CN109529891B - Supported catalyst, preparation method thereof and preparation method of 2,3, 6-trichloropyridine - Google Patents
Supported catalyst, preparation method thereof and preparation method of 2,3, 6-trichloropyridine Download PDFInfo
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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
- C07D213/61—Halogen atoms or nitro radicals
Abstract
A supported catalyst and a preparation method thereof relate to the field of chemical catalysts, and the supported catalyst consists of a carrier material and a Lewis acid catalyst. Wherein the carrier material is activated carbon; the lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride. The supported catalyst has a good catalytic effect on the chlorination reaction of 2, 6-dichloropyridine, and can efficiently obtain the 2,3, 6-trichloropyridine with high yield. The preparation method of the supported catalyst is simple to operate, has low requirements on equipment, and can conveniently and quickly prepare the supported catalyst. The preparation method of 2,3, 6-trichloropyridine comprises the step of mixing 2, 6-dichloropyridine with chlorine gas for reaction under the catalysis of the supported catalyst. The method has the characteristics of high conversion rate, high yield and high product quality, and is suitable for being applied to large-scale industrial production.
Description
Technical Field
The invention relates to the field of chemical catalysts, and particularly relates to a supported catalyst and a preparation method thereof, and a preparation method of 2,3, 6-trichloropyridine.
Background
The 2,3, 6-trichloropyridine is an important fine chemical intermediate, is widely applied to the research field of medicines and pesticides, particularly the pesticide field, is an important intermediate for synthesizing novel pesticides chlorantraniliprole and cyantraniliprole, and has wide application prospect. At present, the production method of 2,3, 6-trichloropyridine mainly comprises a liquid phase catalytic chlorination method and a gas phase catalytic chlorination method. The liquid phase chlorination method under the solvent-free condition has great advantages due to simple raw materials and mild reaction conditions, and most of the methods are industrialized at present.
Different research results show that the main method for improving the conversion rate of 2, 6-dichloropyridine and the yield of 2,3, 6-trichloropyridine is to select catalysts with different properties. The liquid phase chlorination catalysts can be broadly divided into two categories, homogeneous catalysts and heterogeneous catalysts: the earliest catalysts for liquid phase chlorination of pyridine were homogeneous catalysts, mainly including elemental catalysts and lewis acid catalysts. Simple substance catalysts represented by Pb, S, I, Sb and the like have the advantages of low price and easiness in obtaining, but the catalysts have low conversion rate and poor selectivity when being used for catalytic chlorination, so that the catalysts have no applicability to industrial production. The chlorination of 2, 6-dichloropyridine is electrophilic substitution, and commonly used catalysts are lewis acids, including: aluminum chloride, cuprous chloride, stannous chloride, antimony trichloride, ferric trichloride, and the like, with ferric trichloride being the most widely used in industry. Although the Lewis acid catalyst has already shown good activity and selectivity in the liquid phase chlorination of 2, 6-dichloropyridine, there is still room for improvement in the aspect of catalytic effect, and the development of new catalysts with higher activity and better stability is always the direction pursued in the field.
Disclosure of Invention
The first purpose of the present invention is to provide a supported catalyst capable of catalyzing the chlorination reaction of 2, 6-dichloropyridine to obtain 2,3, 6-trichloropyridine with high efficiency and high yield.
The second purpose of the invention is to provide a supported catalyst, which is simple to operate, has low requirements on equipment and can be conveniently and quickly prepared.
The third purpose of the invention is to provide a method for preparing 2,3, 6-trichloropyridine, which has high reaction conversion rate and high yield, and is suitable for application and large-scale industrial production.
The embodiment of the invention is realized by the following steps:
a supported catalyst consisting of a support material and a lewis acid catalyst;
wherein the carrier material is activated carbon; the lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride.
A method for preparing the supported catalyst, comprising:
soaking a carrier material in a solution of a Lewis acid catalyst to obtain a catalyst precursor;
and drying and roasting the catalyst precursor.
A method for preparing 2,3, 6-trichloropyridine, comprising:
under the catalysis of the supported catalyst, 2, 6-dichloropyridine and chlorine are mixed and reacted.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a supported catalyst which is composed of a carrier material and a Lewis acid catalyst. Wherein the carrier material is activated carbon; the lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride. The supported catalyst has a good catalytic effect on the chlorination reaction of 2, 6-dichloropyridine, and can efficiently obtain the 2,3, 6-trichloropyridine with high yield.
The embodiment of the invention also provides a preparation method of the supported catalyst, which comprises the steps of soaking the carrier material in the solution of the Lewis acid catalyst, drying, roasting and the like to obtain the supported catalyst. The method has simple operation and low requirement on equipment, and can conveniently and quickly prepare the supported catalyst.
The embodiment of the invention also provides a preparation method of the 2,3, 6-trichloropyridine, which comprises the step of mixing and reacting the 2, 6-dichloropyridine with chlorine under the catalysis of the supported catalyst. The method has the characteristics of high conversion rate, high yield and high product quality, and is suitable for being applied to large-scale industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows the results of the stability test provided in test example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the supported catalyst and the preparation method thereof and the preparation method of 2,3, 6-trichloropyridine according to the embodiment of the present invention.
The embodiment of the invention provides a supported catalyst, which consists of a carrier material and a Lewis acid catalyst;
wherein the carrier material is activated carbon; the lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride.
The chlorination of 2, 6-dichloropyridine is electrophilic substitution, and commonly used catalysts are lewis acids, including: aluminum chloride, cuprous chloride, stannous chloride, antimony trichloride, ferric trichloride, and the like, with ferric trichloride being the most widely used in industry. Although the Lewis acid catalyst has already shown good activity and selectivity in the liquid phase chlorination of 2, 6-dichloropyridine, there is still room for improvement in the aspect of catalytic effect, and the development of new catalysts with higher activity and better stability is always the direction pursued in the field.
Based on the above reasons, the inventors discovered through their creative work that the composite catalyst formed by combining specific lewis acids exhibits better catalytic effect on the chlorination reaction of 2, 6-dichloropyridine. Particularly, the ternary composite catalyst composed of ferric chloride, cuprous chloride and aluminum chloride has excellent catalytic effect.
Preferably, in the Lewis acid catalyst, the molar ratio of ferric chloride, cuprous chloride and aluminum chloride is 6-8: 1-2: 1 to 2. The supported catalyst prepared according to the proportion has better catalytic effect and higher reaction yield.
Furthermore, the loading amount of the Lewis acid catalyst is 1-8 mmol/g. The inventor finds that the catalytic effect is obviously reduced under the condition of too low load amount through creative work, and the reaction activity is low due to the aggregation of active components when the load amount is too high. In sum, the loading effect of the lewis acid catalyst is better within the above loading range.
Preferably, the activated carbon comprises shell particle activated carbon, and the shell particle activated carbon has a porous structure, a large specific surface area and a better loading effect.
The embodiment of the invention also provides a preparation method of the supported catalyst, which comprises the following steps:
s1, soaking a carrier material in a solution of a Lewis acid catalyst to obtain a catalyst precursor.
And S2, drying and roasting the catalyst precursor.
Alternatively, the support material may be pretreated to remove impurities, moisture, etc. from the support material prior to impregnation. In particular, the pretreatment of the support material comprises: heating the mixture in a 10-15% dilute nitric acid solution to 90-100 ℃ in water bath for 5-8 h; hot filtering and washing until the filtrate is neutral, then roasting the filter cake at 105-120 ℃ for 10-15 h, and then roasting at 300-350 ℃ for 3-5 h.
Further, the impregnation may be carried out by one of an equal-volume impregnation method, an excess impregnation method or a multiple-impregnation method, preferably an equal-volume impregnation method. The method comprises the following steps of firstly measuring the water absorption capacity of a carrier material by using an isometric impregnation method, wherein the specific operations comprise: weighing a certain amount of the pretreated carrier material, such as 1.0000g, dropwise adding deionized water, and stirring until the carrier is wet and sticky. If the water is sticky, the water is slowly absorbed by using filter paper, and the volume of the added deionized water is recorded, namely the saturated water absorption capacity. Taking the shell particle activated carbon as an example, the water absorption capacity is about 1ml, namely the saturated water absorption capacity of the shell particle activated carbon is as follows: 1 ml/g.
Furthermore, the solution of the Lewis acid catalyst is obtained by dissolving the Lewis acid catalyst in ethanol or dilute hydrochloric acid, and the concentration of the Lewis acid catalyst is 2-3 mmol/ml. The impregnation is carried out at room temperature, and the impregnation time is preferably 2-5 h.
Further, the temperature for drying the catalyst precursor is 105-150 ℃, and the time is 10-24 h. And roasting the dried catalyst precursor at the temperature of 300-550 ℃ for 3-10 h. The residual solvent can be removed by drying and roasting, so that the influence of the residual solvent on the catalytic reaction is avoided.
The invention also provides a preparation method of the 2,3, 6-trichloropyridine, which comprises the following steps:
under the catalysis of the supported catalyst, 2, 6-dichloropyridine and chlorine are mixed and reacted.
Wherein the reaction temperature is 170-190 ℃, the reaction time is 3-17 h, and the dosage of the supported catalyst is 1-3 wt%. Under the above reaction conditions, the conversion rate and yield of the reaction are better. Preferably, the reaction is carried out in a chlorination kettle, and the feeding speed of the chlorine is controlled to be 3-3.5 ml/h, so that the generation of byproducts is reduced.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a supported catalyst, which was prepared as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 0.2g of CuCl and dissolving the CuCl in 10% dilute hydrochloric acid to prepare a CuCl hydrochloric acid solution with the concentration of 2 mmol/ml; 2.6g of anhydrous FeCl was weighed out separately3And 0.27g of anhydrous AlCl3Dissolving in absolute ethyl alcohol to prepare FeCl of 2mmol/ml respectively3Ethanol solution and AlCl3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, adding 10ml of the three metal chloride solutions prepared in the step S2 in total, and performing mol ratio (n)FeCl3：nCuCl：nAlCl3When the ratio is 8: 1: 1, 2mmol/g) are mixed evenly and poured into a beaker, the carrier is stirred rapidly for 20min to be in a wet sticky state, and then the carrier is kept stand for 5h at room temperature to obtain the catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Example 2
This example provides a supported catalyst, which was prepared as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a water bath at 100 ℃ for 8 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a vacuum drying oven at 120 ℃ for 15 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 350 ℃, and roasting at the constant temperature of 350 ℃ for 5 hours.
S2, weighing 0.6g of CuCl and dissolving the CuCl in 10% dilute hydrochloric acid to prepare a CuCl hydrochloric acid solution with the concentration of 3 mmol/ml; 2.9g of anhydrous FeCl was weighed out separately3And 0.8g of anhydrous AlCl3Dissolving in absolute ethyl alcohol to prepare FeCl of 3mmol/ml respectively3Ethanol solution and AlCl3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, adding 10ml of the three metal chloride solutions prepared in the step S2 in total, and performing mol ratio (n)FeCl3：nCuCl：nAlCl36: 2: 2,3mmol/g) are mixed evenly and poured into a beaker, the carrier is stirred rapidly for 20min to be in a wet sticky state, and then the mixture is kept stand for 5h at room temperature to obtain the catalyst precursor.
S4, drying the catalyst precursor in a vacuum drying oven at 105 ℃ for 12h, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Example 3
This example provides a supported catalyst, which was prepared as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 0.1g of CuCl and dissolving the CuCl in 10% dilute hydrochloric acid to prepare a 1mmol/ml CuCl hydrochloric acid solution; 1.3g of anhydrous FeCl was weighed out separately3And 0.14g of anhydrous AlCl3Dissolving in absolute ethyl alcohol to respectively prepare FeCl of 1mmol/ml3Ethanol solution and AlCl3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, adding 10ml of the three metal chloride solutions prepared in the step S2 in total, and performing mol ratio (n)FeCl3：nCuCl：nAlCl3When the ratio is 8: 1: 1, 1mmol/g) is mixed evenly and poured into a beaker, the carrier is stirred rapidly for 20min to be in a wet sticky state, and then the carrier is kept stand for 5h at room temperature to obtain the catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Example 4
This example provides a supported catalyst, which was prepared as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 0.8g of CuCl and dissolving the CuCl in 10% dilute hydrochloric acid to prepare a CuCl hydrochloric acid solution with the concentration of 8 mmol/ml; 10.4g of anhydrous FeCl was weighed out separately3And 1.08g of anhydrous AlCl3Dissolving in absolute ethyl alcohol to respectively prepare FeCl with the concentration of 8mmol/ml3Ethanol solution and AlCl3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, adding 10ml of the three metal chloride solutions prepared in the step S2 in total, and performing mol ratio (n)FeCl3：nCuCl：nAlCl3When the ratio is 8: 1: 1, 8mmol/g) are mixed evenly and poured into a beaker, the carrier is stirred rapidly for 20min to be in a wet sticky state, and then the carrier is kept stand for 5h at room temperature to obtain the catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Comparative example 1
This comparative example provides a supported catalyst, the preparation method of which is as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 3.24g of anhydrous FeCl3Dissolving in absolute ethyl alcohol to prepare FeCl of 2mmol/ml3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, and adding FeCl prepared in the step S2310ml of the ethanol solution was poured into a beaker, stirred rapidly for 20min to render the carrier wet and sticky, and then allowed to stand at room temperature for 5 hours to obtain a catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Comparative example 2
This comparative example provides a supported catalyst, the preparation method of which is as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 1.98g of anhydrous CuCl and dissolving the anhydrous CuCl in 10% dilute hydrochloric acid to prepare a CuCl hydrochloric acid solution with the concentration of 2 mmol/ml.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 in a 500ml beaker, pouring 10ml of the CuCl hydrochloric acid solution prepared in the step S2 in the beaker, quickly stirring for 20min to enable the carrier to be in a wet sticky state, and standing for 5h at room temperature to obtain the catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Comparative example 3
This comparative example provides a supported catalyst, the preparation method of which is as follows:
s1, boiling shell particle activated carbon in a 10% dilute nitric acid solution in a 90 ℃ water bath for 5 hours, carrying out suction filtration while the mixture is hot, washing until filtrate is neutral, drying a filter cake in a 110 ℃ vacuum drying oven for 12 hours, grinding the filter cake into powder, then carrying out temperature programming in a muffle furnace to 300 ℃, and roasting at the constant temperature of 300 ℃ for 3 hours.
S2, weighing 2.67g of anhydrous AlCl3Dissolving in absolute ethyl alcohol to prepare FeCl of 2mmol/ml3Ethanol solution.
S3, weighing the shell particle activated carbon roasted in the step 10g S1 into a 500ml beaker, and preparing AlCl in the step S2310ml of the ethanol solution was poured into a beaker, stirred rapidly for 20min to render the carrier wet and sticky, and then allowed to stand at room temperature for 5 hours to obtain a catalyst precursor.
S4, placing the catalyst precursor in a vacuum drying oven, drying for 12 hours at 105 ℃, and grinding the catalyst precursor with agate for a long time to obtain powder.
S5, placing the powdery sample into a crucible, placing the crucible into a muffle furnace, raising the temperature to 450 ℃ by a program, roasting the mixture for 3 hours at the constant temperature of 450 ℃, and taking out the mixture when the temperature is reduced to below 50 ℃ to obtain the required supported catalyst.
Comparative example 4
This comparative example provides a supported catalyst prepared substantially the same as in example 1 except that it employs gas phase SiO2As a carrier material, the pretreatment mode of the carrier is to roast the carrier at the constant temperature of 550 ℃ for 3 hours.
Comparative example 5
This comparative example provides a supported catalyst, which was prepared substantially in the same manner as in example 1, except that nano-ZrO was used in the comparative example2As a carrier material, the pretreatment mode of the carrier is to roast the carrier at the constant temperature of 550 ℃ for 3 hours.
Comparative example 6
This comparative example provides a supported catalyst having substantially the same preparation method as in example 1, except that nano-CeO was used in the comparative example2As a carrier material, the pretreatment mode of the carrier is to roast the carrier at the constant temperature of 550 ℃ for 3 hours.
Test example 1
The supported catalyst provided in example 1 was used to test the catalytic conditions for the chlorination of 2, 6-dichloropyridine by the following specific method:
s1, taking a 500ml four-neck flask, adding 540g of 2, 6-dichloropyridine and a supported catalyst into the flask, installing a thermometer and stirring, starting chlorine introduction (the chlorine introduction rate is 3.125ml/h) after ensuring that the device is airtight, and setting the reaction temperature T, the reaction time T and the mass of the supported catalyst M as follows.
And S2, after the reaction is finished, collecting a liquid phase product while the product is hot, and analyzing the product by using a gas chromatography. The catalyst was recovered by centrifugation.
Wherein: c2, 6-dichloropyridine(conversion of 2, 6-dichloropyridine) — (amount of reactant starting material-amount of material at equilibrium of reactant)/amount of reactant starting material × 100%
Y2,3, 6-trichloropyridineProcess for preparing (2,3, 6-trichloropyridine)Yield) — the amount of material at equilibrium of the product/amount of starting material of the reaction × 100%
The chromatographic analysis conditions were: a hydrogen Flame Ion Detector (FID) is adopted, hydrogen is used as carrier gas, and quantitative analysis is carried out by adopting a normalization method.
The test results are shown in table 1.
TABLE 1 catalytic reaction Condition testing
| Serial number | T/℃ | t/h | M/g | Conversion rate/% | 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, the supported catalyst provided in example 1 of the present invention has the following characteristics in the catalytic process: 1. along with the increase of the temperature (serial number 1-4), the reaction rate is increased, and when the temperature reaches 170 ℃, 2, 6-dichloropyridine can be completely converted after 17 hours; 2. along with the increase of the catalyst dosage (serial number 5-7, catalyst dosage 1 wt% -3 wt%), the reaction rate is increased, and the catalyst dosage of 1 wt% can be selected from the economic benefit viewpoint. 3. The conversion rate of the reaction increased with the increase of the reaction time (Nos. 3, 5, 8), and 2, 6-dichloropyridine was almost completely converted with the reaction time of 17 hours. The reaction condition of the serial number 3 is most suitable in many aspects such as comprehensive cost, energy, reaction effect and the like.
Test example 2
The supported catalysts provided in examples 1-2 and comparative examples 1-3 were used to test the differences in catalytic effects on chlorination of 2, 6-dichloropyridine, and the specific method was as follows:
s1, taking a 500ml four-neck flask, adding 540g of 2, 6-dichloropyridine and 5.4g of supported catalyst into the flask, installing a thermometer and stirring, starting chlorine introduction (the chlorine introduction rate is 3.125ml/h) after ensuring that the device is airtight, and reacting at the temperature of 170 ℃ for 7 h.
And S2, after the reaction is finished, collecting a liquid phase product while the product is hot, and analyzing the product by using a gas chromatography. The catalyst was recovered by centrifugation. The yield and conversion were calculated in the same manner as in test example 1, and the chromatographic conditions were the same as in test example 1. The test results are shown in table 2.
TABLE 2 catalytic results for different supported catalysts
| nFeCl3：nCuCl：nAlCl3 | Conversion rate/% | Yield/% | |
| Example 1 | 8:1:1 | 35 | 32.1 |
| Example 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, the supported catalysts provided in the embodiments 1-2 of the present invention can achieve a conversion of 30% or more at a reaction temperature of 170 ℃ for a reaction time of 7 hoursRate and yield, in contrast to CuCl, FeCl alone3And AlCl3The conversion rate and yield of the prepared supported catalyst (comparative examples 1-3) can not reach 30%, and the best FeCl3Also only 28% conversion, poor CuCl and AlCl3The conversion rate is only about 10%. The multi-element Lewis acid catalyst system adopted by the embodiment of the invention has better catalytic activity.
Test example 3
The supported catalysts provided in example 1 and comparative examples 4 to 6 were used to test the difference in catalytic effect on the chlorination reaction of 2, 6-dichloropyridine, and the specific method was as follows:
s1, taking a 500ml four-neck flask, adding 540g of 2, 6-dichloropyridine and 5.4g of supported catalyst into the flask, installing a thermometer and stirring, starting chlorine introduction (the chlorine introduction rate is 3.125ml/h) after ensuring that the device is airtight, and reacting at the temperature of 170 ℃ for 17 h.
And S2, after the reaction is finished, collecting a liquid phase product while the product is hot, and analyzing the product by using a gas chromatography. The catalyst was recovered by centrifugation. The yield and conversion were calculated in the same manner as in test example 1, and the chromatographic conditions were the same as in test example 1. The test results are shown in table 3.
TABLE 3 catalytic results for different supported catalysts
| Carrier material | Conversion rate/% | Yield/% | |
| Example 1 | Husk particle active carbon | 98 | 95 |
| Comparative example 4 | Gas phase SiO2 | 57.4 | 55.9 |
| Comparative example 5 | Nano ZrO2 | 12.1 | 5.2 |
| Comparative example 6 | Nano CeO2 | 10.8 | 3.5 |
As can be seen from Table 3, the supported catalyst provided in example 1 of the present invention has substantially complete reaction of the raw materials at a reaction temperature of 170 ℃ for a reaction time of 17 hours. In contrast, the supported catalysts prepared by other carrier materials (comparative examples 4 to 6) have the conversion rate and yield not reaching 60 percent, and the best gas-phase SiO has2Also only 57.4% conversion, poor nano-ZrO2And nano CeO2Even less than 15%. It is demonstrated that the support materials used in the examples of the present invention are advantageous for increasing the catalytic activity.
Test example 4
The supported catalyst provided in example 1 was used to test its stability under repeated use, in the following manner:
s1, taking a 500ml four-neck flask, adding 540g of 2, 6-dichloropyridine and 5.4g of supported catalyst into the flask, installing a thermometer and stirring, starting chlorine introduction (the chlorine introduction rate is 3.125ml/h) after ensuring that the device is airtight, and reacting at the temperature of 170 ℃ for 17 h.
And S2, after the reaction is finished, collecting a liquid phase product while the product is hot, and analyzing the product by using a gas chromatography. The catalyst is recovered by centrifugal separation and is dried in a vacuum drying oven for 24 hours at 50 ℃.
S3, repeating the operations from S1 to S2 for 5 times, and comparing the changes of the yield and the conversion rate. The yield and conversion were calculated in the same manner as in test example 1, and the chromatographic conditions were the same as in test example 1. The test results are shown in FIG. 1.
As can be seen from fig. 1, after 5 times of cyclic reactions, the conversion rate of 2, 6-dichloropyridine in the supported catalyst provided in example 1 can still reach more than 95%, which indicates that the supported catalyst provided in the embodiment of the present invention has good stability.
In summary, embodiments of the present invention provide a supported catalyst, which is composed of a support material and a lewis acid catalyst. Wherein the carrier material is activated carbon; the lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride. The supported catalyst has a good catalytic effect on the chlorination reaction of 2, 6-dichloropyridine, and can efficiently obtain the 2,3, 6-trichloropyridine with high yield.
The embodiment of the invention also provides a preparation method of the supported catalyst, which comprises the steps of soaking the carrier material in the solution of the Lewis acid catalyst, drying, roasting and the like to obtain the supported catalyst. The method has simple operation and low requirement on equipment, and can conveniently and quickly prepare the supported catalyst.
The embodiment of the invention also provides a preparation method of the 2,3, 6-trichloropyridine, which comprises the step of mixing and reacting the 2, 6-dichloropyridine with chlorine under the catalysis of the supported catalyst. The method has the characteristics of high conversion rate, high yield and high product quality, and is suitable for being applied to large-scale industrial production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of 2,3, 6-trichloropyridine is characterized by comprising the following steps: under the catalysis of a supported catalyst, 2, 6-dichloropyridine is mixed with chlorine for reaction;
wherein the supported catalyst consists of a support material and a lewis acid catalyst;
wherein the carrier material is activated carbon; the Lewis acid catalyst is a mixture of ferric chloride, cuprous chloride and aluminum chloride;
in the Lewis acid catalyst, the molar ratio of ferric chloride to cuprous chloride to aluminum chloride is 6-8: 1-2: 1-2; the loading capacity of the Lewis acid catalyst is 1-8 mmol/g;
the preparation method of the supported catalyst comprises the following steps: dipping the carrier material into the solution of the Lewis acid catalyst to obtain a catalyst precursor;
and drying and roasting the catalyst precursor.
2. The method according to claim 1, wherein the solution of the Lewis acid catalyst is obtained by dissolving the Lewis acid catalyst in ethanol or dilute hydrochloric acid, and the concentration of the solution is 2 to 3 mmol/ml.
3. The preparation method according to claim 1, wherein the temperature for drying the catalyst precursor is 105 to 150 ℃ for 10 to 24 hours.
4. The preparation method according to claim 3, wherein the temperature for calcining the dried catalyst precursor is 300 to 550 ℃ for 3 to 10 hours.
5. The method according to claim 1, wherein the supported catalyst is used in an amount of 1 to 3 wt%.
6. The preparation method according to claim 1, wherein the reaction temperature is 170-190 ℃ and the reaction time is 3-17 h.
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