CN112295593A - Alkyl aromatic hydrocarbon isomerization catalyst and its preparation and application - Google Patents
Alkyl aromatic hydrocarbon isomerization catalyst and its preparation and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 40
- -1 Alkyl aromatic hydrocarbon Chemical class 0.000 title description 10
- 238000002360 preparation method Methods 0.000 title description 10
- 239000011148 porous material Substances 0.000 claims abstract description 88
- 239000010457 zeolite Substances 0.000 claims abstract description 42
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 17
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 23
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 230000005496 eutectics Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000008096 xylene Substances 0.000 abstract description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052680 mordenite Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006204 deethylation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 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 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
-
- B01J35/615—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
- C07C4/18—Catalytic processes
-
- 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
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
An alkylaromatic isomerization catalyst comprises a composite carrier and 0.005-0.2 mass% of VIII group metal calculated by taking the composite carrier as a reference, wherein the composite carrier comprises 48-75 mass% of high-silicon pentasil zeolite, 0.5-3.0 mass% of molybdenum oxide and 24-50 mass% of macroporous alumina, the total pore volume of the catalyst is 0.4-1.5 mL/g, and the total specific surface area is 350-500 m2(ii) in terms of/g. The catalyst is used for aromatic hydrocarbon isomerization reaction, and can improve xylene isomerizationThe reaction activity of the side chain alkyl of the aromatic hydrocarbon is removed, and the selectivity of the isomerization reaction is improved.
Description
Technical Field
The invention relates to an alkyl aromatic hydrocarbon isomerization catalyst, a preparation method and an application thereof, in particular to a side chain alkyl aromatic hydrocarbon isomerization catalyst, a preparation method and an application thereof.
Background
In the petrochemical equipment, there are several technological processes for producing C8Aromatic hydrocarbon resources, which usually contain ethylbenzene in addition to the three xylenes, p-, m-and o-xylene. The paraxylene product can be obtained by using the paraxylene as a raw material and performing unit technology combined operation such as isomerization, rectification, adsorption separation and the like. Because the boiling points of ethylbenzene and xylene are close, the energy consumption is high, the efficiency is low and the difficulty is high by adopting rectification separation, so a method for converting ethylbenzene is usually adopted to avoid the accumulation of ethylbenzene in the circulating material flow of a combined device. There are two methods of ethylbenzene conversion, one by isomerization to xylenes and the other by deethylation to benzene. The former has relatively low conversion rate and low selectivity, and the ethylbenzene conversion needs C8The naphthenic non-aromatic hydrocarbon is used as an intermediate, and the ethylbenzene conversion rate is high, so that the selectivity is good, the circulation amount of the deethyl type catalytic technology is small, the operation energy consumption of the combined device is low, and the production efficiency of the product is high. Currently, in the global aromatics complex, over 65% of the plants have chosen to use a de-ethylation-type isomerization technology route.
In recent years, as the market demand for xylene products, particularly para-xylene products, has continued to increase, more and more C has become available8Aromatic hydrocarbon resource for producing xylene, including C produced by ethylene cracking rich in ethylbenzene8Aromatic hydrocarbons, resulting in C to produce xylene8The ethylbenzene content in the aromatic hydrocarbon raw material is increased, the material flow circulation volume of the combined device is increased, the operation severity of adsorption and separation is correspondingly increased, but the productivity of the device cannot be effectively increased.Therefore, the isomerization catalyst for converting ethylbenzene into benzene is gradually paid attention, the boiling point of the benzene fraction obtained by ethylbenzene conversion is greatly different from that of xylene, and separation can be realized by rectification.
An isomerization catalyst for converting ethylbenzene into benzene has been reported, and the carrier of the isomerization catalyst is composed of an inert material such as alumina or silica and one or more composite zeolites, and is loaded with one or more composite metal components.
US4482773, US4874731, US4939110, US5877374 disclose ZSM-5 catalysts loaded with Pt and Mg, Bi, Pb, respectively. EP138617a2 discloses Mo-supported ZSM-5 catalysts. US4467129 discloses ZSM-5 and mordenite composite zeolite catalysts loaded with one of the metals Re, Mo, W, V. However, the ethylbenzene conversion rate of the catalysts is low, and the overall performance of the catalysts cannot meet the requirement of the current production.
WO98/05613 describes a catalyst system for isomerization of the deethylation type, comprising a catalyst with three beds, and active alumina loaded with components such as Mo and the like and having a hydrogenation function is introduced into the second bed, which is intended to ensure timely saturation of olefin intermediates such as ethylene and the like generated in the process of removing alkyl groups, and reduce the degree of side reactions such as alkylation and the like caused thereby.
Patents such as US7301064, US7375047, US7381677, US7425660, US7446237, US7456125, etc. add hydrogenation active metal Mo except noble metal in the preparation process of isomerization catalyst, and the binder used is aluminum phosphate, and the introduced metal component exerts functions such as enhancing isomerization activity, stability and process selectivity by means of sulfuration, etc.
CN1102360A discloses an alkylaromatic isomerization catalyst, which is composed of a carrier prepared from alumina, mordenite and ZSM-5 zeolite and loaded with noble metals in VIII families such as Pt or Pd. The ZSM-5 zeolite used in the method has a high silicon-aluminum ratio of more than 90, preferably more than 140. The mordenite content of the catalyst support is also relatively high, being at least 5 mass% or more. The ethylbenzene conversion rate of the catalyst reaches 60 percent.
CN100425343C discloses an alkylaromatic hydrocarbon isomerization catalyst, which comprises 24-75 mass% of high-silicon pentasil zeolite with a silica/alumina molar ratio of 25-90, 1.0-4.5 mass% of mordenite and 24-75 mass% of alumina, and further contains 0.01-0.2 mass% of platinum or palladium for alkylaromatic hydrocarbon isomerization, and has good isomerization performance and side chain alkyl removal performance.
Disclosure of Invention
The invention aims to provide an alkyl aromatic hydrocarbon isomerization catalyst, a preparation method and an application thereof.
The alkylaromatic hydrocarbon isomerization catalyst provided by the invention comprises a composite carrier and 0.005-0.2 mass% of VIII group metal calculated by taking the composite carrier as a reference, wherein the composite carrier comprises 48-75 mass% of high-silicon pentasil zeolite, 0.5-3.0 mass% of molybdenum oxide and 24-50 mass% of macroporous alumina, the total pore volume of the catalyst is 0.4-1.5 mL/g, and the total specific surface area is 350-500 m2/g。
The invention uses macroporous pseudo-boehmite, molybdenum oxide and high-silicon five-membered ring zeolite to mix and prepare a composite carrier, then loads VIII group metal to prepare the catalyst, the catalyst is used for aromatic hydrocarbon isomerization reaction, has higher aromatic hydrocarbon isomerization and side chain alkyl removal activity, and has high isomerization selectivity.
Detailed Description
The invention takes high silicon five-membered ring zeolite as an acidic active component, adds a proper amount of molybdenum oxide, takes macroporous alumina as a binder and an active component dispersion matrix to prepare a composite carrier, and then loads noble metal to prepare the catalyst. The molybdenum oxide not only can play a role of a lubricant in the mixing and forming process, but also can improve the properties of acidic components of the catalyst and the use efficiency of the metal active center, has influence on the distribution of different types of acidic centers such as Bronsted and Lewis besides the acid strength and the total acid amount, and optimizes the function of the metal active center; the catalyst has proper macroporous distribution, can improve the mass transfer rate of reactants and reaction products, is beneficial to the reactants to better contact with an active center, and the reaction products can more quickly leave active components. In addition, the introduction of the macroporous alumina can also microscopically influence the distribution of acidic and metal active components and the position relation of a catalytic active center, and the combination with molybdenum oxide can reduce the degree of aromatic hydrocarbon hydrocracking side reaction, aromatic hydrocarbon disproportionation and alkyl transfer side reaction in the reaction process, improve the activity of aromatic hydrocarbon isomerization reaction and play a role in promoting the removal of side chain alkyl reaction of side chain alkyl aromatic hydrocarbon. In addition, the mass transfer efficiency is improved, the control step effect of the catalytic process is improved, and the side reaction is reduced, so that the selectivity of the catalyst is improved.
The composite carrier preferably comprises 55-75 mass% of high-silicon pentasil zeolite, 1.0-2.5 mass% of molybdenum oxide and 24-45 mass% of macroporous alumina.
In order to reduce carbon deposition in the using process of the catalyst and prolong the service life of the catalyst, the catalyst contains VIII family metal, and the content of the VIII family metal is preferably 0.01-0.1 mass%. The group VIII metal is preferably platinum or palladium. The VIII group metal and molybdenum oxide act synergistically to further improve the isomerization performance of the catalyst.
The total pore volume of the catalyst is preferably 0.4-1.0 mL/g, and the total specific surface area is preferably 350-420 m2(ii) in terms of/g. The total pore volume is the sum of pore volumes of micropores and macropores in the catalyst, and the total specific surface area is the sum of specific surface areas of the micropores and macropores in the catalyst. The micropores in the catalyst come from high-silicon five-membered ring zeolite in the composite carrier, and the macropores come from alumina in the composite carrier. Micropores refer to pores having a pore diameter of not more than 2 nm as measured by the BET method, and macropores refer to pores having a pore diameter of more than 2 nm as measured by the BET method, and generally, macropores have a pore diameter ranging from 2 to 60 nm.
In the catalyst, preferably, the pores with the diameter of less than 30 angstroms account for 5-15% of the total pore volume, the pores with the diameter of 30-150 angstroms account for 60-75% of the total pore volume, the pores with the diameter of 150-300 angstroms account for 7-16% of the total pore volume, and the pores with the diameter of more than 300 angstroms account for 4.5-15% of the total pore volume. More preferably, the pores with a diameter of less than 30 angstroms account for 6.5 to 15% of the total pore volume, the pores with a diameter of 30 to 150 angstroms account for 62 to 75% of the total pore volume, the pores with a diameter of 150 to 300 angstroms account for 8 to 16% of the total pore volume, and the pores with a diameter of greater than 300 angstroms account for 4.5 to 15% of the total pore volume.
The high-silicon five-membered ring zeolite is selected from zeolite with MFI and/or MEL structure, or eutectic zeolite of MFI and MEL. The mass ratio of MFI to MEL crystal phase structure in the eutectic zeolite is 0.2-1.5, preferably 0.3-1.2, and the molar ratio of silicon oxide to aluminum oxide of the eutectic zeolite is preferably 25-200, more preferably 60-100. The zeolite of MFI structure is preferably ZSM-5, and the zeolite of MEL structure is preferably ZSM-11.
The eutectic zeolite of MFI and MEL also contains 0.5-3.0 mass% of rare earth elements, and the rare earth elements can be single rare earth elements or mixed rare earth. The zeolite with the eutectic structure has better hydrothermal stability, and is beneficial to maintaining the stability of activity and selectivity of the catalyst. The eutectic zeolite of MFI and MEL is preferably ZSM-5/ZSM-11 eutectic zeolite, which is described in detail and prepared in CN94113403.2(CN 1041399C).
The high-silicon pentasil zeolite has a silica/alumina molar ratio of 25-200, more preferably 60-100.
The preparation method of the catalyst provided by the invention comprises the following steps:
(1) uniformly mixing sodium type high-silicon pentasil zeolite, molybdenum oxide or a precursor thereof and macroporous pseudo-boehmite, adding an aqueous solution of a peptizing agent, kneading, forming, drying, and roasting at 400-650 ℃ in air;
(2) and (2) carrying out ion exchange on the solid roasted in the step (1) by using an ammonium salt solution, washing and drying the obtained solid, soaking the solid by using a solution of a VIII family metal compound, drying the soaked solid, and roasting the dried solid in the air at 400-600 ℃.
The method (1) comprises the steps of forming a carrier, mixing sodium type high-silicon pentasil zeolite, molybdenum oxide or a precursor thereof and macroporous pseudo-boehmite, adding an aqueous solution of a peptizing agent for kneading, wherein the peptizing agent is preferably nitric acid, and the concentration of the nitric acid solution prepared by adding water is preferably 1-5 mass%, more preferably 1.5-3.5 mass%. The addition amount of the nitric acid aqueous solution is 20-80 mass%, preferably 30-60 mass% of the total amount of the solid powder, namely the mixture of the sodium type high-silicon five-membered ring zeolite and the macroporous pseudo-boehmite. The powder added with the peptizing agent is kneaded and then molded, and the molding method preferably adopts extrusion molding, and then drying and roasting are carried out. The drying temperature is preferably 80-130 ℃, and the roasting temperature is preferably 450-650 ℃. The precursor of the molybdenum oxide is preferably molybdenum nitrate or ammonium molybdate, and the ammonium molybdate is preferably ammonium paramolybdate.
The pore volume of the macroporous pseudo-boehmite is preferably 0.8-1.5 mL/g, and the specific surface area is preferably 350-600 m2Per g, preferably 360 to 550m2(ii) in terms of/g. The diameter range of the pores is 2-60 nanometers, and the pores are basically free of micropores.
The pore distribution of the large-pore pseudo-boehmite is preferably as follows: the pores with the diameter of less than 30 angstroms account for 0-6% of the total pore volume, the pores with the diameter of 30-150 angstroms account for 60-80% of the total pore volume, the pores with the diameter of 150-300 angstroms account for 10-25% of the total pore volume, and the pores with the diameter of more than 300 angstroms account for 5-18% of the total pore volume. More preferably, the pores with the diameter of less than 30 angstroms account for 1-6% of the total pore volume, the pores with the diameter of 30-150 angstroms account for 60-80% of the total pore volume, the pores with the diameter of 150-300 angstroms account for 12-24% of the total pore volume, and the pores with the diameter of more than 300 angstroms account for 5-16% of the large pore volume.
And (2) performing ammonium exchange on the molded carrier prepared in the step (1), then impregnating and introducing VIII-family metal, drying and roasting to obtain the catalyst. The ammonium exchange temperature is preferably 25-120 ℃, and more preferably 65-100 ℃. The ammonium salt used for the ammonium exchange is preferably ammonium chloride or ammonium nitrate, and the concentration thereof is preferably 1 to 30% by mass, more preferably 1 to 10% by mass. The ammonium exchange converts the sodium form of the high silicon pentasil zeolite to the ammonium form, which is converted to the hydrogen form in the subsequent calcination process.
(2) Dipping and introducing a group VIII metal to prepare a dipping solution, wherein the preferable group VIII metal compound is chloroplatinic acid or palladium chloride, the liquid/solid volume ratio of the dipping solution prepared by dipping and introducing the group VIII metal to a solid is 1-3, the dipping temperature is preferably 20-95 ℃, the drying temperature of the dipped solid is preferably 40-90 ℃, and the roasting temperature in the air is preferably 400-550 ℃.
The catalyst loaded with the VIII group metal needs to be reduced before use, the reduction temperature is preferably 400-550 ℃, and hydrogen is preferably used as a reduction gas.
The method for isomerizing the alkyl aromatic hydrocarbon comprises the step of enabling the alkyl aromatic hydrocarbon to be in the presence of hydrogen for 2-30 h at the temperature of 280-450 ℃, the pressure of 0.1-2.0 MPa and the mass space velocity of feeding-1And the hydrogen/hydrocarbon molar ratio is 0.2-4.0, and the catalyst is contacted with the catalyst to carry out isomerization reaction.
The isomerization reaction temperature is preferably 320-400 ℃, the pressure is preferably 0.1-1.2 MPa, and the mass space velocity of the reaction feeding is preferably 2-20 h-1More preferably 4 to 15 hours-1。
The alkyl aromatic hydrocarbon is preferably C8~C10The alkyl aromatic hydrocarbon contains a small amount of aromatic hydrocarbon with side chain alkyl, such as C, and the content of the aromatic hydrocarbon is generally 3-20 mass percent besides the isomerization raw material8Ethylbenzene, C, contained in aromatic hydrocarbons9Methyl ethyl benzene contained in aromatic hydrocarbons.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
The pore volume, specific surface area and macropore pore distribution of the large-pore pseudo-boehmite and the catalyst used in the examples and comparative examples were measured by the BET method.
Comparative example 1
(1) Shaping of
Taking SiO2/Al2O3NaZSM-5, molybdenum oxide and pseudoboehmite (manufactured by southern chemical company, trade name SB) in a molar ratio of 80 were mixed in a ratio of 65: 2: 35, the pore volume of the pseudoboehmite SB is 0.47mL/g, the specific surface area is 287m2The pore distribution is shown in Table 1. Adding 2 mass% nitric acid aqueous solution accounting for 40% of the total mass of the powder, kneading, extruding into strips, drying at 120 ℃ for 2 hours, and roasting at 600 ℃ in the air for 3 hours.
(2) Preparation of the catalyst
Taking 100 g of the solid prepared in the step (1), and adding NH with the concentration of 3 mass percent4Ion exchange of the Cl aqueous solution is carried out at 90 ℃ for 2 hours, and then the chloroplatinic acid solution is added in a liquid/solid volume ratio of 2: ratio of 1Example immersion was carried out at 65 ℃ for 12 hours with a platinum content of 0.025 mass% in the chloroplatinic acid solution (relative to the support), and then the impregnated solid was dried at 60 ℃ for 6 hours and calcined at 500 ℃ in air for 4 hours to obtain catalyst B, the composition of which is shown in Table 2, and the physical properties of which are shown in Table 3.
Comparative example 2
The catalyst was prepared by the method of comparative example 1 except that in step (1), ZSM-5 was replaced with La-ZSM-5/ZSM-11 eutectic zeolite (manufactured by Tanshinite Co., Ltd., trade name CDM-5), and SiO of CDM-5 was used2/Al2O3The molar ratio was 75, wherein the La content was 2.50 mass%, the ZSM-5/ZSM-11 mass ratio was 40:60, and the composition and physical properties of the obtained catalyst D are shown in Table 2 and Table 3, respectively.
Example 1
(1) Preparation of the support
Taking SiO2/Al2O3NaZSM-5, molybdenum oxide and macroporous pseudo-boehmite powder (product of Fushu petrochemical company catalyst factory, trade name YH-2) with the molar ratio of 80 are mixed according to the following ratio of 65: : 2: 35 on a dry basis and mixing. Adding a nitric acid aqueous solution with the concentration of 2 mass percent accounting for 40 percent of the total mass of the powder, kneading, extruding into strips, forming, drying for 2 hours at 120 ℃, roasting for 3 hours at 600 ℃ in the air to obtain a composite carrier, wherein the pore volume of the macroporous pseudo-boehmite YH-2 is 0.96mL/g, and the specific surface area is 364m2The pore distribution is shown in Table 1.
(2) Preparation of the catalyst
Taking 100 g of the composite carrier prepared in the step (1), and adding NH with the concentration of 3 mass percent4Ion exchange of the Cl aqueous solution is carried out at 90 ℃ for 2 hours, and then the chloroplatinic acid solution is added in a liquid/solid volume ratio of 2: 1 at 65 ℃ for 12 hours, the platinum content in the chloroplatinic acid solution was 0.025 mass% (relative to the support). The impregnated solid was then dried at 60 ℃ for 6 hours and calcined in air at 500 ℃ for 4 hours to give catalyst F, the composition of which is shown in Table 2 and the physical properties of which are shown in Table 3.
Example 2
A catalyst was prepared as in example 1 except that macroporous pseudoboehmite YH-2 was replaced with macroporous pseudoboehmite YH-15 (manufactured by Fushun petrochemical Co., Ltd.) in step (1)YH-15 had a pore volume of 1.05mL/g and a specific surface area of 368m2The pore distribution is shown in Table 1, the composition of the catalyst G obtained is shown in Table 2, and the physical properties are shown in Table 3.
Example 3
A catalyst was prepared as in example 1, except that the macroporous pseudoboehmite YH-2 was replaced with the macroporous pseudoboehmite YH-20 (manufactured by Fushun petrochemical Co., Ltd.) in step (1), the macroporous pseudoboehmite YH-20 had a pore volume of 1.28mL/g and a specific surface area of 467m2The pore distribution is shown in Table 1, the composition of the catalyst H obtained is shown in Table 2, and the physical properties are shown in Table 3.
Example 4
A catalyst was prepared as in example 1, except that the macroporous pseudoboehmite YH-2 was replaced in step (1) with a macroporous pseudoboehmite (manufactured by Fushu petrochemical Co., Ltd.) of the brand 4230, the macroporous pseudoboehmite 4230 having a pore volume of 0.90mL/g and a specific surface area of 523m2The pore distribution is shown in Table 1, the composition of the resulting catalyst I is shown in Table 2, and the physical properties are shown in Table 3.
Example 5
A catalyst was prepared as in example 1, except that in step (1) La-ZSM-5/ZSM-11 eutectic zeolite (manufactured by Tanshinite Co., Ltd., trade name CDM-5) was used in place of ZSM-5, and SiO of CDM-5 was used2/Al2O3A molar ratio of 75, wherein the La content is 2.50 mass%, the ZSM-5/ZSM-11 mass ratio is 40:60, the composition of the obtained catalyst K is shown in Table 2, and the physical properties are shown in Table 3.
Example 6
A catalyst was prepared as in example 2, except that in step (1) La-ZSM-5/ZSM-11 eutectic zeolite (manufactured by Takara petrochemical Co., Ltd., trade name CDM-5) was used in place of ZSM-5, and the composition and physical properties of the obtained catalyst L are shown in Table 2 and Table 3, respectively.
Example 7
A catalyst was prepared as in example 3, except that in step (1) La-ZSM-5/ZSM-11 eutectic zeolite (manufactured by Takara petrochemical Co., Ltd., trade name CDM-5) was used in place of ZSM-5, and the composition of the resulting catalyst M is shown in Table 2 and the physical properties are shown in Table 3.
Example 8
A catalyst was prepared as in example 4, except that in step (1) La-ZSM-5/ZSM-11 eutectic zeolite (manufactured by Takara petrochemical Co., Ltd., trade name CDM-5) was used in place of ZSM-5, and the composition and physical properties of the obtained catalyst N were as shown in Table 2 and Table 3, respectively.
Examples 9 to 13
The following examples evaluate the reactivity of the catalysts.
A fixed bed reactor having an inner diameter of 18 mm was charged with 20 g of the catalyst, and the catalyst was reduced in a hydrogen atmosphere at 500 ℃ for 4 hours by introducing hydrogen. Introduction of C as shown in Table 48The aromatic hydrocarbon raw material is subjected to xylene isomerization and ethylbenzene conversion reaction. The reaction conditions are as follows: 380 ℃, 0.45MPa and the feeding mass space velocity of 12h-1The hydrogen/hydrocarbon molar ratio was 1.0. The catalysts used and the reaction results for each example are shown in Table 4.
Examples 14 to 18
The catalysts were evaluated for their reactivity in accordance with the procedure of example 9, and the catalysts used in the examples and the reaction results are shown in Table 5.
Examples 19 to 21
The following example evaluates catalyst C9Aromatic isomerization reaction performance.
The isomerization performance of catalysts B, H and I was evaluated as in example 9, except that C as listed in Table 6 was used9The aromatic hydrocarbons were used as the starting materials, and the catalysts and reaction results used in the examples are shown in Table 6.
As can be seen from tables 4 and 5, the selectivity of ethylbenzene to benzene and the yield of xylenes were higher in the catalyst of the present invention than in the comparative catalyst. The catalyst of the invention has better arene isomerization selectivity, can maintain higher reaction activity, realizes xylene isomerization with high efficiency, and effectively removes ethyl in ethylbenzene to convert the ethyl into benzene.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
The bullets indicate:
C7- NA–C7and C7Light non-aromatic hydrocarbons, C8 NA–C8Nonaromatic hydrocarbons, B-benzene, T-toluene, EB-ethylbenzene, PX-p-xylene, MX-m-xylene, OX-o-xylene, C9+ A–C9And C9The above heavy aromatic hydrocarbon, X-xylene.
PX/X: characterizing the isomerization activity of the catalyst, and the concentration of PX/X is the concentration of PX in the product/X in the product is multiplied by 100 percent;
EBC: characterizing the ethylbenzene conversion capacity of the catalyst, i.e. EBC (EB concentration in raw material-EB concentration in product)/EB concentration in raw material) x 100%;
XY: xylene yield, characterizing catalyst isomerization selectivity, XY ═ X concentration in the product/X concentration in the feed × 100%;
BS: the selectivity of the catalyst ethylbenzene to benzene was characterized by BS ═ B concentration in product/78/(EB concentration in feed-EB concentration in product)/106) × 100% in mol%.
TABLE 5
TABLE 6
Description of the symbols:
NA-nonaromatic hydrocarbons, B-benzene, T-toluene, EB-ethylbenzene, X-xylene, MEB-methylethylbenzene, 135-TMB-mesitylene, 124-TMB-pseudotrimethylbenzene, 123-TMB-hemimellitene, TeMB-tetramethylbenzene, Others-other components, TMB-trimethylbenzene.
Selectivity of mesitylene: 135-TMB/TMB-product 135-TMB concentration/TMB concentration in product × 100%;
conversion of ethylbenzene: cMEB(MEB concentration in feed-MEB concentration in product)/MEB concentration in feed × 100%;
yield of trimethylbenzene: selectivity Y characterizing the isomerization ProcessTMBTMB concentration in product/TMB concentration in feed × 100%.
Claims (18)
1. An alkylaromatic isomerization catalyst comprises a composite carrier and 0.005-0.2 mass% of VIII group metal calculated by taking the composite carrier as a reference, wherein the composite carrier comprises 48-75 mass% of high-silicon pentasil zeolite, 0.5-3.0 mass% of molybdenum oxide and 24-50 mass% of macroporous alumina, the total pore volume of the catalyst is 0.4-1.5 mL/g, and the total specific surface area is 350-500 m2/g。
2. The catalyst according to claim 1, wherein the composite support comprises 55 to 75 mass% of the high-silicon pentasil zeolite, 1.0 to 2.5 mass% of molybdenum oxide, and 24 to 45 mass% of the macroporous alumina.
3. The catalyst according to claim 1 or 2, wherein the catalyst comprises 5 to 15% by volume of total pores of pores having a diameter of less than 30 angstroms, 60 to 75% by volume of total pores of pores having a diameter of 30 to 150 angstroms, 7 to 16% by volume of total pores of pores having a diameter of 150 to 300 angstroms, and 4.5 to 15% by volume of total pores of pores having a diameter of more than 300 angstroms.
4. The catalyst according to claim 1 or 2, wherein the catalyst comprises 6.5 to 15% by volume of total pores of pores having a diameter of less than 30 angstroms, 62 to 75% by volume of total pores of pores having a diameter of 30 to 150 angstroms, 8 to 16% by volume of total pores of pores having a diameter of 150 to 300 angstroms, and 4.5 to 15% by volume of total pores of pores having a diameter of more than 300 angstroms.
5. The catalyst according to claim 1 or 2, characterized in that the total pore volume of the catalyst is 0.4 to 1.0mL/g and the total specific surface area is 350 to 420m2/g。
6. A catalyst according to claim 1 or claim 2 characterised in that the group viii metal is selected from platinum or palladium.
7. Catalyst according to claim 1 or 2, characterized in that the high-silicon pentasil zeolite is selected from zeolites of the MFI and/or MEL structure, or eutectic zeolites of MFI and MEL.
8. The catalyst according to claim 7, wherein the eutectic zeolite of MFI and MEL further contains 0.5 to 3.0 mass% of a rare earth element.
9. Catalyst according to claim 7, characterized in that the zeolite of MFI structure is ZSM-5 and the zeolite of MEL structure is ZSM-11.
10. The catalyst according to claim 1 or 2, wherein the high-silicon pentasil zeolite has a silica/alumina molar ratio of 25 to 200.
11. The catalyst according to claim 1 or 2, wherein the group VIII metal is contained in an amount of 0.01 to 0.1% by mass.
12. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) uniformly mixing sodium type high-silicon pentasil zeolite, molybdenum oxide or a precursor thereof and macroporous pseudo-boehmite, adding an aqueous solution of a peptizing agent, kneading, forming, drying, and roasting at 400-650 ℃ in air;
(2) and (2) carrying out ion exchange on the solid roasted in the step (1) by using an ammonium salt solution, washing and drying the obtained solid, soaking the solid by using a solution of a VIII family metal compound, drying the soaked solid, and roasting the dried solid in the air at 400-600 ℃.
13. The process of claim 12 wherein the group VIII metal compound is chloroplatinic acid or palladium chloride.
14. The method according to claim 12, wherein the precursor of molybdenum oxide in step (1) is molybdenum nitrate or ammonium molybdate.
15. The method according to claim 12, wherein the macroporous pseudoboehmite has a pore volume of 0.8 to 1.5mL/g and a specific surface area of 350 to 600m2/g。
16. The method according to claim 15, wherein the large pore pseudo-boehmite contains 0 to 6% of the total pore volume of pores having a diameter of less than 30 angstroms, 60 to 80% of the total pore volume of pores having a diameter of 30 to 150 angstroms, 10 to 25% of the total pore volume of pores having a diameter of 150 to 300 angstroms, and 5 to 18% of the total pore volume of pores having a diameter of more than 300 angstroms.
17. An alkylaromatic isomerization method comprises the steps of enabling alkylaromatic hydrocarbon to exist in the presence of hydrogen, at the temperature of 280-450 ℃, the pressure of 0.1-2.0 MPa and the feeding mass space velocity of 2-30 h-1And a hydrogen/hydrocarbon molar ratio of 0.2 to 4.0, and the catalyst of claim 1.
18. The method of claim 17 wherein said alkylaromatic hydrocarbon is C8~C10The aromatic hydrocarbon of (1).
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