CN113244934B - Catalyst for producing 2,3,6-trichloropyridine and preparation method thereof - Google Patents
Catalyst for producing 2,3,6-trichloropyridine and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
Disclosed is a catalyst for producing 2,3,6-trichloropyridine and a preparation method thereof, wherein the catalyst comprises a catalytic active substance carried on a silica carrier, the catalytic active substance is selected from one or more of cobalt chloride, lanthanum chloride, barium chloride, ferric chloride, copper chloride, aluminum chloride and zinc chloride, and the catalyst is characterized in that the catalyst is prepared by the following method: a) Mixing silicate ester having the following general formula, the catalyst active material, inorganic acid and water to obtain a mixture; (R) 1 O)(R 2 O)(R 3 O)(R 4 O) Si, wherein R 1 、R 2 、R 3 、R 4 May be the same or different, each being an alkyl group having 1 to 4 carbon atoms; b) Stirring the mixture to obtain a gel; c) Drying the gel, and roasting at 350-500 ℃ in an inert atmosphere; the mixture comprises, by weight: 0.5-5% of a catalyst active substance; 20-50% of silicate ester; 0.1-10% of inorganic acid; the balance of water.
Description
Technical Field
The invention relates to the technical field of catalysis, and particularly relates to a catalyst for continuously producing 2,3,6-trichloropyridine and a preparation method thereof. The catalyst of the present invention has high material converting rate and high material selectivity.
Background
2,3,6-trichloropyridine is an important intermediate for chemical synthesis, and can be used to synthesize low-toxicity and high-efficiency pesticides such as insecticide and herbicide, especially 2,3-dichloropyridine as key raw material for chlorantraniliprole and cyantraniliprole.
The prior art provides a synthesis method of a plurality of 2,3,6-trichloropyridine. For example, chen Xi et al, "2,3,6-trichloropyridine synthesis" ("Fine petrochemical, third generation, 5.2000) discloses synthesis of 2,6-dichloropyridine by photochlorination starting from pyridine followed by synthesis of 2,3,6-trichloropyridine by electrophilic substitution (using Lewis acid catalysts). The electrophilic substitution reaction was carried out at 180-220 ℃ with a reaction yield of 93%. However, this method has problems of slow reaction rate, long reaction time and low product conversion.
Chinese patent CN107759512A provides a method for producing 2,3,6-trichloropyridine, which takes 2,6-dichloropyridine and chlorine as raw materials, 2,6-dichloropyridine gas and chlorine are mixed and then are introduced into a fixed bed reactor filled with an activated carbon supported catalyst, and 2,3,6-trichloropyridine is produced under the action of the activated carbon supported catalyst. The activated carbon supported catalyst adopts AlCl 3 、NiCl 2 、CuCl 2 、FeCl 3 、CaCl 2 、BaCl 2 、MgCl 2 、CoCl 2 And LaCl 2 One or more of the active components are active components, and active carbon is used as a carrier. Although this process can increase the conversion of 2,6-dichloropyridine to 98.3% and the selectivity of 2,3,6-trichloropyridine to 66.5%, the disadvantages are also very significant: firstly, the catalyst is easy to generate carbon deposition in the using process to cause the inactivation of the catalyst, and the inactivated catalyst can not be regenerated; and the conversion rate of 2,6-dichloropyridine and the selectivity of 2,3,6-trichloropyridine still have room for further improvement.
In order to overcome the defects of the activated carbon supported catalyst, chinese patent CN101768107A discloses a silica supported catalyst for producing polychlorinated pyridine by pyridine chlorination. The preparation method of the catalyst comprises the following steps:
(1) Mixing an aqueous solution of at least one of a transition metal salt and an alkaline earth metal salt with silica sol, and then drying and roasting the obtained mixture to prepare a catalyst precursor; and
(2) Contacting the catalyst precursor with chlorine gas under conditions such that at least a portion of the transition metal and alkaline earth metal are present as their chlorides in the product obtained after the contacting.
In example 1, a specific catalyst preparation method thereof comprises dropping an aqueous nitrate solution into silica sol, stirring for 6 hours to mix thoroughly, heating to 90 ℃ to remove moisture to obtain a paste with a water content of 10wt%, drying at 120 ℃ for 48 hours, calcining at 450 ℃ for 8 hours, and then chlorinating at 350 ℃ for 4 hours in a chlorine-nitrogen mixed gas to obtain a catalyst.
Silica sols are dispersions of nanoscale silica particles in water or a solvent. According to the method, a catalyst precursor is formed by drying and roasting silica sol, and the catalyst precursor is chloridized to form the silicon oxide supported metal salt chloride catalyst, so that the catalyst has long service life, and the defect that the active carbon-based catalyst is easy to carbonize and difficult to regenerate is overcome. The catalyst is mainly used for chlorination of pyridine to form tetrachloropyridine or pentachloropyridine, and has the main defects that high-temperature chlorination is needed, so that the cost is high, the conversion rate and the selectivity of the catalyst are not high when the catalyst is used for catalyzing 2,3-dichloropyridine to prepare 2,3,6-trichloropyridine, and the catalytic effect of the catalyst needs to be further improved.
Chinese patent CN112138663A discloses a preparation method of a catalyst for preparing chloropyridine, which comprises the following steps: soaking a carrier in an aqueous solution of an active ingredient precursor compound, and then drying and roasting the carrier in sequence to obtain a catalyst for preparing chloropyridine; the carrier is at least one of gear alumina, activated carbon, molecular sieve and silicon dioxide; the active ingredient precursor compound is FeCl 3 、CuCl 2 、CoCl 2 、ZnCl 2 、FeCl 2 、MnCl 2 、LaCl 3 、NiCl 2 、BiCl 3 、RuCl 3 And H 2 PtCl 6 At least one of (1). When alumina is used as a carrier and ferrous chloride is used as an active ingredient, the selectivity of 2,3,5-trichloropyridine is 40.1% when 2-chloropyridine is chlorinated. Tests show that when the catalyst formed by the impregnation method is used for the reaction of 2,6-dichloropyridine chlorination to form 2,3,6-trichloropyridine, the conversion rate and the selectivity of 2,3,6-trichloropyridine are not high, and the catalytic effect of the catalyst is to be further improved
Wang and others "basic principle, development and current application of sol-gel method" ("chemical industry and engineering" vol.26, no. 3, 2009, no. 5) describe the basic principle of gel-gel method. The article considers that "the preparation of sol is the key of the technology, the quality of sol directly affects the properties of the finally obtained material", which has been studied in recent years mainly from the following aspects: water addition, catalyst, sol concentration, hydrolysis temperature, etc. For the catalyst. This document mentions that: acid and alkali are used as catalysts, and the catalytic mechanisms of the acid and alkali are different, so that polycondensates with different structures and forms are generated by hydrolytic polycondensation of the same system.
There remains a need in the art to provide a highly efficient catalyst suitable for the vapor phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine, which can further improve the selectivity of the desired product. There is also a need to provide a method for preparing the catalyst.
Disclosure of Invention
Therefore, an object of the present invention is to provide a highly efficient catalyst suitable for the gas phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine, which can further improve the selectivity of the target product.
It is another object of the present invention to provide a method for preparing the catalyst.
Accordingly, one aspect of the present invention relates to a catalyst suitable for the gas phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine comprising a catalytically active material selected from the group consisting of cobalt chloride, lanthanum chloride, barium chloride, ferric chloride, copper chloride, aluminum chloride and zinc chloride supported on a silica support, characterized in that said catalyst is prepared by the following process:
a) Mixing silicate ester having the following general formula, the catalyst active material, inorganic acid and water to obtain a mixture;
(R 1 O)(R 2 O)(R 3 O)(R 4 O)Si
wherein R is 1 、R 2 、R 3 、R 4 May be the same or different, each being an alkyl group having 1 to 4 carbon atoms;
b) Stirring the mixture to obtain a gel;
c) Drying the gel, and roasting at 350-500 ℃ in an inert atmosphere;
the mixture comprises, by weight:
0.5-5% of a catalyst active substance;
20-50% of silicate ester;
0.1-10% of inorganic acid; and
the balance being water.
Another aspect of the invention relates to a process for the preparation of a catalyst suitable for the gas phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine, the catalyst comprising a catalytically active material selected from one or more of cobalt chloride, lanthanum chloride, barium chloride, ferric chloride, cupric chloride, aluminum chloride and zinc chloride supported on a silica support, the process comprising:
a) Mixing silicate ester having the following general formula, the catalyst active material, inorganic acid and water to obtain a mixture;
(R 1 O)(R 2 O)(R 3 O)(R 4 O)Si
wherein R is 1 、R 2 、R 3 、R 4 May be the same or different, each being an alkyl group having 1 to 4 carbon atoms;
b) Stirring the mixture to obtain a gel;
c) Drying the gel, and roasting at 350-500 ℃ in an inert atmosphere;
the mixture comprises, by weight:
0.5-5% of a catalyst active material;
20-50% of silicate ester;
0.1-10% of inorganic acid; and
the balance of water.
Detailed Description
The invention relates to a catalyst suitable for the gas-phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine, which comprises a catalytically active substance supported on a silica carrier.
Suitable for the inventionThe catalytically active material of the catalyst is not particularly limited and may be a conventional catalytically active material known in the art. In one embodiment of the invention, the catalytically active material is selected from one or more of cobalt chloride, lanthanum chloride, barium chloride, ferric chloride, cupric chloride and zinc chloride. In a preferred embodiment of the invention, the catalytically active material is selected from AlCl 3 、CoCl 2 、FeCl 3 One or more of (a).
In one embodiment of the invention, the catalytically active material is present in an amount of from 1 to 25%, preferably from 2 to 20%, more preferably from 3 to 18%, preferably from 4 to 15% by weight, based on the total weight of the catalyst.
In one embodiment of the invention, the silica support comprises 75 to 99%, preferably 80 to 98%, more preferably 82 to 97%, preferably 85 to 96%, by weight of the total catalyst.
The catalysts of the invention are prepared using as starting materials silicates having the general formula:
(R 1 O)(R 2 O)(R 3 O)(R 4 O)Si
wherein R is 1 、R 2 、R 3 、R 4 Which may be the same or different, are each an alkyl group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms.
In one embodiment of the invention, R is 1 、R 2 、R 3 、R 4 Which may be the same or different, are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.
In one embodiment of the present invention, ethyl silicate is preferably used as the silicate ester from the viewpoint of availability of raw materials and cost.
The preparation method of the catalyst comprises the step of mixing the silicate, the catalyst active substance, the inorganic acid and water to obtain a mixture.
The inorganic acid suitable for the process of the present invention is not particularly limited as long as it can catalyze the hydrolytic polycondensation reaction as a catalyst and does not adversely affect the final catalyst performance. In one embodiment of the present invention, hydrochloric acid is preferably used as the inorganic acid from the viewpoint of avoiding the contamination element contained in the final catalyst.
The concentration of the inorganic acid to be used is not particularly limited and may be any suitable conventional concentration as long as it does not adversely affect the formation of a gel and does not adversely affect the catalytic performance of the final catalyst. One of ordinary skill in the art, after reading this disclosure, can readily determine an appropriate concentration of the mineral acid.
The mixing step suitable for the method of the present invention is not particularly limited and may be a conventional mixing step known in the art. For example, an aqueous solution of the catalyst active material may be formed and then mixed with hydrochloric acid, silicate and the balance water, if desired.
The raw materials are mixed in such amounts by weight that the resulting mixture comprises:
0.5-5%, preferably 1-4.5%, more preferably 1.5-4%, preferably 2-3.5% of a catalyst active substance;
20-50%, preferably 22-48%, more preferably 25-45%, preferably 28-42% of silicate ester;
0.1-5%, preferably 0.5-4%, more preferably 0.8-3.5%, preferably 1.2-3% of an inorganic acid; and
the balance of water.
The preparation method of the catalyst comprises the step of stirring the mixture to obtain gel.
In the present invention, a method of stirring the mixture and forming a gel is not particularly limited, and may be a method commonly used in the art for preparing silica by a sol-gel method.
In one embodiment of the invention, the process of the invention comprises stirring the mixture at a temperature of from 30 to 50 deg.C, preferably from 32 to 48 deg.C, more preferably from 35 to 45 deg.C, preferably from 38 to 42 deg.C, for a period of from 5 to 12 hours, more preferably from 6 to 11 hours, more preferably from 7 to 10 hours, preferably from 8 to 9 hours to obtain a gel.
The preparation method of the catalyst also comprises the steps of drying the gel and roasting at the temperature of 350-500 ℃ in an inert atmosphere.
The drying method of the gel is not particularly limited, and may be a conventional drying method known in the art, for example, wang, etc., natural drying in an atmospheric atmosphere, supercritical fluid drying, freeze drying, microwave drying, etc., as mentioned in "basic principle, development and application status of sol-gel method" ("chemical industry and engineering, vol.26, no. 3, month 5 2009). In one embodiment of the invention, the gel obtained is dried at a temperature of 60 to 130℃, preferably 65 to 120℃, more preferably 70 to 110℃, for a period of 1 to 80 hours, preferably 2 to 75 hours, more preferably 3 to 60 hours.
In one embodiment of the invention, a two-step drying process is used: drying at 60-90 deg.C, preferably 65-85 deg.C, more preferably 70-80 deg.C, at low temperature for 1-10 hr, preferably 2-8 hr, more preferably 3-7 hr; followed by drying at a high temperature of 100-130 deg.C, preferably 105-120 deg.C, more preferably 108-110 deg.C, for 1-70 hours, preferably 2-65 hours, more preferably 3-50 hours.
The method suitable for firing the dried gel is not particularly limited, and may be a conventional firing method known in the art. In one embodiment of the invention, the dried gel is calcined under an inert atmosphere at a temperature of 350 to 500 deg.C, preferably 380 to 450 deg.C, preferably 400 to 420 deg.C, for 2 to 10 hours, preferably 3 to 8 hours, more preferably 4 to 6 hours.
The inert atmosphere suitable for gel firing is not particularly limited, and may be a conventional inert atmosphere known in the art. From the viewpoint of cost, nitrogen is preferably used.
In one embodiment of the invention, the catalyst is prepared by a process comprising reacting tetraethoxysilane, catalytically active material, hydrochloric acid and C in the amounts previously described 1 -C 3 An alkanol (e.g., absolute ethanol) is added to the reaction vessel at once and stirred. Slowly dripping deionized water into the solution, forming a gel state at 30-50 ℃ after sol is formed, drying the prepared gel in a 70-90 ℃ oven for 10-15 hours, and then roasting for 3-6 hours at 350-450 ℃ in a nitrogen atmosphere. The catalyst is suitable for gas phase chlorination of 2,6-dichloropyridine to generate 2,3,6-trichloropyridine. In one embodiment of the invention, 2,3,6-trichloropyridine is prepared using a fixed bed continuous reaction process: first of all catalyzeTabletting and crushing the agent into particles of 40-60 meshes, then filling 0.4-2g of catalyst into a tubular reactor, and filling the rest with quartz sand of 40-60 meshes. After the reaction tube is placed into a reaction furnace to be fixed and the whole device is subjected to leakage detection, the reaction temperature is controlled to be 250-400 ℃, and the gas flow rate is controlled to be 200-400h -1 Under normal pressure, 2,3-dichloropyridine is fed into a gasification furnace to be gasified (namely, reaction raw materials are gas), and then is mixed with chlorine and is fed into a reactor to react, the volume ratio of the reaction raw materials to the chlorine is 1:1-1:4, reaction gas flows into a liquid storage tank after being condensed and gas-liquid separated after passing through a bed layer, and liquid in the tank is taken out at intervals and analyzed.
In one embodiment of the invention, the catalyst is prepared from AlCl 3 、CoCl 2 、FeCl 3 One or more of the active ingredients are used as active ingredients, silicon dioxide is used as a carrier, and the mass content of the active ingredients is 5-30%. Dissolving a chloride precursor and tetraethoxysilane in water, adding a certain amount of hydrochloric acid, stirring to form gel, and finally drying and roasting to obtain the catalyst.
Examples
The following examples are presented to aid in further understanding of the invention, and are not intended to limit the scope of the invention.
Catalytic performance test method
Firstly, tabletting the catalyst and crushing the catalyst into particles of 40-60 meshes, then loading a certain amount of catalyst into a tubular reactor according to the requirements of each test, filling the rest part with quartz sand of 40-60 meshes, and calculating the proportion of the catalyst (namely the load amount by weight). After the reaction tube is placed into a reaction furnace to be fixed and the whole device is subjected to leak detection, the reaction temperature is controlled to be about 300 ℃, and the gas flow rate is controlled to be 300h -1 And (2) about, introducing 2,3-dichloropyridine into a gasification furnace under normal pressure for gasification, mixing with chlorine, introducing into a reactor for reaction, wherein the volume ratio of the two is about 1:4, condensing the reaction gas after passing through a bed layer, separating gas from liquid, flowing into a liquid storage tank, taking out the liquid in the tank at intervals, and analyzing.
The conversion and selectivity were calculated using the following formula:
2,6-dichloropyridine conversion
Wherein n is in Is the molar concentration of 2,6-dichloropyridine at the inlet of the reactor, n out Is the molar concentration of 2,6-dichloropyridine at the reactor outlet.
2,6-dichloropyridine Selectivity
Wherein m is out Is 2,3,6-trichloropyridine outlet molar concentration.
Example 1
Preparation of 8wt% FeCl by the Sol-gel method 3 -SiO 2 Carrier
34.8g of tetraethoxysilane, 2.320g of ferric chloride, 1ml of hydrochloric acid having a concentration of 37wt% and 20ml of absolute ethanol were added in one portion to a 250ml beaker and stirred. 69.6ml of deionized water is slowly dropped into the solution, a gel state is formed at 40 ℃ after sol is formed, the prepared gel is dried in an oven at 80 ℃ for 12 hours, and then the obtained gel is roasted for 4 hours at 400 ℃ under a nitrogen atmosphere.
The catalyst performance was tested by the above method and the results are shown in table 1 below.
Example 2
Preparation of 5wt% CoCl by the Sol-gel method 2 -SiO 2 Carrier
34.8g of ethyl orthosilicate, 1.767g of cobalt chloride, 1ml of hydrochloric acid with a concentration of 37wt% and 20ml of absolute ethanol were added in one portion to a 250ml beaker and stirred. 69.6ml of ionized water is slowly dropped into the solution, a gel state is formed at 40 ℃ after sol is formed, the prepared gel is dried in an oven at 80 ℃ for 12 hours, and then the obtained product is roasted for 4 hours in a nitrogen atmosphere at 400 ℃.
The catalyst performance was tested by the above method and the results are shown in table 1 below.
Example 3
Preparation of 5wt% FeCl by the Sol-gel method 3 -5wt％CoCl 2 -SiO 2 Carrier
34.8g of tetraethoxysilane, 1.450g of ferric chloride, 1.104g of cobalt chloride, 1ml of hydrochloric acid having a concentration of 37% by weight and 20ml of absolute ethanol were added in one portion to a 250ml beaker and stirred. 69.6ml of deionized water is slowly dropped into the solution, a gel state is formed at 40 ℃ after sol is formed, the prepared gel is dried in an oven at 80 ℃ for 12 hours, and then the obtained gel is roasted for 4 hours at 400 ℃ under a nitrogen atmosphere.
The catalyst performance was tested by the above method and the results are shown in table 1 below.
Example 4
Preparation of 5wt% FeCl by the Sol-gel method 3 -5wt％AlCl 3 -SiO 2 Carrier
34.8g of tetraethoxysilane, 1.450g of ferric chloride, 2.475g of aluminum chloride, 1ml of hydrochloric acid having a concentration of 37% by weight and 20ml of absolute ethanol were added in one portion to a 250ml beaker and stirred. 69.6ml of deionized water is slowly dropped into the solution, a gel state is formed at 40 ℃ after sol is formed, the prepared gel is dried in an oven at 80 ℃ for 12 hours, and then the obtained gel is roasted for 4 hours at 400 ℃ under a nitrogen atmosphere.
The catalyst performance was tested by the above method and the results are shown in table 1 below.
Example 5
Preparation of 4wt% FeCl by the Sol-gel method 3 -3wt％CoCl 2 -3wt％AlCl 3 -SiO 2 Carrier
34.8g of tetraethoxysilane, 1.160g of ferric chloride, 0.662g of cobalt chloride, 1.485g of aluminum chloride, 1ml of hydrochloric acid with the concentration of 37wt% and 20ml of absolute ethyl alcohol were added to a 250ml beaker in one portion and stirred. 69.6ml of deionized water is slowly dropped into the solution, a gel state is formed at 40 ℃ after sol is formed, the prepared gel is dried in an oven at 80 ℃ for 12 hours, and then the obtained gel is roasted for 4 hours at 400 ℃ under a nitrogen atmosphere.
The catalyst performance was tested by the above method and the results are shown in table 1 below.
TABLE 1 catalyst Performance
Comparative example 1
A catalyst was prepared in the same manner as in example 1, except that the active ingredient was introduced by an impregnation method
Adding tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol which are the same in amount as those in example 1 into a 250ml beaker at one time, slowly dropwise adding deionized water which is the same in amount as that in example 1 into the solution, forming a gel state at 40 ℃ after sol is formed, drying the prepared gel in an oven at 80 ℃ for 12 hours, and then roasting the dried gel in a nitrogen atmosphere at 400 ℃ for 4 hours to obtain the silica carrier.
FeCl was added in the same amount as in example 1 by an equal volume impregnation method 3 Loading on silicon oxide carrier, drying at 80 deg.C, and calcining at 400 deg.C in nitrogen atmosphere.
The catalyst performance was tested by the above method and the results are shown in Table 2 below.
Comparative examples 2 to 4
Catalysts were formed by the impregnation method using the method of comparative example 1 in accordance with the amounts of the components of examples 2 to 4, respectively. The catalyst performance was tested and the results are shown in Table 2 below
Table 2: catalyst Performance
Comparative example 6
The catalyst was prepared in the amount of example 1 using CN101768107A, example 1
2.320g of ferric nitrate is dissolved in 20ml of deionized water, after the ferric nitrate is fully dissolved, the ferric nitrate is gradually dripped into 34.4g of tetraethyl silicate under the conditions of room temperature and stirring, and the stirring is continued for 6 hours after the dripping is finished, so that a fully dispersed mixed solution is obtained. Then, the mixture was warmed to 90 ℃ with stirring, and the water in the mixed solution was evaporated at this temperature until the mixture became pasty (water content 10% by weight), and then the pasty mixture was dried in a drying oven at 120 ℃ for 48 hours. Thereafter, the dried mixture was placed in a heating furnace and calcined at 450 ℃ for 8 hours, thereby obtaining a catalyst precursor.
The catalyst precursor was loaded into a fixed bed reactor, the inside diameter of the column of which was 32 mm and the length of which was 1200 mm. The reactor was heated to 350 ℃ by heating, and then the introduction of a mixed gas of chlorine gas and nitrogen gas (the volume of chlorine gas was 60% of the total volume of the mixed gas) into the reactor was started, and the mixed gas was introduced at a flow rate of 1000 ml/min for 4 hours, to thereby prepare a supported catalyst.
The performance of the catalyst tested by the method provided by the invention has the result that the conversion rate of 2,6-dichloropyridine is 85.1%, and the selectivity is 67.3%.
Claims (29)
1. A catalyst suitable for gas-phase chlorination of 2,6-dichloropyridine to 2,3,6-trichloropyridine comprises a catalytically active material selected from one or more of cobalt chloride, lanthanum chloride, barium chloride, ferric chloride, aluminum chloride and zinc chloride supported on a silica carrier,
the method is characterized in that the catalyst is prepared by the following method:
a) Mixing silicate ester having the following general formula, the catalyst active material, inorganic acid and water to obtain a mixture;
(R 1 O)(R 2 O)(R 3 O)(R 4 O)Si
wherein R is 1 、R 2 、R 3 、R 4 May be the same or different, each being an alkyl group having 1 to 4 carbon atoms;
b) Stirring the mixture to obtain a gel;
c) Drying the gel, and roasting at 350-500 ℃ in an inert atmosphere;
the mixture comprises, by weight: 0.5-5% of a catalyst active substance; 20-50% of silicate ester; 0.1-10% of inorganic acid; and the balance water.
2. The catalyst of claim 1 wherein the catalytically active material comprises from 1 to 25% and the silica support comprises from 75 to 99% by weight of the total catalyst.
3. The catalyst of claim 1 wherein the catalytically active material comprises from 2 to 20 percent and the silica support comprises from 80 to 98 percent, based on the total weight of the catalyst.
4. The catalyst of claim 1 wherein the catalytically active material comprises from 3 to 18 percent and the silica support comprises from 82 to 97 percent, based on the total weight of the catalyst.
5. The catalyst of claim 1 wherein the catalytically active material comprises from 4 to 15% and the silica support comprises from 85 to 96% by weight of the total catalyst.
6. The catalyst of claim 1, wherein in the silicate, R is 1 、R 2 、R 3 、R 4 Which may be the same or different, are each an alkyl group having 1 to 3 carbon atoms, and the mineral acid includes hydrochloric acid.
7. The catalyst of claim 1, wherein in the silicate, R is 1 、R 2 、R 3 、R 4 Which may be the same or different, are each an alkyl group having 1 to 2 carbon atoms, and the mineral acid includes hydrochloric acid.
8. The catalyst of claim 1, wherein the silicate is ethyl silicate; the inorganic acid comprises hydrochloric acid.
9. The catalyst of any one of claims 1 to 8, wherein the mixture comprises: 1-4.5% of a catalyst active material; 22-48% of silicate ester; 0.5-4% of inorganic acid; and the balance water.
10. The catalyst of any one of claims 1 to 8, wherein the mixture comprises: 1.5-4% of a catalyst active material; 25-45% of silicate ester; 0.8-3.5% of inorganic acid; and the balance water.
11. The catalyst of any one of claims 1-8, wherein the mixture comprises: 2-3.5% of a catalyst active substance; 28-42% of silicate ester; 1.2-3% of inorganic acid; and the balance water.
12. The catalyst of any one of claims 1 to 8, wherein the mixture is stirred at a temperature of 30 to 50 ℃ for 5 to 12 hours to obtain a gel;
drying the obtained gel at 60-130 deg.C for 1-80 hr.
13. The catalyst of any one of claims 1 to 8, wherein the mixture is stirred at a temperature of 32 to 48 ℃ for 6 to 11 hours to obtain a gel;
drying the obtained gel at 65-120 deg.C for 2-75 hr.
14. The catalyst of any one of claims 1 to 8, wherein the mixture is stirred at a temperature of 35 to 45 ℃ for 7 to 10 hours to obtain a gel;
drying the obtained gel at 70-110 deg.C for 3-60 hr.
15. The catalyst of any one of claims 1 to 8, wherein the mixture is stirred at a temperature of 38 to 42 ℃ for 8 to 9 hours to obtain a gel;
drying the obtained gel at 70-110 deg.C for 3-60 hr.
16. The catalyst of any one of claims 1 to 8, wherein the dried gel is calcined at a temperature of 350 to 500 ℃ for 2 to 10 hours under an inert atmosphere.
17. The catalyst of any one of claims 1 to 8, wherein the dried gel is calcined at a temperature of 380 to 450 ℃ for 3 to 8 hours under an inert atmosphere.
18. The catalyst of any one of claims 1 to 8, wherein the dried gel is calcined at a temperature of 400 to 420 ℃ for 4 to 6 hours under an inert atmosphere.
19. A method of preparing the catalyst of any one of claims 1-18, the method comprising:
a) Mixing silicate ester having the following general formula, the catalyst active material, inorganic acid and water to obtain a mixture;
(R 1 O)(R 2 O)(R 3 O)(R 4 O)Si
wherein R is 1 、R 2 、R 3 、R 4 May be the same or different, each being an alkyl group having 1 to 4 carbon atoms;
b) Stirring the mixture to obtain a gel;
c) Drying the gel, and roasting at 350-500 ℃ in an inert atmosphere;
the mixture comprises, by weight: 0.5-5% of a catalyst active substance; 20-50% of silicate ester; 0.1-10% of inorganic acid; and the balance water.
20. The method of claim 19, wherein the mixture comprises: 1-4.5% of a catalyst active material; 22-48% of silicate ester; 0.5-4% of inorganic acid; and the balance water.
21. The method of claim 19, wherein the mixture comprises: 1.5-4% of a catalyst active material; 25-45% of silicate ester; 0.8-3.5% of inorganic acid; and the balance water.
22. The method of claim 19, wherein the mixture comprises: 2-3.5% of a catalyst active material; 28-42% of silicate ester; 1.2-3% of inorganic acid; and the balance water.
23. The method of any one of claims 19 to 22, wherein the mixture is stirred at a temperature of 30 to 50 ℃ for 5 to 12 hours to obtain a gel;
drying the obtained gel at 60-130 deg.C for 1-80 hr.
24. The method of any one of claims 19 to 22, wherein the mixture is stirred at a temperature of 32 to 48 ℃ for 6 to 11 hours to obtain a gel;
drying the obtained gel at 65-120 deg.C for 2-75 hr.
25. The method of any one of claims 19 to 22, wherein the mixture is stirred at a temperature of 35 to 45 ℃ for 7 to 10 hours to obtain a gel;
drying the obtained gel at 70-110 deg.C for 3-60 hr.
26. The method of any one of claims 19 to 22, wherein the mixture is stirred at a temperature of 38 to 42 ℃ for 8 to 9 hours to obtain a gel;
drying the obtained gel at 70-110 deg.C for 3-60 hr.
27. The method of any one of claims 19 to 22, wherein the dried gel is calcined at a temperature of 350 to 500 ℃ for 2 to 10 hours under an inert atmosphere.
28. The method of any one of claims 19 to 22, wherein the dried gel is calcined at a temperature of 380 to 450 ℃ for 3 to 8 hours under an inert atmosphere.
29. The method of any one of claims 19-22, wherein the dried gel is calcined at a temperature of 400-420 ℃ for 4-6 hours under an inert atmosphere.
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