CN114289061A - Catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene and preparation method and application thereof - Google Patents
Catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene and preparation method and application thereof Download PDFInfo
- Publication number
- CN114289061A CN114289061A CN202111233396.0A CN202111233396A CN114289061A CN 114289061 A CN114289061 A CN 114289061A CN 202111233396 A CN202111233396 A CN 202111233396A CN 114289061 A CN114289061 A CN 114289061A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- alkyl anthracene
- anthracene
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- -1 disubstituted alkyl anthracene Chemical compound 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002808 molecular sieve Substances 0.000 claims abstract description 80
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010555 transalkylation reaction Methods 0.000 claims description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LUACOWBTSAPURU-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)(C)CC)=CC=C3C=C21 LUACOWBTSAPURU-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of synthesis of mono-substituted alkyl anthracene, and discloses a catalyst for converting di-substituted alkyl anthracene into mono-substituted alkyl anthracene, and a preparation method and application thereof. The preparation method comprises the following steps: adding the molecular sieve into an alkali solution with the concentration of 0.05-1.50 mol/L, heating for reaction, and separating out the molecular sieve subjected to alkali treatment; the molecular sieve comprises one or more of a Y-type molecular sieve, a Beta molecular sieve, an MCM-22 molecular sieve, an MCM-41 molecular sieve, a ZSM-5 molecular sieve and an MOR molecular sieve; adding the molecular sieve subjected to alkali treatment into an acid solution with the concentration of 0.05-1.00 mol/L, heating for reaction, separating the molecular sieve subjected to acid treatment, and calcining to obtain the catalyst. The catalyst can realize the conversion from the disubstituted alkyl anthracene to the monosubstituted alkyl anthracene, and has higher catalytic efficiency and selectivity.
Description
Technical Field
The invention relates to the field of synthesis of mono-substituted alkyl anthracene, in particular to a catalyst for converting di-substituted alkyl anthracene into mono-substituted alkyl anthracene, and a preparation method and application thereof.
Background
The 2-alkyl anthraquinone is an important fine chemical product, is mainly used for producing a carrier material of hydrogen peroxide, and can also be used as an intermediate for degrading resin, photosensitive polymeric material or fuel, and the like. The prior production method of 2-alkylanthraquinone mainly adopts a phthalic anhydride acylation-dehydration method, but the method has the problems of serious environmental pollution and equipment corrosion and is difficult to meet the requirements of green chemical production, so that the development of a green production process of 2-alkylanthraquinone is urgently needed.
The existing report proposes that the alkylation-oxidation method of anthracene is adopted to prepare 2-alkyl anthraquinone, and the method has the advantages of mild reaction conditions, simple process flow, small environmental pollution and the like, and is considered as a green and feasible process route. The technical report of preparing 2-alkyl anthraquinone by oxidizing 2-alkyl anthracene with an oxidant at present is wide, and the commonly adopted oxidant comprises tert-butyl peroxide, hydrogen peroxide or oxygen, and the like; however, the technical route for producing 2-alkyl anthracene by anthryl alkylation also has the problems of low reaction conversion rate, poor selectivity, complex separation process and the like, and the key for solving the problems is the selection of an alkylation reaction catalyst. Zeolite molecular sieves have been widely used in the field of industrial catalysis due to their large specific surface area, regular pore structure, good hydrothermal stability and tunable acidity. Patent CN 111068650 discloses a molecular sieve supported organic metal polyacid salt catalyst, which is used for preparing 2-alkyl anthracene by alkylation of anthracene, and then oxidizing the 2-alkyl anthracene into 2-alkyl anthraquinone by oxidant. In addition, patent CN 110935486 discloses a method for producing 2-alkyl anthracene by reacting anthracene with alkylating agent, and oxidizing with organic peroxide to obtain 2-alkyl anthraquinone. The method adopts a multifunctional catalyst, namely Ag is adopted to modify a TS-1 molecular sieve, Zr and SO4 2-For Al2O3Modifying, and then mixing the modified TS-1 and Al2O3Mixing, shaping and calcining.
Although molecular sieve catalysts have certain catalytic activity for alkylation reactions, the selectivity and stability of the products are still insufficient. The Beta type molecular sieve is adopted to catalyze the alkylation reaction of anthracene and tertiary butanol in the paper published in the book No. 1 of university of Liaojinxin at university of Liaoning petrochemical industry, namely Friedel-Crafts alkylation reaction of anthracene and tertiary butanol, and the analysis of products shows that the product not only generates mono-substituted 2-tert-butyl anthracene, but also generates di-substituted 2, 6-di-tert-butyl anthracene by-product, namely that the mono-substituted alkyl anthracene is produced by adopting the molecular sieve catalyst and the generation of the di-substituted alkyl anthracene is often accompanied.
Disclosure of Invention
In order to solve the technical problems, the invention provides a catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene, and a preparation method and application thereof. The catalyst can realize the conversion from the disubstituted alkyl anthracene to the monosubstituted alkyl anthracene, and has higher catalytic efficiency and selectivity.
The specific technical scheme of the invention is as follows:
in a first aspect, the present invention provides a process for preparing a catalyst for converting a disubstituted alkyl anthracene to a monosubstituted alkyl anthracene, comprising the steps of:
(1) adding the molecular sieve into an alkali solution with the concentration of 0.05-1.50 mol/L, heating for reaction, and separating out the molecular sieve subjected to alkali treatment; the molecular sieve comprises one or more of a Y-type molecular sieve, a Beta molecular sieve, an MCM-22 molecular sieve, an MCM-41 molecular sieve, a ZSM-5 molecular sieve and an MOR molecular sieve;
(2) adding the molecular sieve subjected to alkali treatment into an acid solution with the concentration of 0.05-1.00 mol/L, heating for reaction, separating the molecular sieve subjected to acid treatment, and then calcining to obtain the catalyst for converting the disubstituted alkyl anthracene into the monosubstituted alkyl anthracene.
The invention aims at the molecular characteristics of disubstituted alkyl anthracene and monosubstituted alkyl anthracene, changes the acidity and the pore structure of the molecular sieve by sequentially carrying out alkali treatment and acid treatment on the molecular sieve, so that the obtained catalyst can be used for catalyzing the disubstituted alkyl anthracene which has less direct application and is produced and the remained disubstituted alkyl anthracene to carry out transalkylation reaction, and is converted into the monosubstituted alkyl anthracene which has wide application but insufficient supply, and the catalyst has the advantages of simple production process, low production cost, high catalysis efficiency and high selectivity.
The catalyst structure required varies from transalkylation reaction to transalkylation reaction due to the difference in molecular characteristics of the reactants and reaction products. The invention relates to a specific preparation method aiming at the reaction of converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene, so as to obtain a catalyst with specific acidity and a pore channel structure. In the preparation process of the catalyst, the selection of the molecular sieve, the method for changing the acidity and the pore channel structure of the molecular sieve, the acid-base treatment sequence and the design of process parameters in the treatment process all influence the acidity and the pore channel structure of the finally obtained catalyst, wherein the change of any factor can cause that the finally obtained catalyst cannot effectively catalyze the conversion of the disubstituted alkyl anthracene into the monosubstituted alkyl anthracene.
Preferably, in the step (1), the molecular sieve is one or more of a Y-type molecular sieve, a Beta molecular sieve, an MCM-22 molecular sieve and an MOR molecular sieve.
Preferably, in the step (1), the base includes one or more of sodium hydroxide, sodium carbonate, aqueous ammonia, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and more preferably one or more of sodium hydroxide, aqueous ammonia and tetrapropylammonium hydroxide.
Preferably, in the step (1), the mass-to-volume ratio of the molecular sieve to the alkali solution is 1-5 g:100 mL.
Preferably, in the step (2), the acid includes one or more of diluted hydrochloric acid, citric acid, tartaric acid, oxalic acid and acetic acid, and more preferably one or more of diluted hydrochloric acid, citric acid and acetic acid.
Preferably, the mass-to-volume ratio of the molecular sieve in the step (1) to the acid solution in the step (2) is 1-5 g:100 mL.
Preferably, in the steps (1) and (2), the heating reaction is carried out at the temperature of 40-100 ℃ for 1-6 h.
In both the alkali treatment and the acid treatment, the reaction time and temperature affect the acidity and pore structure of the finally obtained catalyst. When the reaction time and the temperature are too high or too low, the obtained catalyst cannot convert the disubstituted alkyl anthracene into the monosubstituted alkyl anthracene, or the catalytic efficiency of the catalyst is too low.
Preferably, in the step (2), the calcining temperature is 400-600 ℃ and the time is 2-6 h.
In a second aspect, the present invention provides a catalyst prepared by the preparation method.
In a third aspect, the invention provides the use of the catalyst for converting a disubstituted alkyl anthracene to a monosubstituted alkyl anthracene.
Preferably, the application comprises the steps of: and adding disubstituted alkyl anthracene serving as a reactant or disubstituted alkyl anthracene and anthracene serving as reactants into a reaction solvent, and adding the catalyst to perform transalkylation reaction to obtain the monosubstituted alkyl anthracene.
Preferably, the reactant is anthracene and disubstituted alkyl anthracene with a molar ratio of 1-20: 1, and more preferably anthracene and disubstituted alkyl anthracene with a molar ratio of 4-18: 1.
Preferably, the mass ratio of the reactant to the catalyst is 1-20: 1, and more preferably 2-10: 1.
Preferably, the mass-to-volume ratio of the reactant to the reaction solvent is 1g:5 to 20mL, and more preferably 1g:8 to 16 mL.
Preferably, the reaction solvent includes one or more of dimethylformamide, tetrahydrofuran, nitrobenzene, chlorobenzene, mesitylene and trifluorotoluene, and more preferably one or more of dimethylformamide, mesitylene and nitrobenzene.
Preferably, the temperature of the transalkylation reaction is 140-220 ℃, the pressure is 1-4 MPa, and the time is 4-12 h.
Compared with the prior art, the invention has the following advantages: the catalyst obtained by the preparation method can convert the disubstituted alkyl anthracene which has less direct use and is produced and remained into the monosubstituted alkyl anthracene which has wide use but insufficient supply, and has high catalytic efficiency and selectivity, simple production process, low production cost and safe and reliable production process.
Drawings
FIG. 1 is a scanning electron microscope photograph of catalysts E-1, E-4, E-7, E-8 and E-9;
FIG. 2 is an X-ray diffraction pattern of catalysts E-1, E-4, E-7, E-8 and E-9.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method of making a catalyst for converting a disubstituted alkyl anthracene to a monosubstituted alkyl anthracene, comprising the steps of:
(1) adding a molecular sieve into an aqueous alkali with the concentration of 0.05-1.50 mol/L, wherein the mass-volume ratio of the molecular sieve to the aqueous alkali is 1-5 g:100mL, heating and reacting at 40-100 ℃ for 1-6 h, and separating out the molecular sieve subjected to alkali treatment; the molecular sieve comprises one or more of a Y-type molecular sieve, a Beta molecular sieve, an MCM-22 molecular sieve, an MCM-41 molecular sieve, a ZSM-5 molecular sieve and an MOR molecular sieve, and preferably one or more of the Y-type molecular sieve, the Beta molecular sieve, the MCM-22 molecular sieve and the MOR molecular sieve; the alkali comprises one or more of sodium hydroxide, sodium carbonate, ammonia water, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and preferably one or more of sodium hydroxide, ammonia water and tetrapropylammonium hydroxide;
(2) adding the molecular sieve subjected to alkali treatment into an acid solution with the concentration of 0.05-1.00 mol/L, wherein the mass-to-volume ratio of the molecular sieve in the step (1) to the acid solution in the step (2) is 1-5 g:100mL, heating and reacting at 40-100 ℃ for 1-6 h, separating the molecular sieve subjected to acid treatment, and calcining at 400-600 ℃ for 2-6 h to obtain a catalyst for converting disubstituted alkyl anthracene into mono-substituted alkyl anthracene; the acid comprises one or more of dilute hydrochloric acid, citric acid, tartaric acid, oxalic acid and acetic acid, preferably one or more of dilute hydrochloric acid, citric acid and acetic acid.
The catalyst is used for catalyzing the disubstituted alkyl anthracene to be converted into the monosubstituted alkyl anthracene, and the method specifically comprises the following steps:
adding disubstituted alkyl anthracene serving as a reactant or anthracene and disubstituted alkyl anthracene serving as reactants with a molar ratio of 1-20: 1 (preferably 4-18: 1) into a reaction solvent, wherein the mass-volume ratio of the reactants to the reaction solvent is 1g: 5-20 mL (preferably 1g: 8-16 mL), adding the catalyst, and the mass ratio of the reactants to the catalyst is 1-20: 1 (preferably 2-10: 1), and performing an alkyl transfer reaction at 140-220 ℃ and 1-4 MPa for 4-12 h to obtain the monosubstituted alkyl anthracene; the reaction solvent comprises one or more of dimethylformamide, tetrahydrofuran, nitrobenzene, chlorobenzene, mesitylene and trifluorotoluene, and preferably one or more of dimethylformamide, mesitylene and nitrobenzene.
Preparation example 1
A method of making a catalyst for converting a disubstituted alkyl anthracene to a monosubstituted alkyl anthracene, comprising the steps of:
(1) mixing 2.0g of MOR molecular sieve with 40mL of tetrapropylammonium hydroxide solution with the concentration of 0.20mol/L, stirring and reacting for 1h at the temperature of 80 ℃, and then filtering and drying to obtain the molecular sieve subjected to alkali treatment;
(2) mixing the molecular sieve after the alkali treatment with 60mL of acetic acid solution with the concentration of 0.70mol/L, stirring and reacting for 4h at the temperature of 60 ℃, then filtering, drying, and calcining for 4h at the temperature of 450 ℃ to obtain the catalyst E-1.
Preparation examples 2 to 22
The catalysts of preparation examples 2 to 22 were prepared according to the method of preparation example 1 to obtain catalysts E-2 to E-22, respectively, except that the preparation conditions of preparation example 1 were replaced with the corresponding preparation conditions (alkali, acid and process parameters) of tables 1 to 3.
TABLE 1 preparation conditions of the catalysts in the respective preparation examples
TABLE 2 preparation conditions of the catalysts in the respective preparation examples
TABLE 3 preparation conditions of the catalysts in the respective preparation examples
Comparative example 1
A method of preparing a catalyst comprising the steps of:
mixing 5.0g of MOR molecular sieve with 150mL of 0.60mol/L ammonia water solution, stirring and reacting for 3h at 40 ℃, then filtering, drying, and calcining for 2h at 500 ℃ to obtain the catalyst E-23.
Comparative example 2
A method of preparing a catalyst comprising the steps of:
mixing 6.0g of MCM-22 molecular sieve with 120mL of oxalic acid solution with the concentration of 0.30mol/L, stirring for 6 hours at the temperature of 80 ℃, then filtering, drying, and calcining for 5 hours at the temperature of 500 ℃ to obtain the catalyst E-24.
Comparative example 3
A method of preparing a catalyst comprising the steps of:
mixing 2.0g of MOR molecular sieve with 40mL of tetrapropylammonium hydroxide solution with the concentration of 0.20mol/L, stirring and reacting for 1h at the temperature of 80 ℃, then filtering, drying, and calcining for 4h at the temperature of 450 ℃ to obtain the catalyst E-25.
Comparative example 4
A method of preparing a catalyst comprising the steps of:
mixing 2.0g of MOR molecular sieve with 60mL of 0.70mol/L acetic acid solution, stirring and reacting for 4 hours at the temperature of 60 ℃, then filtering, drying, and calcining for 4 hours at the temperature of 450 ℃ to obtain the catalyst E-26.
Comparative example 5
A method of preparing a catalyst comprising the steps of:
(1) mixing 2.0g of MOR molecular sieve with 60mL of 0.70mol/L acetic acid solution, stirring and reacting for 4 hours at the temperature of 60 ℃, and then filtering and drying to obtain the molecular sieve subjected to alkali treatment;
(2) mixing the molecular sieve after the alkali treatment with 40mL of tetrapropylammonium hydroxide solution with the concentration of 0.20mol/L, stirring and reacting for 1h at the temperature of 80 ℃, then filtering, drying, and calcining for 4h at the temperature of 450 ℃ to obtain the catalyst E-27.
Comparative examples 6 to 11
Catalysts of comparative examples 6 to 11 were prepared according to the method of preparation example 1 to obtain catalysts E-28 to E-33, respectively, except that the preparation conditions of preparation example 1 were replaced with the corresponding preparation conditions of Table 4.
TABLE 4 preparation conditions of the catalysts in the respective comparative examples
Application example 1
The method for carrying out the transalkylation reaction of the disubstituted alkyl anthracene by using the catalyst E-23 specifically comprises the following steps:
taking anthracene and disubstituted alkyl anthracene with a molar ratio of 14:1 as reactants, adding the reactants and a catalyst E-23 into a sealed reaction kettle (the mass ratio of the reactants to the catalyst is 6:1), and then adding a calculated amount of mesitylene into the reaction kettle (the ratio of a reaction solvent to the reactants is 10 mL/g). The reaction temperature is controlled to be 180 ℃, the reaction time is 8h, and the reaction pressure is 3 MPa.
Application examples 2 to 41
The transalkylation reaction of disubstituted alkylanthracenes was carried out as in application example 1, except that the corresponding process conditions in table 5 were used instead of those in application example 1.
TABLE 5 Process conditions for the respective application examples
Test example
The electron micrographs of catalysts E-1, E-4, E-7, E-8 and E-9 are shown in FIG. 1. As can be seen from FIG. 1, the crystal form of the catalyst treated by the method is complete.
The XRD patterns of catalysts E-1, E-4, E-7, E-8 and E-9 are shown in FIG. 2. As can be seen from fig. 2, the catalyst treated according to the present invention has high crystallinity.
In application examples 1 to 41, after the reaction is completed, the reaction kettle is cooled to room temperature, the product is dissolved in dichloromethane, the product is analyzed by gas chromatography, and the evaluation results are shown in table 6.
TABLE 6 evaluation results of respective catalysts
Analyzing the data of table 6, the following conclusions can be drawn:
(1) 3-10, 12 and 14-22, the catalyst of the invention is used for catalyzing the transalkylation reaction of disubstituted alkyl anthracene, the conversion rate of anthracene and 2, 6-di-tert-amyl anthracene and the selectivity of the product 2-tert-amyl anthracene are high, which shows that the catalyst obtained by treating a specific molecular sieve by using the method of the invention can realize the conversion from disubstituted alkyl anthracene to monosubstituted alkyl anthracene, and has high catalytic efficiency and selectivity.
(2) Comparative examples 1 and 3 only carry out alkali treatment on the molecular sieve, comparative examples 2 and 4 only carry out acid treatment, comparative example 5 replaces the sequence of the acid-base treatment, and comparative examples 6 to 11 adopt the concentration of the acid-base solution outside the range of the invention and the treatment temperature and time in the acid-base treatment process. When the catalysts prepared in these comparative examples were used to conduct transalkylation of disubstituted alkyl anthracenes (i.e., application examples 1-2, 11, 13, and 23-41), the conversion of anthracene and 2, 6-di-t-amylanthracene and the selectivity of the product 2-t-amylanthracene decreased. The method for changing the acidity and the pore structure of the molecular sieve, the sequence of acid and base treatment and the design of process parameters in the treatment process in the preparation process of the catalyst all influence the acidity and the pore structure of the finally obtained catalyst, wherein the change of any factor can cause that the finally obtained catalyst can not effectively catalyze the conversion of the disubstituted alkyl anthracene into the monosubstituted alkyl anthracene.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method of making a catalyst for converting a disubstituted alkyl anthracene to a monosubstituted alkyl anthracene, comprising the steps of:
(1) adding the molecular sieve into an alkali solution with the concentration of 0.05-1.50 mol/L, heating for reaction, and separating out the molecular sieve subjected to alkali treatment; the molecular sieve comprises one or more of a Y-type molecular sieve, a Beta molecular sieve, an MCM-22 molecular sieve, an MCM-41 molecular sieve, a ZSM-5 molecular sieve and an MOR molecular sieve;
(2) adding the molecular sieve subjected to alkali treatment into an acid solution with the concentration of 0.05-1.00 mol/L, heating for reaction, separating the molecular sieve subjected to acid treatment, and then calcining to obtain the catalyst for converting the disubstituted alkyl anthracene into the monosubstituted alkyl anthracene.
2. The method of claim 1, wherein in step (1), the base comprises one or more of sodium hydroxide, sodium carbonate, aqueous ammonia, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
3. The method of claim 1, wherein in step (2), the acid comprises one or more of dilute hydrochloric acid, citric acid, tartaric acid, oxalic acid, and acetic acid.
4. The preparation method according to claim 1, wherein in the steps (1) and (2), the heating reaction is carried out at a temperature of 40-100 ℃ for 1-6 h.
5. The preparation method according to claim 1, wherein in the step (2), the calcining temperature is 400-600 ℃ and the calcining time is 2-6 h.
6. A catalyst obtained by the production method according to any one of claims 1 to 5.
7. Use of the catalyst of claim 6 to convert a di-substituted alkyl anthracene to a mono-substituted alkyl anthracene.
8. Use according to claim 7, characterized in that it comprises the following steps: and adding disubstituted alkyl anthracene serving as a reactant or disubstituted alkyl anthracene and anthracene serving as reactants into a reaction solvent, and adding the catalyst to perform transalkylation reaction to obtain the monosubstituted alkyl anthracene.
9. The use of claim 8, wherein:
the reactants are anthracene and disubstituted alkyl anthracene with a molar ratio of 1-20: 1; and/or
The mass ratio of the reactant to the catalyst is 1-20: 1; and/or
The mass volume ratio of the reactant to the reaction solvent is 1g: 5-20 mL.
10. The use according to claim 8, wherein the transalkylation reaction is carried out at a temperature of 140 to 220 ℃, a pressure of 1 to 4MPa and a time of 4 to 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111233396.0A CN114289061B (en) | 2021-10-22 | 2021-10-22 | Application of catalyst in conversion of disubstituted alkylanthracene into monosubstituted alkylanthracene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111233396.0A CN114289061B (en) | 2021-10-22 | 2021-10-22 | Application of catalyst in conversion of disubstituted alkylanthracene into monosubstituted alkylanthracene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114289061A true CN114289061A (en) | 2022-04-08 |
| CN114289061B CN114289061B (en) | 2024-05-10 |
Family
ID=80964146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111233396.0A Active CN114289061B (en) | 2021-10-22 | 2021-10-22 | Application of catalyst in conversion of disubstituted alkylanthracene into monosubstituted alkylanthracene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114289061B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206813A (en) * | 2020-09-30 | 2021-01-12 | 天长市润源催化剂有限公司 | Preparation method of high-silica-alumina-ratio desulfurization catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935379A (en) * | 2011-08-16 | 2013-02-20 | 中国科学院大连化学物理研究所 | Preparation method of MCM-22 molecular sieve catalyst |
| CN109174169A (en) * | 2018-10-18 | 2019-01-11 | 西安元创化工科技股份有限公司 | A kind of modified molecular sieve catalyst of producing ethylene from dehydration of ethanol and its application |
| CN110203945A (en) * | 2019-06-11 | 2019-09-06 | 太原大成环能化工技术有限公司 | A kind of preparation method of the Modified Zeolite Y of high-crystallinity and high silica alumina ratio |
| CN111484402A (en) * | 2020-04-07 | 2020-08-04 | 浙江恒澜科技有限公司 | Process for preparing anthraquinone and its hydrocarbyl derivatives |
| CN113045375A (en) * | 2021-03-22 | 2021-06-29 | 浙江大学衢州研究院 | Method for preparing 2-pentylanthracene from diamyl anthracene through transalkylation |
-
2021
- 2021-10-22 CN CN202111233396.0A patent/CN114289061B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935379A (en) * | 2011-08-16 | 2013-02-20 | 中国科学院大连化学物理研究所 | Preparation method of MCM-22 molecular sieve catalyst |
| CN109174169A (en) * | 2018-10-18 | 2019-01-11 | 西安元创化工科技股份有限公司 | A kind of modified molecular sieve catalyst of producing ethylene from dehydration of ethanol and its application |
| CN110203945A (en) * | 2019-06-11 | 2019-09-06 | 太原大成环能化工技术有限公司 | A kind of preparation method of the Modified Zeolite Y of high-crystallinity and high silica alumina ratio |
| CN111484402A (en) * | 2020-04-07 | 2020-08-04 | 浙江恒澜科技有限公司 | Process for preparing anthraquinone and its hydrocarbyl derivatives |
| CN113045375A (en) * | 2021-03-22 | 2021-06-29 | 浙江大学衢州研究院 | Method for preparing 2-pentylanthracene from diamyl anthracene through transalkylation |
Non-Patent Citations (1)
| Title |
|---|
| KEFENG LIU ET AL.: "Alkali-treatment of template-containing MCM-22 zeolite and itsapplication in alkylation and transalkylation reactions", 《APPLIED CATALYSIS A: GENERAL》, vol. 468, pages 288 - 295, XP028762251, DOI: 10.1016/j.apcata.2013.09.009 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112206813A (en) * | 2020-09-30 | 2021-01-12 | 天长市润源催化剂有限公司 | Preparation method of high-silica-alumina-ratio desulfurization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114289061B (en) | 2024-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108046288A (en) | A kind of method for preparing the multi-stage porous ZSM-5 molecular sieve for preparing propylene from methanol | |
| CN105102374B (en) | Dehydration-method for hydrolysis and its catalyst | |
| CN111217656B (en) | Catalyst for reaction of preparing 1, 3-butadiene from ethanol and preparation and application thereof | |
| CN114213250A (en) | Method for synthesizing methyl acetate by dimethyl ether carbonylation | |
| CN109641194A (en) | Catalyst comprising small 10- ring zeolite crystallite and the method for preparing hydrocarbon by making oxygenatedchemicals via the catalyst reaction | |
| CN114289061A (en) | Catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene and preparation method and application thereof | |
| CN112206811B (en) | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof | |
| CN112657534A (en) | Preparation method and application of catalyst for synthesizing 2-alkyl anthracene | |
| CN109928943B (en) | Method for synthesizing propylene oxide by using microchannel reactor | |
| CN115970748A (en) | Catalyst for heterogeneous synthesis of piperidine nitroxide free radicals | |
| CN101279957B (en) | Method for preparing epoxypropane by epoxidation of propene | |
| CN111960430B (en) | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve | |
| CN113828352A (en) | Preparation method of supported palladium/titanium silicalite molecular sieve catalyst | |
| CN111977663A (en) | Hierarchical pore structure zeolite molecular sieve and preparation method and application thereof | |
| KR102312033B1 (en) | Catalyst system for oxidative dehydrogenation of ethane, preparation method thereof, and preparation method of ethylene from ethane by using the catalyst system | |
| EP3689845A1 (en) | Method for directly producing ethanol from syngas | |
| CN118022814A (en) | Iron-molybdenum catalyst taking SBA-15 as carrier and preparation method and application thereof | |
| CN113184875B (en) | Preparation method of all-silicon type short b-axis ZSM-5 zeolite molecular sieve | |
| CN111517929A (en) | Method for producing acetone | |
| CN117443447A (en) | TS-1 catalyst, preparation method thereof and application thereof in preparation of dimethyl sulfoxide | |
| CN106866583A (en) | A kind of two（2 ethoxys）The preparation method of piperazine | |
| CN116020560B (en) | Catalyst for preparing unsaturated carbonate, preparation method and application thereof | |
| KR102391647B1 (en) | Synthesis of 2-isopropoxy- 1-propanol using zeolite based heterogeneous catalysts and their production method | |
| CN115722256B (en) | Preparation method of alkylation catalyst, catalyst and application | |
| CN112387267B (en) | Preparation method and application of methanol conversion catalyst with magnesia-alumina spinel as carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |