CN115041225B - Catalyst for reducing ortho-isomer in mixed diisopropylbenzene and preparation method thereof - Google Patents
Catalyst for reducing ortho-isomer in mixed diisopropylbenzene and preparation method thereof Download PDFInfo
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- CN115041225B CN115041225B CN202210849722.9A CN202210849722A CN115041225B CN 115041225 B CN115041225 B CN 115041225B CN 202210849722 A CN202210849722 A CN 202210849722A CN 115041225 B CN115041225 B CN 115041225B
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- diisopropylbenzene
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- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- 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 55
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000001953 recrystallisation Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical group [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 claims description 3
- UPMCDOMOBNMTPH-UHFFFAOYSA-N 6-phenyl-5,6-dihydroimidazo[2,1-b][1,3]thiazole Chemical compound N1=C2SC=CN2CC1C1=CC=CC=C1 UPMCDOMOBNMTPH-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 3
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 claims description 2
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 claims description 2
- VMJQVRWCDVLJSI-UHFFFAOYSA-M tetraheptylazanium;chloride Chemical compound [Cl-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC VMJQVRWCDVLJSI-UHFFFAOYSA-M 0.000 claims description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 abstract description 22
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 41
- 229910004298 SiO 2 Inorganic materials 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229910001868 water Inorganic materials 0.000 description 22
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- XDTRNDKYILNOAP-UHFFFAOYSA-N phenol;propan-2-one Chemical compound CC(C)=O.OC1=CC=CC=C1 XDTRNDKYILNOAP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000010555 transalkylation reaction Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for reducing ortho-isomer in mixed diisopropylbenzene and a preparation method thereof, wherein the catalyst is Beta or MCM-22 molecular sieve catalyst, and the mesoporous volume is 0.3-0.7cm 3 Per gram, the micropore volume is 0.11-0.17cm 3 /g; the percentage of the mesoporous accounts for 63-86% of the total pore volume. The preparation method of the catalyst comprises the steps of preparing synthetic gel, performing low-temperature pre-crystallization, and adding macromolecular organic amine into a pre-crystallization system for re-crystallization. The invention can effectively improve the mesoporous content in the molecular sieve and blend the micro-mesoporous proportion of the obtained molecular sieve catalyst. The molecular sieve catalyst prepared by the method has proper micro-mesoporous proportion, and can effectively reduce the content of ortho-isomer in the mixed diisopropylbenzene<1 percent) without affecting the content of the m-diisopropylbenzene with higher value, and provides convenience for obtaining the m-diisopropylbenzene and the p-diisopropylbenzene with high purity by the way of rectification and the like in the follow-up process.
Description
Technical Field
The invention belongs to the technical field of catalysis, relates to a transalkylation catalyst, and in particular relates to a catalyst for reducing ortho-isomer in mixed diisopropylbenzene and a preparation method thereof.
Background
Diisopropylbenzene is a product of benzene and propylene alkylation or benzene and polyisopropylbenzene transalkylation in a phenol-acetone workshop, and is a very important fine organic chemical raw material, wherein the diisopropylbenzene and the p-diisopropylbenzene can be respectively oxidized into resorcinol and hydroquinone; the diisopropylbenzene can also be used for preparing products with high added value such as rubber, plastic and the like through dehydrogenation reaction. However, crude Diisopropylbenzene (DIPB) is a mixture containing the ortho, meta, and para three isomers, and is usually mixed in the ratio of meta: and (3) pairing: neighbor=45:46:7. The boiling points of the m-diisopropylbenzene and the p-diisopropylbenzene are 203.75 ℃ and 210.37 ℃ respectively, and although the relative volatilities of the m-diisopropylbenzene and the p-diisopropylbenzene are small, the m-diisopropylbenzene and the p-diisopropylbenzene can be separated by methods such as rectification, extraction, biological enzyme, membrane separation, molecular rectification, crystallization and the like. And the o-diisopropylbenzene (203.18 ℃) has a boiling point almost consistent with that of the m-diisopropylbenzene, so that the o-diisopropylbenzene has high separation difficulty with the m-diisopropylbenzene, the purity of the m-diisopropylbenzene is influenced, and the price loss of the m-diisopropylbenzene with high value is directly caused.
The modified beta zeolite catalyzed diisopropylbenzene isomerization reaction research of university of great company in 2005 mainly examines the capability of isomerizing diisopropylbenzene into m-diisopropylbenzene on a modified H beta molecular sieve, and the para-position conversion rate is up to 52.92 percent, wherein the isomerization capability of o-diisopropylbenzene is not involved, but for mixed diisopropylbenzene with higher ortho-position content, because the ortho-position boiling point and the meta-position boiling point are very close, high-purity m-diisopropylbenzene cannot be separated by utilizing the prior art, and waste of mixed diisopropylbenzene with higher ortho-position content is caused.
In 2004 petrochemical industry, influence of temperature and space velocity on the isomerization reaction of mixed diisopropylbenzene on beta zeolite catalyst, volume 33, phase 6, examine the capability of isomerizing diisopropylbenzene into m-diisopropylbenzene under different temperatures and mass space velocities on beta zeolite catalyst, and the conversion rate of diisopropylbenzene is obviously reduced along with the progress of the reaction, and the stability of the catalyst is poor. The isomerization capacity of the ortho-diisopropylbenzene is not related, and the ortho-isomer has the highest diffusion energy barrier, so that the ortho-isomer is least likely to permeate into the twelve-membered ring pore canal of the zeolite catalyst under the same condition, and the conversion rate of the ortho-isomer is extremely poor.
Chinese patent 200810011124.4 provides a method for preparing m-diisopropylbenzene by shape selective catalytic cracking, which is mainly to crack p-diisopropylbenzene entering a molecular sieve pore canal, but the m-diisopropylbenzene which cannot enter the molecular sieve pore canal is reserved, and rectify a condensation product to obtain m-diisopropylbenzene with the content of more than 99%, but the conversion of o-diisopropylbenzene is not mentioned.
Disclosure of Invention
The invention aims to provide a catalyst for reducing ortho-isomer in mixed diisopropylbenzene and a preparation method thereof, wherein the mixed diisopropylbenzene is from a phenol-acetone device, and the content of the ortho-diisopropylbenzene is higher (5% -8%). In order to reduce the content of ortho-isomer (< 1%) in mixed diisopropylbenzene, but not affect the content of m-diisopropylbenzene, the molecular sieve catalyst is used for carrying out shape selective isomerization reaction on the mixed diisopropylbenzene, and the diffusion energy barrier of three isomers is greatly different due to the different molecular sizes of three isomers of the diisopropylbenzene, especially the diffusion energy barrier of the o-diisopropylbenzene is as high as 223.5KJ/mol, but the diffusion energy barrier of the diisopropylbenzene is only 14.2KJ/mol. Therefore, the diffusion resistance of the o-diisopropylbenzene is reduced by micro-mesoporous proportion, so that on the basis of rapidly diffusing m-diisopropylbenzene and p-diisopropylbenzene, the diffusion rate of the o-diisopropylbenzene is relatively improved, the shape-selective isomerization of the o-diisopropylbenzene in the mixed diisopropylbenzene is promoted, the content (less than 1%) of the ortho-isomer in the mixed diisopropylbenzene is reduced, and convenience is provided for obtaining the high-purity m-diisopropylbenzene and p-diisopropylbenzene by means of rectification and the like.
The technical scheme of the invention is as follows:
a catalyst for reducing ortho-isomer in mixed diisopropylbenzene is Beta or MCM-22 molecular sieve catalyst with mesoporous volume of 0.3-0.7cm 3 Per gram, the micropore volume is 0.11-0.17cm 3 /g; the percentage of the mesoporous accounts for 63-86% of the total pore volume.
The invention also provides a preparation method of the catalyst, which is prepared through the following steps:
the first step: preparing synthetic gel, and performing low-temperature pre-crystallization
Preparing synthetic gel for synthesizing Beta or MCM-22 molecular sieve; placing the gel in a synthesis kettle, and pre-crystallizing for 12-24 hours at a low temperature of 50-100 ℃;
the gel for synthesizing Beta, MCM-22 molecular sieves can be formulated by techniques known to those skilled in the art, both from published literature and from published patents. Gels for synthesizing Beta and MCM-22 molecular sieves are configured as described in accordance with the published patent ZL00107486.5 and published patent ZL 200510025147.7;
and a second step of: adding macromolecular organic amine into the pre-crystallization system for re-crystallization
After the low-temperature pre-crystallization of the gel is finished, adding macromolecular organic amine into a synthesis kettle under ultrasonic oscillation, enabling the macromolecular organic amine to fully contact and react with the surface of a molecular sieve for 1-10 hours, crystallizing at the high temperature of 110-200 ℃ for 24-200 hours at the reaction temperature of 25-80 ℃; the addition amount of the macromolecular organic amine is calculated according to the addition amount of a silicon source, and the macromolecules areThe molar ratio of the organic amine to the silicon source is: siO (SiO) 2 =0.01-0.5, wherein the components of the silicon source are metered in oxides;
and a third step of: collecting molecular sieve catalyst product
After the high-temperature secondary crystallization is finished, the solid product is washed, dried and roasted to obtain the catalyst (Beta or MCM-22 molecular sieve catalyst product) for reducing ortho-isomer in the mixed diisopropylbenzene.
The macromolecular organic amine is tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetrabutylammonium tribromide, tetrahexylammonium hydroxide, tetraheptyl ammonium bromide, tetraheptyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl dimethyl phenyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium bromide.
The washing process in the step three comprises washing the solid product with deionized water to a ph=8-9; the drying temperature is 100-120 ℃ and the drying time is 12-24 hours; the roasting temperature is 500-600 ℃ and the roasting time is 5-12 hours.
The invention also provides application of the catalyst in reducing ortho-isomer in mixed diisopropylbenzene.
Compared with the prior art, the invention has the following beneficial effects:
the basic unit of the corresponding topological structure is formed through low-temperature molecular sieve pre-crystallization, organic amine macromolecules are added in the later stage, and the basic structural unit of the molecular sieve is made to build mesopores around the organic amine macromolecules under the high-temperature crystallization condition. The mesoporous content in the molecular sieve can be effectively improved by selecting organic amine macromolecules with different molecular sizes, and the micro-mesoporous proportion of the obtained molecular sieve catalyst is regulated. The molecular sieve catalyst prepared by the method has proper micro-mesoporous proportion, can effectively reduce the content of ortho-isomer (< 1%) in the mixed diisopropylbenzene without influencing the content of the m-diisopropylbenzene with higher value, and provides convenience for obtaining the m-diisopropylbenzene with high purity and p-diisopropylbenzene by the following modes of rectification and the like.
Detailed Description
Comparative example 1
According to the report of the published patent ZL00107486.5, a typical formula is selected to synthesize the Beta molecular sieve. Namely, the molar ratio of coarse pore silica gel, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethylammonium hydroxide (TEAOH) is SiO 2 /Al 2 O 3 ＝30、Na 2 O/SiO 2 ＝0.075、TEAOH/SiO 2 ＝0.09、H 2 O/SiO 2 =6.5, vacuum pump oil/SiO 2 =0.5, prepared as a homogeneous synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, crystallizing for 24h at 120 ℃, and then heating to 148 ℃ for 48h. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24h, and calcined at 540 ℃ for 6h to give the classical Beta molecular sieve (designated C-Beta).
Comparative example 2
According to the report of the published patent ZL200510025147.7, a typical formula is selected to synthesize the MCM-22 molecular sieve. I.e. NaAlO 2 The mol proportion of NaOH, water, silica sol and Hexamethyleneimine (HMI) is SiO 2 /A1 2 O 3 ＝30.0、OH - /SiO 2 ＝0.15、H 2 O/SiO 2 ＝15.0、Na + /SiO 2 ＝0.09、HMI/SiO 2 =0.35 to prepare a homogeneous gel, and MCM-22 molecular sieve seeds were added to the gel at 5% of the total weight of the mixed dry basis to obtain a synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, and crystallizing at 140 ℃ for 120h. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24h, and calcined at 540 ℃ for 6h to give the classical MCM-22 molecular sieve (designated C-MCM 22).
Example 1
Synthetic gels were formulated as reported in the published patent ZL 00107486.5. Coarse pore silica gel, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethylammonium hydroxide (TEAOH) with a molar ratio of SiO 2 /Al 2 O 3 ＝30、Na 2 O/SiO 2 ＝0.075、TEAOH/SiO 2 ＝0.09、H 2 O/SiO 2 =6.5, vacuum pump oil/SiO 2 =0.5, prepared as a homogeneous synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, and crystallizing for 24h at 65 ℃. Decompression, opening the synthesis kettle (high pressure hydrothermal kettle), adding tetrabutylammonium bromide and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 The macromolecular organic amine was allowed to react in sufficient contact with the molecular sieve surface for 3.5 hours at a reaction temperature of 60 ℃. Closing the synthesis kettle, and heating to 152 ℃ for crystallization for 48 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 6 hours to give the Beta molecular sieve catalyst (designated S-Beta-1).
Example 2
Synthetic gels were formulated as reported in the published patent ZL 00107486.5. Coarse pore silica gel, water, sodium hydroxide, pseudo-boehmite, vacuum pump oil and tetraethylammonium hydroxide (TEAOH) with a molar ratio of SiO 2 /Al 2 O 3 ＝30、Na 2 O/SiO 2 ＝0.075、TEAOH/SiO 2 ＝0.09、H 2 O/SiO 2 =6.5, vacuum pump oil/SiO 2 =0.5, prepared as a homogeneous synthetic gel. After mechanically stirring the reaction gel for 1h, transferring the reaction gel into a high-pressure hydrothermal kettle, and crystallizing for 24h at 65 ℃. Decompression, opening the synthesis kettle, adding tetrahexyl ammonium hydroxide and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 The macromolecular organic amine was allowed to react in sufficient contact with the molecular sieve surface for 6 hours at a reaction temperature of 65 ℃. Closing the synthesis kettle, and heating to 165 ℃ for crystallization for 60 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 6 hours to give the Beta molecular sieve catalyst (designated S-Beta-2).
Example 3
Synthetic gels were formulated as reported in the published patent ZL 00107486.5. Coarse pore silica gel, water, sodium hydroxide and quasi-thin aluminum hydrateThe molar ratio of the stone, the vacuum pump oil and the tetraethylammonium hydroxide (TEAOH) is SiO 2 /Al 2 O 3 ＝30、Na 2 O/SiO 2 ＝0.075、TEAOH/SiO 2 ＝0.09、H 2 O/SiO 2 =6.5, vacuum pump oil/SiO 2 =0.5, prepared as a homogeneous gel. After mechanically stirring the reaction gel for 1h, transferring the reaction gel into a high-pressure hydrothermal kettle, and crystallizing for 24h at 65 ℃. Decompression, opening the synthesis kettle, adding benzyl trimethyl ammonium bromide and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 The macromolecular organic amine was allowed to react in sufficient contact with the molecular sieve surface for 10 hours at a reaction temperature of 80 ℃. Closing the synthesis kettle, and heating to 165 ℃ for crystallization for 75 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 6 hours to give the Beta molecular sieve catalyst (designated S-Beta-3).
Example 4
According to the report of the published patent ZL200510025147.7, a typical formula is selected to synthesize the MCM-22 molecular sieve. I.e. NaAlO 2 The mol proportion of NaOH, water, silica sol and Hexamethyleneimine (HMI) is SiO 2 /A1 2 O 3 ＝30.0、OH - /SiO 2 ＝0.15、H 2 O/SiO 2 ＝15.0、Na + /SiO 2 ＝0.09、HMI/SiO 2 =0.35 to prepare a homogeneous gel, and MCM-22 molecular sieve seeds were added to the gel at 5% of the total weight of the mixed dry basis to obtain a synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, and crystallizing at 80 ℃ for 20h. Decompression, opening the synthesis kettle, adding dodecyl trimethyl ammonium bromide and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 The macromolecular organic amine was allowed to react in sufficient contact with the molecular sieve surface for 10 hours at a reaction temperature of 80 ℃. Closing the synthesis kettle, and heating to 145 ℃ for crystallization for 80 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The obtained solid product is washed by deionized water to pH=8-9, dried for 24 hours at 110 ℃ and baked for 6 hours at 540 ℃ to obtain MCM-22 molecular sieve catalyst (designated S-MCM 22-1).
Example 5
According to the report of the published patent ZL200510025147.7, a typical formula is selected to synthesize the MCM-22 molecular sieve. I.e. NaAlO 2 The mol proportion of NaOH, water, silica sol and Hexamethyleneimine (HMI) is SiO 2 /A1 2 O 3 ＝30.0、OH - /SiO 2 ＝0.15、H 2 O/SiO 2 ＝15.0、Na + /SiO 2 ＝0.09、HMI/SiO 2 =0.35 to prepare a homogeneous gel, and MCM-22 molecular sieve seeds were added to the gel at 5% of the total weight of the mixed dry basis to obtain a synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, and crystallizing at 80 ℃ for 20h. Decompression, opening the synthesis kettle, adding benzyl dimethyl phenyl ammonium chloride and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 The macromolecular organic amine was allowed to react in sufficient contact with the molecular sieve surface for 10 hours at a reaction temperature of 80 ℃. Closing the synthesis kettle, and heating to 145 ℃ for crystallization for 80 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 6 hours to give MCM-22 molecular sieve catalyst (designated S-MCM 22-2).
Example 6
According to the report of the published patent ZL200510025147.7, a typical formula is selected to synthesize the MCM-22 molecular sieve. I.e. NaAlO 2 The mol proportion of NaOH, water, silica sol and Hexamethyleneimine (HMI) is SiO 2 /A1 2 O 3 ＝30.0、OH - /SiO 2 ＝0.15、H 2 O/SiO 2 ＝15.0、Na + /SiO 2 ＝0.09、HMI/SiO 2 =0.35 to prepare a homogeneous gel, and MCM-22 molecular sieve seeds were added to the gel at 5% of the total weight of the mixed dry basis to obtain a synthetic gel. After mechanically stirring the synthetic gel for 1h, transferring the synthetic gel into a high-pressure hydrothermal kettle, and crystallizing at 80 ℃ for 20h. Decompression, opening the synthesis kettle, adding hexadecyl trimethyl ammonium bromide and organic amine/SiO into the synthesis kettle under ultrasonic vibration 2 =0.22, make macromolecules haveThe organic amine and the surface of the molecular sieve are fully contacted and reacted for 10 hours, and the reaction temperature is 80 ℃. Closing the synthesis kettle, and heating to 145 ℃ for crystallization for 80 hours. After crystallization, the pressure reducing valve is opened to evaporate partial water in the crystallized material liquid and the water is condensed and discharged. The resulting solid product was washed with deionized water to ph=8-9, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 6 hours to give MCM-22 molecular sieve catalyst (designated S-MCM 22-3).
Test example 1
The molecular sieve products prepared in examples 1-6 and comparative examples 1 and 2 were subjected to material texture structure measurement by nitrogen physical adsorption, and the results are shown in table 1. As can be seen from the data of table 1, the samples prepared in comparative examples 1 and 2 are conventional microporous molecular sieve materials, and a small amount of mesopores due to crystal accumulation is generated; the samples prepared in examples 1-6 of the present invention have a molecular sieve catalyst based on a microporous molecular sieve and a large number of mesopores, which would facilitate the diffusion of the o-diisopropylbenzene and shape selective isomerization near the catalytic center.
Table 1 material texture structure of molecular sieve products prepared in examples 1-6 and comparative examples 1 and 2
Application example 1
The main reaction steps of the mixed diisopropylbenzene in the phenol-acetone device are as follows: zeolite molecular sieve products are used as catalysts to react in a fixed bed reactor, and the reaction conditions are as follows: the pressure is 3.2MPa, the temperature is 195 ℃, and the mass airspeed is 1.72h -1 . Raw materials enter a reaction system through a double-plunger micro metering pump, enter from the lower part of the reactor, continuously flow out of the upper part of the reactor, accumulate in a gas-liquid separation tank, intermittently take out liquid-phase products in the gas-liquid separation tank, and obtain the m-diisopropylbenzene with the content of less than 1.0% in the liquid-phase products, which is obtained by taking molecular sieve products of examples 1-6 as catalysts, wherein the m-diisopropylbenzene with higher value is not affected, but also has a certain increase. Although a part of the heavy component is contained in the liquid phase compositionBut the heavy component can be eliminated by subsequent rectification without affecting the rectification and purification of meta-position and para-position isomers.
Table 2 reaction test results for the molecular sieve products prepared in examples 1-6 and comparative examples 1 and 2
Claims (1)
1. A preparation method of a catalyst for reducing ortho-isomer in mixed diisopropylbenzene is characterized by comprising the following steps: the catalyst is Beta or MCM-22 molecular sieve catalyst, and the mesoporous volume is 0.3-0.7cm 3 Per gram, the micropore volume is 0.11-0.17cm 3 /g; the percentage of the mesoporous accounts for 63% -86% of the total pore volume; the preparation method comprises the following steps:
the first step: preparing synthetic gel, and performing low-temperature pre-crystallization
Preparing synthetic gel for synthesizing Beta or MCM-22 molecular sieve; placing the gel in a synthesis kettle, and pre-crystallizing for 12-24 hours at a low temperature of 50-100 ℃;
and a second step of: adding macromolecular organic amine into the pre-crystallization system for re-crystallization
After the low-temperature pre-crystallization of the gel is finished, adding macromolecular organic amine into a synthesis kettle under ultrasonic oscillation, enabling the macromolecular organic amine to fully contact and react with the surface of a molecular sieve for 1-10 hours, crystallizing at the high temperature of 110-200 ℃ for 24-200 hours at the reaction temperature of 25-80 ℃; the molar ratio of the macromolecular organic amine to the silicon source is organic amine: siO (SiO) 2 =0.01-0.5；
And a third step of: collecting molecular sieve catalyst product
After the high-temperature secondary crystallization is finished, washing, drying and roasting the solid product to obtain a catalyst for reducing ortho-isomer in the mixed diisopropylbenzene;
the macromolecular organic amine is tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium bromide, tetrabutylammonium tribromide, tetrahexylammonium hydroxide, tetraheptyl ammonium bromide, tetraheptyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl dimethyl phenyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium bromide.
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| CN1597516A (en) * | 2004-09-21 | 2005-03-23 | 太原理工大学 | Micropore mesopore composite molecular sieve and its preparation method |
| CN101260019A (en) * | 2008-04-18 | 2008-09-10 | 大连理工大学 | Shape selective catalytic cracking preparation method for m-diisopropylbenzene |
| CN112919492A (en) * | 2021-02-23 | 2021-06-08 | 浙江浙能技术研究院有限公司 | Preparation method of hollow-structure hierarchical pore Beta molecular sieve |
| CN114162833A (en) * | 2020-09-11 | 2022-03-11 | 中国石油大学(北京) | Thin-layer MCM-22 molecular sieve microsphere with microporous mesoporous structure, preparation and application thereof |
| CN114715908A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1597516A (en) * | 2004-09-21 | 2005-03-23 | 太原理工大学 | Micropore mesopore composite molecular sieve and its preparation method |
| CN101260019A (en) * | 2008-04-18 | 2008-09-10 | 大连理工大学 | Shape selective catalytic cracking preparation method for m-diisopropylbenzene |
| CN114162833A (en) * | 2020-09-11 | 2022-03-11 | 中国石油大学(北京) | Thin-layer MCM-22 molecular sieve microsphere with microporous mesoporous structure, preparation and application thereof |
| CN114715908A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method and application thereof |
| CN112919492A (en) * | 2021-02-23 | 2021-06-08 | 浙江浙能技术研究院有限公司 | Preparation method of hollow-structure hierarchical pore Beta molecular sieve |
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