rate, high income, and the high feature of product quality is suitble to be applied in large-scale industrial production.
Description
Technical field
The present invention relates to chemical catalyst field, in particular to a kind of supported catalyst and preparation method thereof and
The preparation method of 2,3,6- trichloropyridine.
Background technique
2,3,6- trichloropyridines are important fine-chemical intermediate, are widely used in medicine and pesticide research field, special
It is not pesticide field, it is the important intermediate of synthesizing new insecticide Rynaxypyr and cyanogen insect amide, is had wide
Application prospect.Currently, the production method of 2,3,6- trichloropyridines mainly includes liquid-phase catalysis chloridising and gas phase catalytic chlorination process.
Liquid phase chlorination method under condition of no solvent has great advantages since raw material is simple, reaction condition is mild, at present work
Industry is such method mostly.
Different research achievements shows to improve 2,6- dichloropyridine conversion ratio and 2, the main side of 3,6- trichloropyridine yields
Method is to select the catalyst of different performance.The catalyst of liquid phase chlorination is broadly divided into homogeneous catalyst and heterogeneous catalysis two
Major class: be used for pyridine liquid phase chlorination earliest is homogeneous catalyst, mainly includes simple substance class catalyst and lewis acid catalyst.
Simple substance class catalyst with Pb, S, I, Sb etc. for representative have the advantages that it is cheap, be easy to get, but such catalyst is being urged
When changing chlorination, conversion ratio is lower and selectivity is poor, therefore does not have the application of industrialized production.2,6- dichloropyridine
Chlorination belong to parental materials, common catalyst is lewis acid, comprising: aluminium chloride, stannous chloride, stannous chloride, trichlorine
Change antimony and ferric trichloride etc., wherein industrially most widely used is ferric trichloride.Although lewis acid catalyst is 2,6-
Good activity and selectivity has been shown in dichloropyridine liquid phase chlorination, but still has promotion in catalytic effect this respect
The direction that new activity is higher, the better catalyst of stability is this field pursuit always is developed in space.
Summary of the invention
The first object of the present invention is to provide a kind of supported catalyst, and the chlorination that can be catalyzed 2,6- dichloropyridine is anti-
It answers, efficient high productivity obtains 2,3,6- trichloropyridines.
The second object of the present invention is to provide a kind of supported catalyst, easy to operate, not high to equipment requirement, can
Conveniently and efficiently produce above-mentioned supported catalyst.
The third object of the present invention be to provide it is a kind of prepare 2,3,6- trichloropyridines, reaction conversion ratio is high, high income,
It is suitble to application and large-scale industrial production.
The embodiment of the present invention is achieved in that
A kind of supported catalyst, is made of carrier material and lewis acid catalyst；
Wherein, carrier material is active carbon；Lewis acid catalyst is the mixing of iron chloride, stannous chloride and aluminium chloride
Object.
A kind of preparation method of above-mentioned supported catalyst comprising:
Carrier material is impregnated in the solution of lewis acid catalyst, catalyst precursor is obtained；
Catalyst precursor is dried, is roasted.
The preparation method of one kind 2,3,6- trichloropyridine comprising:
Under the catalysis of above-mentioned supported catalyst, by 2,6- dichloropyridine and chlorine hybrid reaction.
The beneficial effect of the embodiment of the present invention is:
The embodiment of the invention provides a kind of supported catalysts, are made of carrier material and lewis acid catalyst.Its
In, carrier material is active carbon；Lewis acid catalyst is the mixture of iron chloride, stannous chloride and aluminium chloride.The load is urged
Agent has preferable catalytic effect for the chlorination reaction of 2,6- dichloropyridine, efficiently can obtain 2,3,6- tri- by high productivity
Chloropyridine.
The embodiment of the invention also provides a kind of preparation methods of above-mentioned supported catalyst, by impregnating carrier material
In the solution of lewis acid catalyst, the operations such as drying, roasting obtain above-mentioned supported catalyst.It operates letter
It is single, it is not high to equipment requirement, it can conveniently and efficiently produce above-mentioned supported catalyst.
The embodiment of the invention also provides a kind of preparation methods of 2,3,6- trichloropyridines comprising in above-mentioned supported catalyst
Under the catalysis of agent, by 2,6- dichloropyridine and chlorine hybrid reaction.It has high conversion rate, high income, the high spy of product quality
Point is suitble to be applied in large-scale industrial production.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is stability test result provided by test example 4 of the present invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the system of a kind of supported catalyst of the embodiment of the present invention and preparation method thereof and 2,3,6- trichloropyridine
Preparation Method is specifically described.
The embodiment of the invention provides a kind of supported catalysts, are made of carrier material and lewis acid catalyst；
Wherein, carrier material is active carbon；Lewis acid catalyst is the mixing of iron chloride, stannous chloride and aluminium chloride
Object.
The chlorination of 2,6- dichloropyridines belongs to parental materials, and common catalyst is lewis acid, comprising: aluminium chloride, chlorine
Change cuprous, stannous chloride, antimony trichloride and ferric trichloride etc., wherein industrially most widely used is ferric trichloride.Although
Lewis acid catalyst has shown good activity and selectivity in 2,6- dichloropyridine liquid phase chlorination, but imitates in catalysis
Fruit this respect, which remains unchanged, the space of promotion, and developing new active higher, the better catalyst of stability is that this field is pursued always
Direction.
Based on the above reasons, inventor has found by itself creative work, is composed using specific lewis acid
Composite catalyst shows better catalytic effect in the catalysis for 2,6- dichloropyridine chlorination reaction.Especially, chlorine
Change the ternary complex catalyst of iron, stannous chloride and aluminium chloride composition, catalytic effect is excellent.
Preferably, in the lewis acid catalyst, the molar ratio of iron chloride, stannous chloride and aluminium chloride be 6~8:1~
2:1~2.Supported catalyst is made according to aforementioned proportion, catalytic effect is more preferable, and the yield of reaction is higher.
Further, the load capacity of lewis acid catalyst is 1~8mmol/g.Inventor by creative work find,
In the case that load capacity is too low, catalytic effect has apparent reduction, and when load capacity is excessively high, active component aggregation be will cause
Reactivity is low.Under synthesis, within the scope of above-mentioned load capacity, the load effect of lewis acid catalyst is preferable.
Preferably, active carbon includes shell granular activated carbon, and shell granular activated carbon has porous structure and larger compares table
Area, load effect are more preferable.
The embodiment of the invention also provides a kind of preparation methods of above-mentioned supported catalyst comprising:
S1. carrier material is impregnated in the solution of lewis acid catalyst, obtains catalyst precursor.
S2. catalyst precursor is dried, roasted.
Optionally, carrier material can be pre-processed first before being impregnated, remove carrier material in impurity,
Moisture etc..Specifically, to the pretreatment of carrier material include: will be heated to 90 in 10%~15% dilute nitric acid solution~
100 DEG C of 5~8h of water-bath；Heat filtering and washing to filtrate is in neutrality, then by filter cake at 105~120 DEG C 10~15h, then
3~5h is roasted at 300~350 DEG C.
Further, the mode of dipping can be using one in equi-volume impregnating, excessive infusion process or multiple maceration
Kind, preferentially use equi-volume impregnating.Equi-volume impregnating is used, the water absorption of carrier material, concrete operations are first measured
Include: weigh it is a certain amount of, such as 1.0000g, above-mentioned pretreated carrier material, deionized water is added dropwise dropwise, after agitated
Carrier of being subject to is wet glutinous.If being in sticky shape, slowly moisture is siphoned away with filter paper, records the volume of added deionized water, as
Saturated water adsorptive value.By taking shell granular activated carbon as an example, water absorption is about 1ml, i.e. the saturation water suction of shell granular activated carbon
Amount are as follows: 1ml/g.
Further, the solution of lewis acid catalyst is to be dissolved in lewis acid catalyst in ethyl alcohol or dilute hydrochloric acid obtaining
, concentration is 2~3mmol/ml.Dipping carries out at room temperature, and dip time is advisable with 2~5h.
Further, temperature catalyst precursor being dried is 105~150 DEG C, the time is 10~for 24 hours.To dry
The temperature that catalyst precursor after dry is roasted is 300~550 DEG C, and the time is 3~10h.Dry and roasting can remove
Remaining solvent avoids it from impacting catalysis reaction.
The present invention also provides a kind of preparation methods of 2,3,6- trichloropyridines comprising:
Under the catalysis of above-mentioned supported catalyst, by 2,6- dichloropyridine and chlorine hybrid reaction.
Wherein, the temperature of reaction is 170~190 DEG C, and the time is 3~17h, the dosage of supported catalyst be 1wt%~
3wt%.Under the above-described reaction conditions, the conversion ratio and yield of reaction are preferable.Preferably, reaction carries out in chlorination tank, controls
The rate that is passed through of chlorine is 3~3.5ml/h, to reduce the generation of by-product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of supported catalyst is present embodiments provided, preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the dilute hydrochloric acid that 0.2g CuCl is dissolved in 10% is weighed, the CuCl hydrochloric acid solution of 2mmol/ml is made into；It weighs respectively
The anhydrous FeCl of 2.6g3With the anhydrous AlCl of 0.27g3It is dissolved in dehydrated alcohol, is made into the FeCl of 2mmol/ml respectively3Ethanol solution and
AlCl3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Three kinds of good metal chloride solutions add up to 10ml, in molar ratio (nFeCl3: nCuCl: nAlCl3=8:1:1,2mmol/g) mixing is
It is poured into beaker after even, quickly stirring 20min makes carrier in wet glutinous shape, then stands 5h at room temperature, obtains catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Embodiment 2
A kind of supported catalyst is present embodiments provided, preparation method is as follows:
S1. by shell granular activated carbon, 8h is boiled in 100 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 15h in 120 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 350 DEG C, the constant temperature calcining 5h at 350 DEG C.
S2. the dilute hydrochloric acid that 0.6g CuCl is dissolved in 10% is weighed, the CuCl hydrochloric acid solution of 3mmol/ml is made into；It weighs respectively
The anhydrous FeCl of 2.9g3With the anhydrous AlCl of 0.8g3It is dissolved in dehydrated alcohol, is made into the FeCl of 3mmol/ml respectively3Ethanol solution and
AlCl3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Three kinds of good metal chloride solutions add up to 10ml, in molar ratio (nFeCl3: nCuCl: nAlCl3=6:2:2,3mmol/g) mixing is
It is poured into beaker after even, quickly stirring 20min makes carrier in wet glutinous shape, then stands 5h at room temperature, obtains catalyst precarsor.
S4. above-mentioned catalyst precursor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground, is made for a long time with agate
It becomes powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Embodiment 3
A kind of supported catalyst is present embodiments provided, preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the dilute hydrochloric acid that 0.1g CuCl is dissolved in 10% is weighed, the CuCl hydrochloric acid solution of 1mmol/ml is made into；It weighs respectively
The anhydrous FeCl of 1.3g3With the anhydrous AlCl of 0.14g3It is dissolved in dehydrated alcohol, is made into the FeCl of 1mmol/ml respectively3Ethanol solution and
AlCl3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Three kinds of good metal chloride solutions add up to 10ml, in molar ratio (nFeCl3: nCuCl: nAlCl3=8:1:1,1mmol/g) mixing is
It is poured into beaker after even, quickly stirring 20min makes carrier in wet glutinous shape, then stands 5h at room temperature, obtains catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Embodiment 4
A kind of supported catalyst is present embodiments provided, preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the dilute hydrochloric acid that 0.8g CuCl is dissolved in 10% is weighed, the CuCl hydrochloric acid solution of 8mmol/ml is made into；It weighs respectively
10.4g anhydrous FeCl3With the anhydrous AlCl of 1.08g3It is dissolved in dehydrated alcohol, is made into the FeCl of 8mmol/ml respectively3Ethanol solution and
AlCl3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Three kinds of good metal chloride solutions add up to 10ml, in molar ratio (nFeCl3: nCuCl: nAlCl3=8:1:1,8mmol/g) mixing is
It is poured into beaker after even, quickly stirring 20min makes carrier in wet glutinous shape, then stands 5h at room temperature, obtains catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Comparative example 1
This comparative example provides a kind of supported catalyst, and preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the anhydrous FeCl of 3.24g is weighed3It is dissolved in dehydrated alcohol, is made into the FeCl of 2mmol/ml3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Good FeCl3Ethanol solution 10ml is poured into beaker, and quickly stirring 20min makes carrier in wet glutinous shape, is then stood at room temperature
5h obtains catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Comparative example 2
This comparative example provides a kind of supported catalyst, and preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the dilute hydrochloric acid that the anhydrous CuCl of 1.98g is dissolved in 10% is weighed, the CuCl hydrochloric acid solution of 2mmol/ml is made into.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Good CuCl hydrochloric acid solution 10ml is poured into beaker, and quickly stirring 20min makes carrier in wet glutinous shape, is then stood at room temperature
5h obtains catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Comparative example 3
This comparative example provides a kind of supported catalyst, and preparation method is as follows:
S1. by shell granular activated carbon, 5h is boiled in 90 DEG C of water-baths in 10% dilute nitric acid solution, filters and washs while hot
It is in neutrality, then filter cake is dried to 12h in 110 DEG C of vacuum ovens and is ground into powder to filtrate, then in Muffle furnace
It is middle through temperature programming to 300 DEG C, the constant temperature calcining 3h at 300 DEG C.
S2. the anhydrous AlCl of 2.67g is weighed3It is dissolved in dehydrated alcohol, is made into the FeCl of 2mmol/ml3Ethanol solution.
S3. the shell granular activated carbon after roasting in 10g S1 step is weighed in 500ml beaker, will be prepared in S2 step
Good AlCl3Ethanol solution 10ml is poured into beaker, and quickly stirring 20min makes carrier in wet glutinous shape, then stands 5h at room temperature,
Obtain catalyst precarsor.
S4. above-mentioned catalyst precarsor is placed in a vacuum drying oven 105 DEG C of dry 12h, is ground for a long time with agate, makes it
Become powder.
S5. above-mentioned powdered samples are put into crucible, are placed in Muffle furnace through temperature programming to 450 DEG C, at 450 DEG C
Constant temperature calcining 3h, the taking-up when temperature is down to 50 DEG C or less obtain required supported catalyst.
Comparative example 4
This comparative example provides a kind of supported catalyst, and preparation method is substantially the same manner as Example 1, and difference is,
This comparative example uses gas phase SiO2As carrier material, the pretreatment mode of carrier is 550 DEG C of constant temperature calcining 3h.
Comparative example 5
This comparative example provides a kind of supported catalyst, and preparation method is substantially the same manner as Example 1, and difference is,
This comparative example uses nanometer ZrO2As carrier material, the pretreatment mode of carrier is 550 DEG C of constant temperature calcining 3h.
Comparative example 6
This comparative example provides a kind of supported catalyst, and preparation method is substantially the same manner as Example 1, and difference is,
This comparative example uses nano Ce O2As carrier material, the pretreatment mode of carrier is 550 DEG C of constant temperature calcining 3h.
Test example 1
Using supported catalyst provided by embodiment 1, it is tested for the catalysis item of 2,6- dichloropyridine chlorination reaction
Part, the specific method is as follows:
S1. 500ml four-hole boiling flask is taken, 540g 2,6- dichloropyridine and supported catalyst are added thereto, loads onto thermometer
And stirring, it is ensured that after device is air tight, start logical chlorine (logical chlorine rate is 3.125ml/h), reaction temperature T, the reaction time is
T, the quality of supported catalyst are M.
S2. after reaction, liquid product is collected while hot, is analyzed with gas-chromatography.Catalyst passes through centrifuge separation
It is recycled.
Wherein: C2,6- dichloropyridine(conversion ratio of 2,6- dichloropyridine)=(when the amount of reactant initial substance-reactant balance
The amount of substance)/reactant initial substance amount × 100%
Y2,3,6- trichloropyridineAmount/reactant initial substance of substance when (yield of 2,3,6- trichloropyridine)=product balance
Amount × 100%
Chromatographiccondition are as follows: use hydrogen flame ionization detector (FID), hydrogen is legal using normalizing as carrier gas
Amount analysis.
Test result is as shown in table 1.
The test of 1. catalytic reaction condition of table
| Serial number | T/℃ | t/h | M/g | Conversion ratio/% | Yield/% |
| 1 | 150 | 17 | 5.4 | 27.4 | 25.9 |
| 2 | 160 | 17 | 5.4 | 59.5 | 58.7 |
| 3 | 170 | 17 | 5.4 | 98 | 95 |
| 4 | 180 | 17 | 5.4 | 98.2 | 95.4 |
| 5 | 170 | 7 | 5.4 | 35 | 32.1 |
| 6 | 170 | 7 | 10.8 | 45.2 | 40.9 |
| 7 | 170 | 7 | 16.2 | 53.8 | 49.1 |
| 8 | 170 | 14 | 5.4 | 73.8 | 62.5 |
As can be seen from Table 1, supported catalyst provided by the embodiment of the present invention 1 has following characteristics in catalytic process:
1. reaction rate increases, when temperature reaches 170 DEG C, by 17h, 2,6- dichloro pyrroles with the raising (serial number 1~4) of temperature
Pyridine can convert completely；2. with the increase (serial number 5~7, catalyst amount 1wt%~3wt%) of catalyst amount, reaction rate
Increase, selects dosage for the catalyst of 1wt% from the point of view of economic benefit.3. with the increase (sequence in reaction time
Numbers 3,5,8), the conversion ratio of reaction increases, when reacted between when being 17h, 2,6- dichloropyridines can almost convert completely.It is comprehensive
The reaction condition of the various aspects such as cost, the energy, reaction effect, serial number 3 is the most suitable.
Test example 2
Using supported catalyst provided by Examples 1 to 2 and comparative example 1~3, it is tested for 2,6- dichloropyridine
The catalytic effect difference of chlorination reaction, the specific method is as follows:
S1. 500ml four-hole boiling flask is taken, 540g 2,6- dichloropyridine and 5.4g supported catalyst are added thereto, loads onto temperature
Degree meter and stirring, it is ensured that after device is air tight, start logical chlorine (logical chlorine rate is 3.125ml/h), 170 DEG C of reaction temperature, instead
It is 7h between seasonable.
S2. after reaction, liquid product is collected while hot, is analyzed with gas-chromatography.Catalyst passes through centrifuge separation
It is recycled.The calculation of yield and conversion ratio is with test example 1, and chromatographiccondition is the same as test example 1.Test result such as table 2
It is shown.
The catalytic result of 2. different loads catalyst of table
| nFeCl3: nCuCl: nAlCl3 | Conversion ratio/% | Yield/% | |
| Embodiment 1 | 8:1:1 | 35 | 32.1 |
| Embodiment 2 | 6:2:2 | 32.4 | 30.8 |
| Comparative example 1 | 10:0:0 | 28 | 25.5 |
| Comparative example 2 | 0:10:0 | 10.2 | 8.1 |
| Comparative example 3 | 0:0:10 | 9.1 | 7.9 |
As can be seen from Table 2, supported catalyst provided by the embodiment of the present invention 1~2, at 170 DEG C of reaction temperature, reaction
In the case that time is 7h, CuCl, FeCl is used alone in available 30% or more conversion ratio and yield in contrast3With
AlCl3Manufactured supported catalyst (comparative example 1~3), conversion ratio and yield fail to reach 30%, best FeCl3Also only
28% conversion ratio, poor CuCl and AlCl can be reached3Conversion ratio only has 10% or so.The embodiment of the present invention is demonstrated to be adopted
Polynary lewis acid catalyst system has better catalytic activity.
Test example 3
Using supported catalyst provided by embodiment 1 and comparative example 4~6, it is tested for 2,6- dichloropyridine chlorine
Change the catalytic effect difference of reaction, the specific method is as follows:
S1. 500ml four-hole boiling flask is taken, 540g 2,6- dichloropyridine and 5.4g supported catalyst are added thereto, loads onto temperature
Degree meter and stirring, it is ensured that after device is air tight, start logical chlorine (logical chlorine rate is 3.125ml/h), 170 DEG C of reaction temperature, instead
It is 17h between seasonable.
S2. after reaction, liquid product is collected while hot, is analyzed with gas-chromatography.Catalyst passes through centrifuge separation
It is recycled.The calculation of yield and conversion ratio is with test example 1, and chromatographiccondition is the same as test example 1.Test result such as table 3
It is shown.
The catalytic result of 3. different loads catalyst of table
| Carrier material | Conversion ratio/% | Yield/% | |
| Embodiment 1 | Shell granular activated carbon | 98 | 95 |
| Comparative example 4 | Gas phase SiO2 | 57.4 | 55.9 |
| Comparative example 5 | Nanometer ZrO2 | 12.1 | 5.2 |
| Comparative example 6 | Nano Ce O2 | 10.8 | 3.5 |
As can be seen from Table 3, supported catalyst provided by the embodiment of the present invention 1, at 170 DEG C of reaction temperature, reaction
Between in the case where 17h, raw material fundamental reaction is complete.It is (right using supported catalyst made of other carrier materials in contrast
Ratio 4~6), conversion ratio and yield fail to reach 60%, best gas phase SiO2Also it is only capable of reaching 57.4% conversion
Rate, poor nanometer ZrO2With nano Ce O2Conversion ratio even less than 15%.Demonstrate carrier used by the embodiment of the present invention
Material is advantageous for improving catalytic activity.
Test example 4
Using supported catalyst provided by embodiment 1, its stability in the case where being recycled for multiple times, specific method are tested
It is as follows:
S1. 500ml four-hole boiling flask is taken, 540g 2,6- dichloropyridine and 5.4g supported catalyst are added thereto, loads onto temperature
Degree meter and stirring, it is ensured that after device is air tight, start logical chlorine (logical chlorine rate is 3.125ml/h), 170 DEG C of reaction temperature, instead
It is 17h between seasonable.
S2. after reaction, liquid product is collected while hot, is analyzed with gas-chromatography.Catalyst passes through centrifuge separation
It is recycled, is put into 50 DEG C of dryings of vacuum oven for 24 hours.
S3. operation 5 times of S1~S2 are repeated, the variation of yield and conversion ratio is compared.The calculation of yield and conversion ratio
With test example 1, chromatographiccondition is the same as test example 1.Test result is as shown in Figure 1.
As seen from Figure 1, supported catalyst provided by embodiment 1 is after 5 circular responses, 2,6- dichloro pyrroles
The conversion ratio of pyridine, which still this concludes the description of supported catalyst provided by the embodiment of the present invention up to 95%, has good stablize
Property.
In conclusion the embodiment of the invention provides a kind of supported catalysts, by carrier material and Louis acid catalysis
Agent composition.Wherein, carrier material is active carbon；Lewis acid catalyst is the mixture of iron chloride, stannous chloride and aluminium chloride.
The supported catalyst has preferable catalytic effect for the chlorination reaction of 2,6- dichloropyridine, can efficiently high productivity obtain
2,3,6- trichloropyridine.
The embodiment of the invention also provides a kind of preparation methods of above-mentioned supported catalyst, by impregnating carrier material
In the solution of lewis acid catalyst, the operations such as drying, roasting obtain above-mentioned supported catalyst.It operates letter
It is single, it is not high to equipment requirement, it can conveniently and efficiently produce above-mentioned supported catalyst.
The embodiment of the invention also provides a kind of preparation methods of 2,3,6- trichloropyridines comprising in above-mentioned supported catalyst
Under the catalysis of agent, by 2,6- dichloropyridine and chlorine hybrid reaction.It has high conversion rate, high income, the high spy of product quality
Point is suitble to be applied in large-scale industrial production.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of supported catalyst, which is characterized in that be made of carrier material and lewis acid catalyst；
Wherein, the carrier material is active carbon；The lewis acid catalyst is the mixed of iron chloride, stannous chloride and aluminium chloride
Close object.
2. supported catalyst according to claim 1, which is characterized in that in the lewis acid catalyst, iron chloride, chlorine
Changing cuprous and aluminium chloride molar ratio is 6~8:1~2:1~2.
3. supported catalyst according to claim 1, which is characterized in that the load capacity of the lewis acid catalyst is 1
~8mmol/g.
4. a kind of preparation method of supported catalyst as claimed in any one of claims 1 to 3 characterized by comprising
The carrier material is impregnated in the solution of the lewis acid catalyst, obtains catalyst precursor；
The catalyst precursor is dried, is roasted.
5. the preparation method according to claim 4, which is characterized in that the solution of the lewis acid catalyst is will be described
Lewis acid catalyst is dissolved in obtained in ethyl alcohol or dilute hydrochloric acid, and concentration is 2~3mmol/ml.
6. the preparation method according to claim 4, which is characterized in that the temperature that the catalyst precursor is dried
Be 105~150 DEG C, the time be 10~for 24 hours.
7. preparation method according to claim 6, which is characterized in that roasted to the catalyst precursor after drying
The temperature of burning is 300~550 DEG C, and the time is 3~10h.
8. one kind 2,3, the preparation method of 6- trichloropyridine characterized by comprising
Under the catalysis of the described in any item supported catalysts of claims 1 to 3,2,6- dichloropyridine is mixed instead with chlorine
It answers.
9. preparation method according to claim 8, which is characterized in that the dosage of the supported catalyst be 1wt%~
3wt%.
10. preparation method according to claim 8, which is characterized in that the temperature of reaction is 170~190 DEG C, the time 3
~17h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887870A (en) * | 2006-08-07 | 2007-01-03 | 海宁钱江慧谷精化有限责任公司 | One-step process for producing tetrachloropyridine in high content |
| CN104557683A (en) * | 2013-10-09 | 2015-04-29 | 郁建涵 | Preparation method of 2,3-dichloro-5-trifluoromethylpyridine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1887870A (en) * | 2006-08-07 | 2007-01-03 | 海宁钱江慧谷精化有限责任公司 | One-step process for producing tetrachloropyridine in high content |
| CN104557683A (en) * | 2013-10-09 | 2015-04-29 | 郁建涵 | Preparation method of 2,3-dichloro-5-trifluoromethylpyridine |
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| CN113244934A (en) * | 2021-05-25 | 2021-08-13 | 上海华谊（集团）公司 | Catalyst for producing 2,3, 6-trichloropyridine and preparation method thereof |
| CN113244934B (en) * | 2021-05-25 | 2022-11-08 | 上海华谊（集团）公司 | Catalyst for producing 2,3,6-trichloropyridine and preparation method thereof |
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