CN114849757B - Immobilized catalyst, preparation method, use method and application - Google Patents

Immobilized catalyst, preparation method, use method and application Download PDF

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CN114849757B
CN114849757B CN202210560850.1A CN202210560850A CN114849757B CN 114849757 B CN114849757 B CN 114849757B CN 202210560850 A CN202210560850 A CN 202210560850A CN 114849757 B CN114849757 B CN 114849757B
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catalyst
mesoporous
boiling
aza
alcl
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CN114849757A (en
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李兵兵
雷宏
柳青媛
谢建伟
郑云峰
胡家啟
展喜兵
陈道伟
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ZHEJIANG KAIHUA SYNTHETIC MATERIAL CO Ltd
Quzhou University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a solid-supported catalyst, a preparation method, a use method and application thereof, and belongs to the technical field of catalysts. A solid-supported catalyst takes mesoporous aza-carbon material as a carrier, and AlCl is supported on the carrier 3 And a cocatalyst. The application of the immobilized catalyst as an organosilicon high-boiling-point substance cracking catalyst. The preparation method of the immobilized catalyst comprises the following steps: p1, alCl 3 And the cocatalyst are fully dissolved in absolute ethyl alcohol to prepare a solution; p2, slowly pouring the solution into the fully dried mesoporous aza-carbon material, continuously stirring and impregnating; and P3, drying the mesoporous aza-carbon material immersed in the step P2 to obtain the catalyst immobilized on the mesoporous aza-carbon material. The catalyst can be used as a catalyst for preparing the dimethyl dichlorosilane by cracking the organosilicon high-boiling-point substances, the reaction condition is mild, the reaction is not required to be carried out under the conditions of high temperature and high pressure, the organosilicon high-boiling-point substances can be cracked to obtain a better conversion rate, and the dimethyl dichlorosilane can obtain a better yield.

Description

Immobilized catalyst, preparation method, use method and application
Technical Field
The invention relates to the technical field of catalysts, in particular to an immobilized catalyst, a preparation method, a use method and application.
Background
The organosilicon high-boiling-point substances have high corrosiveness and inflammability, have few application in organosilicon industry chains, have little industrial value, and are one of the focuses of attention of various macromer manufacturers along with the rapid expansion of organosilicon productivity in China and the improvement of national environmental protection requirements.
The catalytic cracking method is an effective high-boiling-point substance treatment mode, and a series of catalysts with different performances and operating conditions, such as Lewis acid, organic amine, palladium-phosphorus coordination compound, molecular sieve and the like, are developed in the market at present, wherein AlCl 3 Is an extremely effective cracking catalyst for the organosilicon high-boiling-point substances.
US5629438 discloses the use of AlCl in a pneumatically stirred autoclave 3 As a catalyst, the reaction temperature is 325 ℃, the pressure is 4-7 MPa, the high-boiling-point substance, trimethylchlorosilane and hydrogen chloride are reacted to prepare silane monomers, the conversion rate of the high-boiling-point substance reaches 81.2%, the yield of the dimethyldichlorosilane monomers is 70.3%, but the method for improving the yield of the dimethyldichlorosilane by adopting trimethylchlorosilane is economically unreasonable.
EP 0634418B 1 AlCl 3 Loading on activated carbon, silicon dioxide or alumina, reacting high-boiling substance with hydrogen chloride at 500 deg.C and normal pressure in a packed tower or fluidized bed reactor to obtain single pass yield of methyltrichlorosilane and dimethyldichlorosilane of 39%, wherein dimethyldichlorosilane accounts for about 37.5%, and the high-boiling substance is crackedThe reaction temperature is high, and the yield of the dimethyldichlorosilane is low.
AlCl reported at present 3 The catalytic organosilicon high-boiling-point substance cracking process mainly has the following defects:
1)AlCl 3 the activity is low, sublimation (about 180 ℃ under normal pressure) is easy to lose, a pipeline valve is blocked, the operation is required to be carried out at high temperature and high pressure, the process condition is harsh, and the energy consumption is high;
2) The yield of dimethyldichlorosilane is low.
Aiming at the technical problems, the invention aims to develop a catalyst with high activity, high stability and high selectivity for cracking organic silicon high-boiling-point substances.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems existing in the prior art, the invention aims to provide a solid-supported catalyst, a preparation method, a use method and an application thereof, wherein the catalyst provided by the invention is used as a catalyst for preparing dimethyl dichlorosilane by cracking an organosilicon high-boiling-point substance, the reaction condition is mild, the reaction is not required to be carried out under the conditions of high temperature and high pressure, the organosilicon high-boiling-point substance can be cracked to obtain a better conversion rate, and the dimethyl dichlorosilane can obtain a better yield.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A solid-supported catalyst takes mesoporous aza-carbon material as a carrier, and AlCl is supported on the carrier 3 And a cocatalyst.
Further, the cocatalyst is selected from one or more of europium chloride, lanthanum chloride and cerium chloride.
Further, alCl 3 And the mass ratio of the cocatalyst is 3-15:1; alCl 3 And mesoporous aza-carbon in a mass ratio of 6-30:100.
Further, alCl 3 And the mass ratio of the cocatalyst was 10:1.
The application of the immobilized catalyst as an organosilicon high-boiling-point substance cracking catalyst.
The preparation method of the immobilized catalyst comprises the following steps:
p1, alCl 3 And the cocatalyst are fully dissolved in absolute ethyl alcohol to prepare a solution;
p2, slowly pouring the solution into the fully dried mesoporous aza-carbon material, continuously stirring and impregnating;
and P3, drying the mesoporous aza-carbon material immersed in the step P2 to obtain the catalyst immobilized on the mesoporous aza-carbon material.
The application method of the immobilized catalyst comprises the following steps:
s1, carrying out reduced pressure distillation on an organosilicon high-boiling-point substance to remove solid impurities, thereby obtaining a pretreated high-boiling-point substance;
s2, adding the organic silicon high-boiling residues subjected to impurity removal into a cracking reactor, and then adding the immobilized catalyst;
s3, introducing hydrogen chloride gas into the reaction liquid in the cracking reactor, heating to a certain temperature, and reacting under normal pressure to obtain a mixed product mainly comprising dimethyl dichlorosilane;
s4, recycling the mixed product mainly comprising the dimethyldichlorosilane through a post-treatment process.
Further, the mass ratio of the organosilicon high-boiling-point substance to the catalyst is 100-500:1.
Further, the molar ratio of the organosilicon high-boiling-point substance to the hydrogen chloride is 1:1-5.
Further, the reaction temperature is 60-150 ℃, the reaction pressure is normal pressure, and the reaction time is 3-9h.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) The solid supported catalyst provided by the invention is prepared by mixing AlCl 3 And a cocatalyst is fixedly supported on the mesoporous aza-carbon material, and nitrogen atoms and rich pore channel structures on the surface of the mesoporous aza-carbon material can play a role in dispersing and stabilizing AlCl 3 Active center effect, alCl inhibition 3 Improves activity and selectivity; addition of promoter further stabilizes AlCl 3 And extend the life thereof.
(2) The immobilized catalyst provided by the invention is applied to the reaction of cracking the organic silicon high-boiling-point substances, so that the cracking reaction condition of the organic silicon high-boiling-point substances is mild, the yield of the dimethyl dichlorosilane is high, the conversion rate of the organic silicon high-boiling-point substances can reach more than 95%, and the yield of the dimethyl dichlorosilane can reach more than 80%, and the immobilized catalyst is suitable for industrial application.
(3) The supported catalyst provided by the invention can be repeatedly recycled, the yield of the dimethyl dichlorosilane can reach 76.3% after being recycled for 10 times, the supported catalyst is relatively stable, the supported catalyst can be repeatedly recycled, further, the resource waste can be reduced, the environment is protected, the cost is saved, and the supported catalyst is suitable for industrial application.
(4) The catalyst provided by the invention is applied to the reaction of cracking the organosilicon high-boiling-point substances, the reaction condition of cracking the organosilicon high-boiling-point substances is mild, and the yield of the dimethyldichlorosilane is high.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Examples 1-7 are methods of preparing catalysts of different concentrations, comprising the steps of: p1, alCl 3 And the cocatalyst are fully dissolved in absolute ethyl alcohol to prepare a solution; p2, slowly pouring the solution into the fully dried mesoporous aza-carbon material, continuously stirring and impregnating; and P3, drying the mesoporous aza-carbon material immersed in the step P2 to obtain the catalyst immobilized on the mesoporous aza-carbon material.
Examples 8-14 are experiments for catalytically cracking high-boiling organosilicon compounds using the catalysts prepared in examples 1-7, comprising the following steps: s1, carrying out reduced pressure distillation on an organosilicon high-boiling-point substance to remove solid impurities, thereby obtaining a pretreated high-boiling-point substance; s2, adding the organic silicon high-boiling residues subjected to impurity removal into a cracking reactor, and then adding the immobilized catalyst; s3, introducing hydrogen chloride gas into the reaction liquid in the cracking reactor, heating to a certain temperature, and reacting under normal pressure to obtain a mixed product mainly comprising dimethyl dichlorosilane; s4, recycling the mixed product mainly comprising the dimethyldichlorosilane through a post-treatment process.
Example 15 is a catalyst recycling performance test, in which the catalyst having the best catalytic performance was recovered, and the recycling performance was tested under the same reaction conditions as in example 8.
Example 1
0.6g AlCl 3 And 0.06g of cerium chloride is dissolved in 20ml of absolute ethyl alcohol to prepare an impregnating solution, the impregnating solution is slowly poured into 10g of mesoporous aza-carbon carrier which is fully dried, the impregnating solution is continuously stirred, the impregnating solution is impregnated for 2 hours at room temperature, the ethanol is slowly evaporated in a water bath, then the impregnated solution is placed in an oven for drying at 60 ℃ for standby, and the catalyst is marked as aluminum trichloride-cerium chloride/mesoporous aza-carbon (6:0.6:100).
Example 2
An immobilized catalyst was prepared by the same procedure as in example 1, except that the impregnation solution was slowly poured into 3.33g of the mesoporous azacarbon support which was sufficiently dried, and the catalyst was labeled as aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100).
Example 3
An immobilized catalyst was prepared by the same procedure as in example 1, except that the impregnation solution was slowly poured into 2g of the mesoporous azacarbon support which was sufficiently dried, and the catalyst was labeled as aluminum trichloride-cerium chloride/mesoporous azacarbon (30:3:100).
Example 4
An immobilized catalyst was prepared by the same procedure as in example 1, except that 0.6g of AlCl was used 3 And 0.2g of cerium chloride was dissolved in absolute ethanol to prepare an impregnation solution, which was slowly poured into 3.33g of a mesoporous azacarbon support which was sufficiently dried, and the catalyst was labeled as aluminum trichloride-cerium chloride/mesoporous azacarbon (18:6:100).
Example 5
An immobilized catalyst was prepared by the same procedure as in example 1, except that 0.6g of AlCl was used 3 And 0.04g of cerium chloride are dissolved in deionized water to prepare an impregnating solution, and 3.3g of mesoporous aza after being fully dried is slowly poured into the impregnating solutionIn the carbon support, the catalyst was labeled as aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.2:100).
Example 6
An immobilized catalyst was prepared by the same procedure as in example 1, except that 0.6g of AlCl was used 3 And 0.06g of lanthanum chloride was dissolved in absolute ethanol to prepare an impregnation solution, which was slowly poured into 3.3g of mesoporous azacarbon carrier which was sufficiently dried, and the catalyst was labeled as aluminum trichloride-lanthanum chloride/mesoporous azacarbon (18:1.8:100).
Example 7
A catalyst was prepared by the same procedure as in example 1, except that 0.6g AlCl was added 3 And 0.06g of europium chloride are dissolved in absolute ethyl alcohol to prepare an impregnating solution, the impregnating solution is slowly poured into 3.3g of mesoporous aza-carbon carrier which is fully dried, and the catalyst is marked as aluminum trichloride-europium chloride/mesoporous aza-carbon (18:1.8:100).
Example 8
Catalyst Activity test
And (3) carrying out reduced pressure distillation on the organosilicon high-boiling-point substances to remove solid impurities, thereby obtaining the pretreated high-boiling-point substances. Adding the organic silicon high-boiling residue after impurity removal into a cracking reactor, adding a solid-supported catalyst, and introducing hydrogen chloride gas into the reaction solution, wherein the reaction conditions are as follows: the mass ratio of the organic silicon high-boiling-point substance to the catalyst is 100:1, the molar ratio of the organic silicon high-boiling-point substance to the hydrogen chloride is 1:3, the reaction temperature is 100 ℃, the reaction time is 6 hours, and the reaction pressure is normal pressure. The reaction produces a mixed product mainly comprising dimethyldichlorosilane, and the mixed product is recovered through a post-treatment process. The catalytic activity data are shown in Table 1.
Table 1:
solid-supported catalyst Cleavage conversion (%) Yield of Dichlorosilane (%)
Aluminum trichloride-cerium chloride/mesoporous azacarbon (6:0.6:100) 75.5 60.4
Aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) 90.2 80.6
Aluminum trichloride-cerium chloride/mesoporous azacarbon (30:3:100) 91.9 73.8
Aluminum trichloride-cerium chloride/mesoporous azacarbon (18:6:100) 71.3 56.5
Aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.2:100) 90.2 75.4
Aluminum trichloride-lanthanum chloride/mesoporous azacarbon (18:1.8:100) 78.6 66.2
Aluminum trichloride-europium chloride/mesoporous azacarbon (18:1.8:100) 80.1 68.3
Example 9
Catalyst activity tests were carried out by using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst and adopting the same operation as in example 8, except that the mass ratio of the organosilicon high-boiling substances to the catalyst was 300:1 and the catalytic activity data are shown in Table 2.
Example 10
The catalyst activity test was performed by using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst, and the same procedure as in example 8 was adopted, except that the mass ratio of the organosilicon high-boiling substance to the catalyst was 500:1 and the catalytic activity data are shown in Table 2.
Example 11
Catalyst activity tests were carried out in the same manner as in example 8, except that the molar ratio of the organosilicon high-boiling substance to hydrogen chloride was 1:1, using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst, and the catalytic activity data are shown in Table 2.
Example 12
Catalyst activity tests were carried out in the same manner as in example 8, except that the molar ratio of the organosilicon high-boiling substance to hydrogen chloride was 1:5, using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst, and the catalytic activity data are shown in Table 2.
Example 13
Catalyst activity tests were carried out in the same manner as in example 8, except that the reaction temperature was 60℃and the reaction time was 3 hours, using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst, and the catalytic activity data were shown in Table 2.
Example 14
Catalyst activity tests were carried out in the same manner as in example 8, except that the reaction temperature was 150℃and the reaction time was 9 hours, using aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) as a catalyst, and the catalytic activity data were shown in Table 2.
Table 2:
Figure BDA0003656515230000071
example 15
Catalyst cycle performance test
The aluminum trichloride-cerium chloride/mesoporous azacarbon (18:1.8:100) catalyst with the best catalytic performance is recovered, and the recycling performance of the catalyst is tested. Under the same reaction conditions as in example 8, after recycling for 10 times, the degradation conversion rate of the high boiling substance was 86.8%, and the yield of dimethyldichlorosilane was 76.3%.
From tables 1 and 2 and the catalyst recycling performance test, the aluminum trichloride-cerium chloride/mesoporous aza-carbon catalyst prepared by the invention has the advantages of high activity and selectivity, long service life and easy recovery; under the action of the catalyst provided by the invention, the reaction conditions are mild, the reaction is carried out under normal pressure, the reaction is not required to be carried out under the conditions of high temperature and high pressure, the high-boiling-point organosilicon material can be cracked to obtain a better conversion rate, and the dimethyl dichlorosilane can obtain a better yield.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (8)

1. An immobilized catalyst, characterized in that: the catalyst takes mesoporous aza-carbon material as a carrier, and the carrier is loaded with AlCl 3 And a cocatalyst;
the promoter is selected from one or more of europium chloride, lanthanum chloride and cerium chloride;
AlCl 3 and the mass ratio of the cocatalyst is 3-15:1; alCl 3 And mesoporous aza-carbon in a mass ratio of 6-30:100.
2. An immobilized catalyst according to claim 1, characterized in that: alCl 3 And the mass ratio of the cocatalyst was 10:1.
3. Use of the supported catalyst according to any one of claims 1-2 as a cracking catalyst for high boilers of silicones.
4. The method for preparing the supported catalyst according to any one of claims 1 to 2, wherein: the preparation method comprises the following steps:
p1, alCl 3 And the cocatalyst are fully dissolved in absolute ethyl alcohol to prepare a solution;
p2, slowly pouring the solution into the fully dried mesoporous aza-carbon material, continuously stirring and impregnating;
and P3, drying the mesoporous aza-carbon material immersed in the step P2 to obtain the catalyst immobilized on the mesoporous aza-carbon material.
5. The method of using the supported catalyst according to any one of claims 1-2, wherein: the using method comprises the following steps:
s1, carrying out reduced pressure distillation on an organosilicon high-boiling-point substance to remove solid impurities, thereby obtaining a pretreated high-boiling-point substance;
s2, adding the organic silicon high-boiling residues subjected to impurity removal into a cracking reactor, and then adding the immobilized catalyst;
s3, introducing hydrogen chloride gas into the reaction liquid in the cracking reactor, heating to a certain temperature, and reacting under normal pressure to obtain a mixed product mainly comprising dimethyl dichlorosilane;
s4, recycling the mixed product mainly comprising the dimethyldichlorosilane through a post-treatment process.
6. The method for using the supported catalyst according to claim 5, wherein: the mass ratio of the organosilicon high-boiling-point substance to the catalyst is 100-500:1.
7. The method for using the supported catalyst according to claim 5, wherein: the molar ratio of the organic silicon high-boiling-point substance to the hydrogen chloride is 1:1-5.
8. The method for using the supported catalyst according to claim 5, wherein: the reaction temperature is 60-150 ℃, the reaction pressure is normal pressure, and the reaction time is 3-9h.
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