CN117342930A - Process for preparing alkylbenzene containing substituent - Google Patents
Process for preparing alkylbenzene containing substituent Download PDFInfo
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- CN117342930A CN117342930A CN202210742773.1A CN202210742773A CN117342930A CN 117342930 A CN117342930 A CN 117342930A CN 202210742773 A CN202210742773 A CN 202210742773A CN 117342930 A CN117342930 A CN 117342930A
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- catalyst bed
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- intramolecular dehydration
- hydrogenation
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- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 172
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 61
- 230000018044 dehydration Effects 0.000 claims abstract description 49
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 125000001424 substituent group Chemical group 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 150000008365 aromatic ketones Chemical class 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 11
- -1 aryl ketone Chemical class 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 20
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 230000005587 bubbling Effects 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/002—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by transformation of a functional group, e.g. oxo, carboxyl
-
- 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
Abstract
The invention relates to a preparation method of alkylbenzene containing substituent groups. The method comprises the following steps: the aromatic ketone containing substituent groups flows through a catalyst bed layer to react, and the catalyst bed layer comprises: the hydrogenation catalyst bed layers and the intramolecular dehydration catalyst bed layers are alternately arranged, and the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers; the reaction is carried out in the presence of a non-alcoholic solvent. In the presence of a non-alcohol solvent, aryl ketone containing substituent groups is adopted to synthesize alkylbenzene containing substituent groups in the catalyst bed layer which is provided with hydrogenation catalyst bed layers and intramolecular dehydration catalyst bed layers which are alternately arranged, and the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers, so that the method has the advantages of high reactant conversion rate, high selectivity of aryl ketone containing substituent groups of products and simple post-treatment.
Description
Technical Field
The invention relates to a preparation method of alkylbenzene containing substituent groups.
Background
The alkylbenzene containing substituent is a very important fine chemical and synthetic intermediate, and has wide application in the fields of medicines, pesticides, foods, synthetic materials and the like. The preparation method mainly comprises a natural separation method, an alkylaniline diazotization hydrolysis method, an alkylbenzene chlorination hydrolysis method, a phenol alkylation method and the like. The natural separation method is replaced by chemical synthesis method due to limited resources and complex separation process. The diazotization and hydrolysis method of alkyl aniline uses a large amount of sulfuric acid, which is serious in equipment corrosion, and consumes a large amount of alkali for neutralization after the reaction is finished, so that the method is gradually eliminated. The alkylbenzene chlorination hydrolysis method is seriously polluted and is basically eliminated at present. Phenol alkylation processes tend to yield a mixture of three ethyl-substituted phenols, reducing product selectivity while increasing separation costs.
Disclosure of Invention
The invention aims to solve the problems of low reactant conversion rate, low product selectivity and high process cost of the existing technology for preparing the alkylbenzene containing the substituent, and provides a preparation method of the alkylbenzene containing the substituent.
In order to achieve the above object, the present invention provides a process for producing a substituted alkylbenzene, comprising:
the aromatic ketone containing substituent groups flows through a catalyst bed layer to react, and the catalyst bed layer comprises: the hydrogenation catalyst bed layers and the intramolecular dehydration catalyst bed layers are alternately arranged, and the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers;
the reaction is carried out in the presence of a non-alcoholic solvent.
Through the technical scheme, the invention has the following advantages:
the invention synthesizes the alkyl benzene containing substituent groups in the catalyst bed layer with hydrogenation catalyst bed layers and intramolecular dehydration catalyst bed layers which are alternately arranged in the presence of non-alcohol solvents, wherein the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers, and the invention has the advantages of high conversion rate of reactants, high selectivity of aromatic ketone containing substituent groups of products and simple post-treatment.
For example, the method for preparing ethylphenol realizes 100% conversion of the reactant hydroxyacetophenone, has 99.2% selectivity to ethylphenol and can be applied to continuous production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a preparation method of alkylbenzene containing substituent groups, which comprises the following steps:
the aromatic ketone containing substituent groups flows through a catalyst bed layer to react, and the catalyst bed layer comprises: the hydrogenation catalyst bed layers and the intramolecular dehydration catalyst bed layers are alternately arranged, and the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers; the reaction is carried out in the presence of a non-alcoholic solvent.
According to a preferred embodiment of the invention, the filling volume ratio of the hydrogenation catalytic bed layer and the intramolecular dehydration catalytic bed layer of two adjacent sections is 1-10:1.
the invention synthesizes the alkyl benzene containing substituent groups in the catalyst bed layer with hydrogenation catalyst bed layers and intramolecular dehydration catalyst bed layers which are alternately arranged in the presence of non-alcohol solvents, wherein the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers, and the invention has the advantages of high conversion rate of reactants, high selectivity of aromatic ketone containing substituent groups of products and simple post-treatment.
In the present invention, the number of stages of the hydrogenation catalyst bed and the intramolecular dehydration catalyst bed in the catalyst bed is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the catalyst bed includes 2 to 4 stages of hydrogenation catalyst beds and 1 to 2 stages of intramolecular dehydration catalyst beds. By adopting the preferable scheme, the conversion rate of reactants and the selectivity of the aryl ketone containing the substituent in the product can be further improved.
According to a preferred embodiment of the invention, the catalyst bed comprises a 2-stage hydrogenation catalyst bed and a 1-stage intramolecular dehydration catalyst bed.
In the present invention, the installation manner of the catalyst bed may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the catalyst bed is installed in two fixed bed reactors connected in series, the first fixed bed reactor is filled with a hydrogenation catalyst bed, the second fixed bed reactor is filled with a hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, and the discharge port of the first fixed bed reactor is communicated with the feed port of the intramolecular dehydration catalyst bed of the second fixed bed reactor.
According to a preferred embodiment of the present invention, it is preferred that the volume ratio of the first fixed bed reactor packed hydrogenation catalyst bed, the second fixed bed reactor packed hydrogenation catalyst bed and the second fixed bed reactor packed intramolecular dehydration catalyst bed is 1 to 10:1-10:1.
in the present invention, the fixed bed reactor may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the fixed bed reactor is a trickle bed reactor.
In the present invention, the catalyst of the hydrogenation catalyst bed may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the catalyst of the hydrogenation catalyst bed is one or more of a copper-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a nickel-based catalyst, and a ruthenium-based catalyst.
According to a preferred embodiment of the invention, the copper-based catalyst contains 10-40% by weight of copper, calculated as element, and 60-90% by weight of carrier.
According to a preferred embodiment of the present invention, the support of the copper-based catalyst is selected from one or more of alumina, a silicon-based material and titania; preferably a silicon-based material; still more preferably, it is silica.
The catalyst of the preferential hydrogenation catalytic bed layer can further improve the conversion rate of reactants and the selectivity of aryl ketone with substituent groups in the product.
In the present invention, the catalyst of the intramolecular dehydration catalyst bed may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the catalyst of the intramolecular dehydration catalyst bed is a resin and/or a molecular sieve, preferably one or more of an a36 ion exchange resin, an a25 ion exchange resin, an hβ molecular sieve, a USY molecular sieve and an Hmor molecular sieve. The invention can further improve the conversion rate of reactants and the selectivity of aryl ketone containing substituent groups by adopting the catalyst of the preferential intramolecular dehydration catalytic bed layer.
In the present invention, the conditions under which the substituent-containing aromatic ketone is reacted by passing through the catalyst bed are not particularly limited, and according to a preferred embodiment of the present invention, the reaction is carried out in the presence of a solvent.
In the present invention, the non-alcoholic solvent may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the non-alcoholic solvent is selected from one or more of toluene, chlorobenzene, ethyl acetate, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide and tetrahydrofuran. By adopting the preferable scheme, the conversion rate of reactants and the selectivity of the aryl ketone containing the substituent in the product can be further improved.
According to a preferred embodiment of the invention, the reaction conditions include: the temperature is 20-250 ℃, preferably 70-200 ℃.
According to a preferred embodiment of the invention, the reaction conditions include: the pressure is from normal pressure to 10MPa, preferably from normal pressure to 4MPa.
According to a preferred embodiment of the invention, the reaction conditions include: the space velocity of the liquid phase is 0.01 to 50h -1 Preferably 0.1-5h -1 。
The invention can further improve the conversion rate of reactants and the selectivity of aryl ketone containing substituent groups by adopting the preferable reaction conditions.
According to a preferred embodiment of the present invention, the substituted alkylbenzene has a structural formula represented by formula a or formula b,
wherein R is 2 Any one selected from H, C to C6 alkyl, methoxy, ester, nitro and hydroxy;
R 1 、R 3 independently selected from C1-C6 alkyl and C6-C9 aryl;
x is selected from one of F, cl, br, I.
The present invention will be described in detail by examples.
Example 1
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and a discharge port of the first trickle bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, the second trickle bed reactor is cooled to 170 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 100%, and the selectivity of p-ethylphenol is 99.2%.
Example 2
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and a discharge port of the first trickle bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 10% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 70 ℃, the second trickle bed reactor is cooled to 70 ℃ and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, and the liquid phase space velocity of the dimethyl sulfoxide solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 100.0%, and the selectivity of p-ethylphenol is 97.5%.
Example 3
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and a discharge port of the first trickle bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 40% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 200 ℃, the second trickle bed reactor is cooled to 200 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the 5% hydroxy acetophenone N, N-dimethylformamide solution is 0.2h -1 . GC analysis of the reacted sampleThe conversion rate of hydroxyacetophenone is 100%, and the selectivity of p-ethylphenol is 95.1%.
Example 4
Three trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, the discharge port of the first trickle bed reactor is communicated with the feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor, the third trickle bed reactor is filled with the hydrogenation catalyst bed and the intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and the discharge port of the second trickle bed reactor is communicated with the feed port of the intramolecular dehydration catalyst bed of the third trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, the second trickle bed reactor is cooled to 170 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 100%, and the selectivity of p-ethylphenol is 86.3%.
Example 5
Two bubbling bed reactors connected in series are adopted, wherein the first bubbling bed reactor is filled with a hydrogenation catalytic bed layer, the catalyst filling amount is 5ml, the second bubbling bed reactor is filled with a hydrogenation catalytic bed layer and an intramolecular dehydration catalytic bed layer, the catalyst filling amount is 5ml and 2.5ml respectively, and the discharge port of the first bubbling bed reactor is communicated with the feed port of the intramolecular dehydration catalytic bed layer of the second bubbling bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ionSub-exchange resin, at 280 ℃, H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first bubbling bed reactor is cooled to 120 ℃, the second bubbling bed reactor is cooled to 170 ℃ and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 100%, and the selectivity of p-ethylphenol is 87.9%.
Example 6
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and a discharge port of the first trickle bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 5% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, the second trickle bed reactor is cooled to 170 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 100.0%, and the selectivity of p-ethylphenol is 87.5%.
Comparative example 1
Two trickle bed reactors connected in series are adopted, the two trickle bed reactors are filled with hydrogenation catalyst beds, and the catalyst filling amount is 5ml and 5ml respectively;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 At 280 ℃, H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, and the second trickle bed reactor is used for reactionCooling to 170 deg.C, and regulating H 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 84.6 percent, and the selectivity of p-ethylphenol is 68.5 percent.
Comparative example 2
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and the discharge port of the first trickle bed reactor is communicated with the feed port of the hydrogenation catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate 45ml/min, N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, the second trickle bed reactor is cooled to 170 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the tetrahydrofuran solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 95.1 percent, and the selectivity of p-ethylphenol is 71.4 percent.
Comparative example 3
Two trickle bed reactors connected in series are adopted, wherein the first trickle bed reactor is filled with a hydrogenation catalyst bed, the catalyst filling amount is 5ml, the second trickle bed reactor is filled with the hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, the catalyst filling amount is 5ml and 2.5ml respectively, and a discharge port of the first trickle bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second trickle bed reactor;
wherein the catalyst of the hydrogenation catalyst bed layer is 28% Cu/SiO 2 The catalyst of the intramolecular dehydration catalytic bed layer is A36 ion exchange resin, and is prepared by the steps of at 280 ℃ and H 2 Flow rate45ml/min，N 2 The flow rate is 155ml/min, and the reaction time is reduced for 20h. Then the first trickle bed reactor is cooled to 120 ℃, the second trickle bed reactor is cooled to 170 ℃, and H is regulated 2 Flow rate 65ml/min, N 2 The flow rate is 0ml/min, the pressure is 1mpa, the liquid phase space velocity of the isopropanol solution of 5% hydroxyacetophenone is 0.2h -1 . After the reaction, the sample is analyzed by GC, the conversion rate of hydroxyacetophenone is 90.5 percent, and the selectivity of p-ethylphenol is 75.2 percent.
In conclusion, the invention realizes 100% conversion rate of the reactant hydroxyacetophenone, the selectivity of the p-ethylphenol reaches more than 85%, and the invention can be applied to continuous production.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for the preparation of a substituted alkylbenzene comprising:
the aromatic ketone containing substituent groups flows through a catalyst bed layer to react, and the catalyst bed layer comprises: the hydrogenation catalyst bed layers and the intramolecular dehydration catalyst bed layers are alternately arranged, and the first section and the last section of the catalyst bed layer are both hydrogenation catalyst bed layers; the reaction is carried out in the presence of a non-alcoholic solvent.
2. The preparation method according to claim 1, wherein,
the filling volume ratio of the hydrogenation catalytic bed layer and the intramolecular dehydration catalytic bed layer of two adjacent sections is 1-10:1, a step of;
the catalyst bed layer comprises 2-4 sections of hydrogenation catalytic bed layers and 1-2 sections of intramolecular dehydration catalytic bed layers;
preferably, the catalyst bed comprises a 2-stage hydrogenation catalyst bed and a 1-stage intramolecular dehydration catalyst bed.
3. The preparation method according to claim 1 or 2, wherein,
the catalyst beds are arranged in two serially connected fixed bed reactors, the first fixed bed reactor is filled with a hydrogenation catalyst bed, the second fixed bed reactor is filled with a hydrogenation catalyst bed and an intramolecular dehydration catalyst bed, and a discharge port of the first fixed bed reactor is communicated with a feed port of the intramolecular dehydration catalyst bed of the second fixed bed reactor;
preferably, the volume ratio of the hydrogenation catalyst bed layer filled in the first fixed bed reactor to the hydrogenation catalyst bed layer filled in the second fixed bed reactor to the intramolecular dehydration catalyst bed layer filled in the second fixed bed reactor is 1-10:1-10:1.
4. a production process according to claim 3, wherein the fixed bed reactor is a trickle bed reactor.
5. The process according to any one of claims 1 to 4, wherein the catalyst of the hydrogenation catalyst bed is one or more of a copper-based catalyst, a palladium-based catalyst, a platinum-based catalyst, a nickel-based catalyst, and a ruthenium-based catalyst.
6. The preparation method according to claim 5, wherein,
the copper-based catalyst contains 10-40 wt% of copper and 60-90 wt% of a carrier in terms of elements;
preferably the support is selected from one or more of alumina, a silica-based material and titania; preferably a silicon-based material; still more preferably, it is silica.
7. The process according to any one of claim 1 to 6, wherein,
the catalyst of the intramolecular dehydration catalytic bed layer is resin and/or molecular sieve, preferably one or more of A36 ion exchange resin, A25 ion exchange resin, H beta molecular sieve, USY molecular sieve and Hmor molecular sieve.
8. The production process according to any one of claims 1 to 7, wherein,
the non-alcoholic solvent is selected from one or more of toluene, chlorobenzene, ethyl acetate, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide and tetrahydrofuran.
9. The production method according to any one of claims 1 to 8, wherein the reaction conditions include:
the temperature is 20-250deg.C, preferably 70-200deg.C; and/or
The pressure is between normal pressure and 10MPa, preferably between normal pressure and 4MPa; and/or
The space velocity of the liquid phase is 0.01 to 50h -1 Preferably 0.1-5h -1 。
10. The production process according to any one of claims 1 to 9, wherein,
the alkyl benzene containing substituent has a structural formula shown in a chemical formula a or a chemical formula b,
wherein R is 2 Selected from H, C-C6 alkyl, methoxy, ester, nitro and hydroxy;
R 1 、R 3 independently selected from C1-C6 alkyl and C6-C9 aryl;
x is selected from one of F, cl, br, I.
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