CN111905778A - Supported catalyst, preparation method thereof and application thereof in synthesis of ethylbenzyl chloride - Google Patents
Supported catalyst, preparation method thereof and application thereof in synthesis of ethylbenzyl chloride Download PDFInfo
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- CN111905778A CN111905778A CN202010854168.4A CN202010854168A CN111905778A CN 111905778 A CN111905778 A CN 111905778A CN 202010854168 A CN202010854168 A CN 202010854168A CN 111905778 A CN111905778 A CN 111905778A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- MZMVVHAHSRJOEO-UHFFFAOYSA-N 1-chloropropylbenzene Chemical compound CCC(Cl)C1=CC=CC=C1 MZMVVHAHSRJOEO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 41
- 239000004917 carbon fiber Substances 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 20
- 238000004108 freeze drying Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims abstract description 3
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000741 silica gel Substances 0.000 claims abstract description 3
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002121 nanofiber Substances 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000009941 weaving Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 241000195493 Cryptophyta Species 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a supported catalyst, which is prepared by processing activated carbon fibers into a net structure; then immersing into silica gel, and then freeze-drying; obtaining a silica aerogel/activated carbon fiber porous net-shaped composite carrier; then loading zinc chloride and aluminum chloride as composite active components; the activated carbon fiber is porous carbon fiber which is prepared by carrying out microwave treatment on fiber prepared by spinning polyacrylonitrile spinning solution. The invention also discloses a preparation method of the supported catalyst and application of the supported catalyst in synthesis of ethyl benzyl chloride. The supported catalyst has the advantages of large specific surface area, high catalytic activity and good stability; the preparation is simple; the method is used for preparing the ethyl benzyl chloride, and can effectively improve the yield and the purity of a target product.
Description
The technical field is as follows:
the invention relates to the field of organic synthesis, in particular to a supported catalyst, a preparation method thereof and application thereof in synthesis of ethyl benzyl chloride.
Background art:
ethylbenzyl chloride, also known as ethylbenzyl chloride, is an organic raw material having a molecular formula of C8H9Cl, molecular weight 140.6101; has broad-spectrum and high-efficiency sterilization and algae killing capability, can effectively control the propagation of bacteria and algae and the growth of slime in water, and has good slime stripping effectCertain dispersion and permeation, and certain deoiling, deodorizing and corrosion-retarding effects; can be widely applied to the protection of pipelines in petroleum exploration and chemical raw material transportation.
The purity and yield of the currently prepared ethyl benzyl chloride are low, and the requirement on equipment is high; the process is relatively complex.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a supported catalyst, a preparation method thereof and application thereof in synthesis of ethyl benzyl chloride aiming at the defects of the prior art, wherein the supported catalyst has large specific surface area, high catalytic activity and good stability; the preparation is simple; the method is used for preparing the ethyl benzyl chloride, and can effectively improve the yield and the purity of a target product.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a supported catalyst is prepared by processing activated carbon fiber to form a net structure; then immersing into silica gel, and then freeze-drying; obtaining a silica aerogel/activated carbon fiber porous net-shaped composite carrier; then loading zinc chloride and aluminum chloride as composite active components; the activated carbon fiber is porous carbon fiber which is prepared by carrying out microwave treatment on fiber prepared by spinning polyacrylonitrile spinning solution.
Preferably, in the above technical solution, the mass ratio of the composite carrier to the composite active component is 2: (1-1.5).
In the above aspect, the molar ratio of the zinc chloride to the aluminum chloride is preferably 1: 1.
A method for preparing a supported catalyst, comprising the steps of:
(1) dissolving polyacrylonitrile in an organic solvent to prepare a spinning solution, and then preparing nano-fibers by adopting a solution spinning method; carrying out microwave activation treatment on the nano-fibers to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) mixing and stirring the tetraethoxysilane and the absolute ethyl alcohol uniformly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol/L, carrying out hydrolysis treatment for 30-50min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then adding the prepared porous carbon fiber net, and standing and aging for 15-20 h; taking out, and soaking in ethanol solution for 20-30 h; finally, freeze drying is carried out; preparing a composite carrier;
(3) and (2) putting zinc chloride and aluminum chloride into absolute methanol, stirring until the solid is completely dissolved, then adding the prepared composite carrier, standing and adsorbing for 10-20h at normal temperature, then removing the absolute methanol, and drying in vacuum to obtain the supported catalyst.
Preferably, the power of the microwave activation treatment is 500-800W, and the time of the microwave treatment is 10-20 min; the temperature of the microwave activation treatment is 900-1000 ℃.
Preferably, in the above technical solution, the usage ratio of the tetraethoxysilane to the porous carbon fiber web is 1 mol: (5-10) g.
Preferably, the temperature of the freeze drying is-15 to-25 ℃, and the time of the freeze drying is 1 to 2 hours.
The application of the supported catalyst in the synthesis of the ethyl benzyl chloride comprises the following steps:
firstly, adding ethylbenzene, hydrochloric acid and paraformaldehyde into a reactor, uniformly mixing, adding the prepared supported catalyst, and reacting to obtain a crude product of ethyl benzyl chloride; in the reaction process, introducing hydrogen chloride gas into the reactor;
and secondly, sequentially washing and alkaline washing the prepared ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
Preferably, in the step (1), the amount ratio of ethylbenzene, 12mol/L hydrochloric acid, paraformaldehyde, supported catalyst and hydrogen chloride gas is (0.5-2) mol: 85 ml: 1 mol: (1-5) g: (1-5) mol.
Preferably, the reaction conditions are as follows: reacting at 60-90 deg.C under 0.2-0.3Mpa for 5-11 h.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
according to the supported catalyst provided by the invention, a carrier is spun by taking polyacrylonitrile solution as a raw material to prepare nano fibers, then microwave activation treatment is carried out under certain conditions to prepare porous carbon fibers, and then staggered weaving is carried out to prepare a porous carbon fiber net; and placing it in the prepared wet gel containing silicon; finally, freeze drying is carried out to prepare the honeycomb carrier; the active carbon fiber is used as a carrier skeleton; the prepared carrier has good stability, large specific surface area and good adsorbability; active components of the catalyst can be effectively adsorbed in pores of the catalyst; in the reaction process, the reaction liquid can effectively enter pores of the carrier to fully contact with the catalyst active component, so that the purity and the yield of the prepared target product are high.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are provided for the purpose of illustration only and are not intended to be limiting.
Example 1
(1) Dissolving polyacrylonitrile in N, N-dimethylacetamide to obtain a spinning solution, and preparing nano-fibers by adopting a solution spinning method; performing microwave activation treatment on the nano-fibers at 500W and 900 ℃ for 10min to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) 1mol of tetraethoxysilane and absolute ethyl alcohol are mixed and stirred evenly; then dropwise adding 0.1mol/L hydrochloric acid solution, carrying out hydrolysis treatment for 30min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then adding 5g of the prepared porous carbon fiber net, and standing and aging for 15 h; taking out, and soaking in ethanol solution for 20 h; finally, freeze-drying for 1h at-15 ℃; preparing a composite carrier;
(3) putting 0.1mol of zinc chloride and 0.1mol of aluminum chloride into 100ml of anhydrous methanol, stirring until the solid is completely dissolved, then adding 30g of the prepared composite carrier, standing and adsorbing for 10h at normal temperature, then removing the anhydrous methanol, and drying in vacuum to prepare a supported catalyst;
(4) adding 0.5mol of ethylbenzene, 85ml of hydrochloric acid and 1mol of paraformaldehyde into a reactor, uniformly mixing, adding 1g of the prepared supported catalyst, and reacting at 60 ℃ and 0.2Mpa for 5 hours to obtain a crude product of ethyl benzyl chloride; in the reaction process, 1mol of hydrogen chloride gas is introduced into the reactor;
(5) and (3) sequentially washing and alkali washing the obtained ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
Example 2
(1) Dissolving polyacrylonitrile in N, N-dimethylacetamide to obtain a spinning solution, and preparing nano-fibers by adopting a solution spinning method; performing microwave activation treatment on the nano-fibers at 800W and 1000 ℃ for 20min to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) 1mol of tetraethoxysilane and absolute ethyl alcohol are mixed and stirred evenly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol/L, carrying out hydrolysis treatment for 50min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then 10g of the porous carbon fiber net prepared above is added, and standing and aging treatment is carried out for 20 hours; taking out, and soaking in ethanol solution for 30 h; finally, freeze-drying for 12h at-25 ℃; preparing a composite carrier;
(3) putting 0.1mol of zinc chloride and 0.1mol of aluminum chloride into 100ml of anhydrous methanol, stirring until the solid is completely dissolved, then adding 40g of the prepared composite carrier, standing and adsorbing for 20h at normal temperature, then removing the anhydrous methanol, and drying in vacuum to prepare a supported catalyst;
(4) adding 1mol of ethylbenzene, 85ml of hydrochloric acid and 1mol of paraformaldehyde into a reactor, uniformly mixing, adding 5g of prepared supported catalyst, and reacting at 90 ℃ and 0.3Mpa for 11 hours to obtain a crude product of ethyl benzyl chloride; in the reaction process, 5mol of hydrogen chloride gas is introduced into the reactor;
(5) and (3) sequentially washing and alkali washing the obtained ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
Example 3
(1) Dissolving polyacrylonitrile in N, N-dimethylacetamide to obtain a spinning solution, and preparing nano-fibers by adopting a solution spinning method; performing microwave activation treatment on the nano-fibers at 600W and 900 ℃ for 10min to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) 1mol of tetraethoxysilane and absolute ethyl alcohol are mixed and stirred evenly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol/L, carrying out hydrolysis treatment for 35min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then 6g of the prepared porous carbon fiber net is added, and standing and aging treatment is carried out for 16 h; taking out, and soaking in ethanol solution for 23 h; finally, freeze-drying for 1.5h at the temperature of minus 20 ℃; preparing a composite carrier;
(3) putting 0.1mol of zinc chloride and 0.1mol of aluminum chloride into 100ml of anhydrous methanol, stirring until the solid is completely dissolved, then adding 305g of the prepared composite carrier, standing and adsorbing for 15h at normal temperature, then removing the anhydrous methanol, and drying in vacuum to prepare a supported catalyst;
(4) adding 2mol of ethylbenzene, 85ml of hydrochloric acid and 1mol of paraformaldehyde into a reactor, uniformly mixing, adding 2g of the prepared supported catalyst, and reacting at 70 ℃ and 0.2Mpa for 7 hours to obtain a crude product of ethyl benzyl chloride; in the reaction process, 5mol of hydrogen chloride gas is introduced into the reactor;
(5) and (3) sequentially washing and alkali washing the obtained ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
Example 4
(1) Dissolving polyacrylonitrile in N, N-dimethylacetamide to obtain a spinning solution, and preparing nano-fibers by adopting a solution spinning method; performing microwave activation treatment on the nano-fibers at 700W and 1000 ℃ for 20min to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) 1mol of tetraethoxysilane and absolute ethyl alcohol are mixed and stirred evenly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol, carrying out hydrolysis treatment for 45min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then 8g of the porous carbon fiber net prepared above is added, and standing and aging treatment is carried out for 18 h; taking out, and soaking in ethanol solution for 28 hr; finally, freeze-drying for 2h at-20 ℃; preparing a composite carrier;
(3) putting 0.1mol of zinc chloride and 0.1mol of aluminum chloride into 100ml of anhydrous methanol, stirring until the solid is completely dissolved, then adding 40g of the prepared composite carrier, standing and adsorbing for 18h at normal temperature, then removing the anhydrous methanol, and drying in vacuum to prepare a supported catalyst;
(4) adding 2mol of ethylbenzene, 85ml of hydrochloric acid and 1mol of paraformaldehyde into a reactor, uniformly mixing, adding 4g of the prepared supported catalyst, and reacting at 80 ℃ and 0.23Mpa for 8 hours to obtain a crude product of ethyl benzyl chloride; in the reaction process, 5mol of hydrogen chloride gas is introduced into the reactor;
(5) and (3) sequentially washing and alkali washing the obtained ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
Example 5
(1) Dissolving polyacrylonitrile in N, N-dimethylacetamide to obtain a spinning solution, and preparing nano-fibers by adopting a solution spinning method; performing microwave activation treatment on the nanofiber at 5800W and 1000 ℃ for 10min to obtain porous carbon fiber; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) 1mol of tetraethoxysilane and absolute ethyl alcohol are mixed and stirred evenly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol/L, carrying out hydrolysis treatment for 40min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then 58g of the porous carbon fiber net prepared in the previous step is added, and standing and aging treatment is carried out for 15 hours; taking out, and soaking in ethanol solution for 20 h; finally, freeze-drying for 2h at-25 ℃; preparing a composite carrier;
(3) putting 0.1mol of zinc chloride and 0.1mol of aluminum chloride into 100ml of anhydrous methanol, stirring until the solid is completely dissolved, then adding 40g of the prepared composite carrier, standing and adsorbing for 10-20h at normal temperature, then removing the anhydrous methanol, and drying in vacuum to prepare a supported catalyst;
(4) adding 2mol of ethylbenzene, 85ml of hydrochloric acid and 1mol of paraformaldehyde into a reactor, uniformly mixing, adding 4g of the prepared supported catalyst, and reacting at 90 ℃ and 0.3Mpa for 11 hours to obtain a crude product of ethyl benzyl chloride; in the reaction process, 5mol of hydrogen chloride gas is introduced into the reactor;
(5) and (3) sequentially washing and alkali washing the obtained ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
The purity and yield of the prepared carrier and the target product are correspondingly detected. The test results are shown in table 1:
TABLE 1
| Specific surface area of support, m2/g | Product yield% | Product purity% | |
| Example 1 | 1235 | 93.4 | 98.3 |
| Example 2 | 1245 | 91.9 | 98.9 |
| Example 3 | 1230 | 92.3 | 98.6 |
| Example 4 | 1233 | 92.5 | 99.1 |
| Example 5 | 1237 | 92.5 | 98.9 |
The test results show that the carrier prepared by the method has large specific surface area, large adsorption capacity and high catalytic activity of the loaded catalyst, and can effectively improve the yield and purity of the target product.
Although specific embodiments of the invention have been described, many other forms and modifications of the invention will be apparent to those skilled in the art. It is to be understood that the appended claims and this invention generally cover all such obvious forms and modifications which are within the true spirit and scope of the present invention.
Claims (10)
1. A supported catalyst characterized by: firstly, processing activated carbon fibers into a net structure by the supported catalyst; then immersing into silica gel, and then freeze-drying; obtaining a silica aerogel/activated carbon fiber porous net-shaped composite carrier; then loading zinc chloride and aluminum chloride as composite active components; the activated carbon fiber is porous carbon fiber which is prepared by carrying out microwave treatment on fiber prepared by spinning polyacrylonitrile spinning solution.
2. A supported catalyst according to claim 1, wherein: the mass ratio of the composite carrier to the composite active component is 2: (1-1.5).
3. A supported catalyst according to claim 1, wherein: the molar ratio of the zinc chloride to the aluminum chloride is 1: 1.
4. A process for preparing a supported catalyst according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) dissolving polyacrylonitrile in an organic solvent to prepare a spinning solution, and then preparing nano-fibers by adopting a solution spinning method; carrying out microwave activation treatment on the nano-fibers to prepare porous carbon fibers; finally, weaving the prepared porous carbon fibers into a porous carbon fiber net in a staggered manner;
(2) mixing and stirring the tetraethoxysilane and the absolute ethyl alcohol uniformly; then dropwise adding a hydrochloric acid solution with the mass concentration of 0.1mol/L, carrying out hydrolysis treatment for 30-50min, and then dropwise adding ammonia water to adjust the pH of the solution to 4.5-5.5; then adding the prepared porous carbon fiber net, and standing and aging for 15-20 h; taking out, and soaking in ethanol solution for 20-30 h; finally, freeze drying is carried out; preparing a composite carrier;
(3) and (2) putting zinc chloride and aluminum chloride into absolute methanol, stirring until the solid is completely dissolved, then adding the prepared composite carrier, standing and adsorbing for 10-20h at normal temperature, then removing the absolute methanol, and drying in vacuum to obtain the supported catalyst.
5. The process for preparing a supported catalyst according to claim 4, wherein: the power of the microwave activation treatment is 500-800W, and the time of the microwave treatment is 10-20 min; the temperature of the microwave activation treatment is 900-1000 ℃.
6. The process for preparing a supported catalyst according to claim 4, wherein: the using amount ratio of the ethyl orthosilicate to the porous carbon fiber net is 1 mol: (5-10) g.
7. The process for preparing a supported catalyst according to claim 4, wherein: the temperature of the freeze drying is-15 to-25 ℃, and the time of the freeze drying is 1 to 2 hours.
8. Use of a supported catalyst prepared by the process of claim 4 in the synthesis of ethylbenzyl chloride, wherein: the method comprises the following steps:
firstly, adding ethylbenzene, hydrochloric acid and paraformaldehyde into a reactor, uniformly mixing, adding the prepared supported catalyst, and reacting to obtain a crude product of ethyl benzyl chloride; in the reaction process, introducing hydrogen chloride gas into the reactor;
and secondly, sequentially washing and alkaline washing the prepared ethyl benzyl chloride crude product, dehydrating, and finally rectifying to obtain the target product.
9. Use of a supported catalyst according to claim 8 in the synthesis of ethylbenzyl chloride, wherein: in the step (1), the dosage ratio of the ethylbenzene, the 12mol/L hydrochloric acid, the paraformaldehyde, the supported catalyst and the hydrogen chloride gas is (0.5-2) mol: 85 ml: 1 mol: (1-5) g: (1-5) mol.
10. Use of a supported catalyst according to claim 8 in the synthesis of ethylbenzyl chloride, wherein: the reaction conditions are as follows: reacting at 60-90 deg.C under 0.2-0.3Mpa for 5-11 h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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