CN115155650B - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
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- CN115155650B CN115155650B CN202210918350.0A CN202210918350A CN115155650B CN 115155650 B CN115155650 B CN 115155650B CN 202210918350 A CN202210918350 A CN 202210918350A CN 115155650 B CN115155650 B CN 115155650B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 23
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000011068 loading method Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- 238000006317 isomerization reaction Methods 0.000 claims description 75
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 238000001354 calcination Methods 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 150000002989 phenols Chemical class 0.000 claims description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 15
- 229940010552 ammonium molybdate Drugs 0.000 claims description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 15
- 239000011609 ammonium molybdate Substances 0.000 claims description 15
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 239000004254 Ammonium phosphate Substances 0.000 claims description 10
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 10
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 74
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 18
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 4
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention provides a catalyst, a preparation method and application thereof. The catalyst comprises a carrier, silicon dioxide and an active component; wherein the carrier is a molecular sieve; the active component is metal phosphate and/or oxide formed by heteropolyacid; the silica and the active ingredient are dispersed on a carrier. By loading active components, the pore structure and the reaction sites of the carrier can be effectively improved, so that the problems of low activity, poor selectivity and short service life of the catalyst are solved. Under the action of ion exchange, metal in the carrier skeleton can be replaced by metal in the active component, so that the acid site in the catalyst is changed, and the activity of the catalyst is improved. The phosphorus element in the metal phosphate and the polyatoms in the heteropoly acid are dispersed in the carrier framework, so that the pore channel structure of the catalyst can be improved, and the selectivity of the catalyst is improved; and the carbon deposition resistance of the catalyst can be improved, so that the activity and stability of the catalyst are improved, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst and a preparation method and application thereof.
Background
The m-cresol and p-cresol mixture is an important chemical intermediate and is widely applied to the fields of pesticides, plastics, medicines, wire enamels and the like. High-purity m-cresol can be obtained by utilizing an isobutene reaction method and a urea complexation crystallization method, and high-purity m-cresol and p-cresol can be respectively obtained by adopting an adsorption separation method.
The method for obtaining m-cresol and p-cresol mainly comprises a natural separation method and a chemical synthesis method. The natural separation method, i.e. the separation of m-cresol from coal tar, is characterized by limited resources, complex process and continuous elimination of natural separation devices since the success of chemical synthesis. The main methods for synthesizing the m-cresol by a chemical method are a p-chlorotoluene hydrolysis method, an o-cresol isomerization method and a phenol alkylation method. Wherein, the o-cresol isomerization method has the highest atom economy and accords with the environment-friendly concept.
2, 6-dimethylphenol is a very important chemical intermediate, and as with o-cresol, 2, 6-dimethylphenol can also undergo isomerization reactions. 2, 6-dimethylphenol is isomerized to form 2, 5-dimethylphenol, 2, 4-dimethylphenol, 2, 3-dimethylphenol, 3, 4-dimethylphenol and 3, 5-dimethylphenol with wider application and higher added value.
However, most of catalysts used for isomerization reaction in the prior art are homogeneous catalysts, and cannot be recycled; in the catalytic isomerization reaction of the existing heterogeneous catalyst, the activity of the catalyst is low, the selectivity is poor, and the catalyst is easy to deactivate.
Disclosure of Invention
The invention mainly aims to provide a catalyst, a preparation method and application thereof, and aims to solve the problems of low activity, poor selectivity and short service life of the catalyst for isomerization reaction in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a catalyst comprising a support, silica, and an active component; wherein the carrier is a molecular sieve; the active component is metal phosphate and/or oxide formed by heteropolyacid; the silica and the active ingredient are dispersed on a carrier.
Further, the mass content of the active component is 3-15% of the carrier, and the mass content of the silicon dioxide is 3-15% of the carrier.
Further, the carrier is selected from any one or more of HZSM-5, MCM-22, MCM-41 and SAPO-11 molecular sieves; preferably the metal phosphate is aluminium phosphate and/or iron phosphate, preferably the heteropolyacid is ammonium molybdate and/or silicotungstic acid.
Further, the active component is an oxide formed by metal phosphate and heteropolyacid; preferably, the active component is an oxide formed from two or more of aluminum phosphate, iron phosphate or ammonium molybdate.
Further, the pore volume of the carrier is 0.2-0.7 mL/g, the pore diameter is 1.5-5 nm, and the specific surface area is 300-600 m 2 Preferably, the pore volume of the carrier is 0.25-0.5 mL/g, the pore diameter is 2.0-5.0 nm, and the specific surface area is 400-500 m 2 /g。
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for producing the above catalyst, comprising: carrying out a first calcination reaction on the carrier loaded with the active compound to obtain a carrier loaded with the active component; the active compound is a metal phosphate precursor and/or a heteropoly acid precursor; mixing the carrier loaded with the active components with an adhesive and performing a second calcination reaction to obtain a catalyst; the binder is a silica precursor, preferably the binder is a silica sol.
Further, the active compound is a metal phosphate and/or a heteropolyacid; preferably, when the active compound is a metal phosphate precursor, the active compound-loaded carrier is prepared by the following method: loading an aqueous metal salt solution, phosphoric acid and/or ammonium phosphate solution onto a carrier to obtain a carrier loaded with an active compound; wherein the metal salt is metal nitrate and/or metal sulfate, and metal ions in the metal salt are the same as metal ions in the metal phosphate precursor; when the active compound is a heteropoly acid precursor, the aqueous solution of the heteropoly acid precursor is loaded onto a carrier to obtain the carrier loaded with the active compound.
Further, the temperature of the first calcination reaction is 400-600 ℃, and the time of the first calcination reaction is 1-4 hours; the temperature of the second calcination reaction is 400-600 ℃, and the time of the second calcination reaction is 2-6 h.
According to another aspect of the present invention, there is provided an isomerisation reaction comprising: introducing a phenolic compound, toluene and the catalyst into a fixed bed reactor for reaction; the phenolic compound has the following general structure:
wherein R is 1 、R 2 Independently C 1 ～C 5 Alkyl or H.
Further, the mass ratio of the phenolic compound to the toluene is 9:1-7:3; preferably, the phenolic compound is o-cresol and/or 2, 6-dimethylphenol.
Further, the mass of the phenolic compound is emptyThe speed is 0.4-6 hr -1 Or 1-20 hr -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is preferably 330 to 350℃or 280 to 310 ℃.
By adopting the technical scheme of the invention, the pore structure and the reaction site of the carrier can be effectively improved by loading the active components, so that the problems of low activity, poor selectivity and short service life of the catalyst are solved. Under the effect of ion exchange, because different metals have different electron donating capacities, metal elements in the active component can replace metals in the carrier framework, so that acid sites in the catalyst are changed, and the activity of the catalyst is improved. The phosphorus element in the metal phosphate and the polyatoms in the heteropoly acid are dispersed in the carrier framework, so that the pore channel structure of the catalyst can be improved, and the selectivity of the catalyst is improved; and the carbon deposition resistance of the catalyst can be improved, so that the activity and stability of the catalyst are improved, and the service life of the catalyst is prolonged.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background art, the prior art has the problems of low activity and poor selectivity of the catalyst used for the isomerization reaction. In order to solve the problems, the application provides a catalyst, and a preparation method and application thereof.
In one exemplary embodiment of the present application, a catalyst is provided that includes a support, silica, and an active component; wherein the carrier is a molecular sieve; the active component is metal phosphate and/or oxide formed by heteropolyacid; the silica and the active ingredient are dispersed on a carrier.
The catalyst provided by the application can effectively improve the pore structure and the reaction site of the carrier through loading the active components so as to solve the problems of low catalyst activity, poor selectivity and short service life. Under the effect of ion exchange, because different metals have different electron donating capacities, metal elements in the active component can replace metals in the carrier framework, so that acid sites in the catalyst are changed, and the activity of the catalyst is improved. The phosphorus element in the metal phosphate and the polyatoms in the heteropoly acid are dispersed in the carrier framework, so that the pore channel structure of the catalyst can be improved, and the selectivity of the catalyst is improved; and the carbon deposition resistance of the catalyst can be improved, so that the activity and stability of the catalyst are improved, and the service life of the catalyst is prolonged.
Particularly, for the isomerization reaction of the phenolic compound, if the pore canal of the catalyst is smaller or narrower, the reaction molecules are not easy to overflow, so that the raw material residence time is too long, excessive reaction is caused, the reaction is caused on other sites of the phenolic compound, the reaction selectivity is poor, and the yield of the target product is low; meanwhile, carbon deposition is easy to occur to the catalyst under the acidic condition, and the catalyst active site is covered, so that the service life of the catalyst is short. The pore structure of the catalyst has an important influence on the progress of the reaction. The catalyst can effectively solve the problems of low catalyst activity, poor selectivity and short service life in the isomerization reaction of the phenolic compound.
In some embodiments, to further increase the activity and selectivity of the catalyst, the active component is present in an amount of 3 to 15% by mass of the support and the silica is present in an amount of 3 to 15% by mass of the support. Excessive content of active components can cause excessive acidity of the catalyst, thereby causing carbon deposition; too little active component content does not act to increase the catalyst reaction sites.
In some embodiments, the support is selected from any one or more of HZSM-5, MCM-22, MCM-41, SAPO-11 molecular sieves. The molecular sieve has a proper pore structure and strong surface acidity, and has high activity and selectivity when being applied to isomerization reaction. Preferably the metal phosphate is aluminium phosphate and/or iron phosphate, preferably the heteropolyacid is ammonium molybdate and/or silicotungstic acid. As the activity of the catalyst can be improved by improving the acidity, compared with alkali metal elements such as Na, K and the like, the metal elements selected by the method can form Lewis acid and increase the acidic sites, thereby improving the activity of the catalyst. Particularly, when the carrier itself contains aluminum, the aluminum can more remarkably increase the acid sites of the catalyst, improve the acid strength and distribution, and further improve the activity of the catalyst.
In some embodiments, the active component is an oxide formed from a metal phosphate and a heteropolyacid; preferably, the active component is an oxide formed from two or more of aluminum phosphate, iron phosphate or ammonium molybdate. The metal phosphate and the heteropolyacid are loaded on the carrier at the same time to have synergistic effect, so that the activity and stability of the catalyst can be further improved. And, when the catalyst is applied to the isomerization reaction, the reaction site can be effectively improved, thereby improving the selectivity. And because of the existence of elements such as P, the pore channel structure can be improved, carbon deposition is inhibited, and the service life of the catalyst is prolonged.
In some embodiments, in order to ensure the activity and selectivity of the catalyst, the pore structure of the support should not be too small or too narrow, it is preferable that the pore volume of the support be 0.2 to 0.7mL/g, the pore diameter be 1.5 to 5nm, and the specific surface area be 300 to 600m 2 Preferably, the support has a pore volume of 0.25 to 0.5mL/g, a pore diameter of 2.0 to 5.0nm, and a specific surface area of 400 to 500m 2 /g。
In another exemplary embodiment of the present application, there is provided a method for preparing the above catalyst, the method comprising: carrying out a first calcination reaction on the carrier loaded with the active compound to obtain a carrier loaded with the active component; the active compound is a metal phosphate precursor and/or a heteropoly acid precursor; mixing the carrier loaded with the active components with an adhesive and performing a second calcination reaction to obtain a catalyst; the binder is a silica precursor. Preferably the binder is a silica sol.
The method comprises the steps of mixing the carrier with the active compound, fully loading the active component on the carrier, mixing the carrier with the adhesive, and calcining, so that the catalyst has good stability. The preparation method is simple, and the prepared catalyst has high activity, high selectivity and long service life.
To further increase the stability and activity of the catalyst, in some embodiments, the active compound is a metal phosphate and/or a heteropolyacid, preferably, when the active compound is a metal phosphate precursor, the support carrying the active compound is prepared by the following method: loading an aqueous metal salt solution, phosphoric acid and/or ammonium phosphate solution onto a carrier to obtain a carrier loaded with an active compound; wherein the metal salt is metal nitrate and/or metal sulfate, and metal ions in the metal salt are the same as metal ions in the metal phosphate precursor; when the active compound is a heteropoly acid precursor, the aqueous solution of the heteropoly acid precursor is loaded onto a carrier to obtain the carrier loaded with the active compound.
The concentration of the aqueous metal salt solution is not particularly limited as long as the metal salt is completely dissolved. The present application preferably employs an isovolumetric impregnation method to support the active compounds described above on a support. For example, an aqueous solution containing 5g of aluminum nitrate and an aqueous solution containing 2.3g of phosphoric acid were successively supported on 50g of HZSM-5 molecular sieve by an isovolumetric impregnation method to obtain an aluminum phosphate-supported molecular sieve.
When the active compound is a metal phosphate precursor, the metal salt solution phosphoric acid or ammonium phosphate aqueous solution is loaded on the carrier by adopting an equal-volume impregnation method, so that the active components are fully loaded on the carrier, the stability between the carrier and the active components is improved, and meanwhile, the active components are uniformly dispersed, so that the service life of the catalyst is effectively prolonged.
In order to bring the content of the active component in the catalyst into the above range, thereby improving the activity of the catalyst and suppressing carbon deposition, in some embodiments, the active compound is preferably contained in an amount of 10 to 85% by mass of the carrier, and the binder is preferably contained in an amount of 5 to 20% by mass of the carrier.
The conditions of the calcination reaction are not particularly limited, and the conditions commonly used in the art can be applied to the present application. For example, in some embodiments, the temperature of the first calcination reaction is 400 to 600 ℃, and the time of the first calcination reaction is 1 to 4 hours; the second calcination reaction time is 400-600 ℃, and the second calcination reaction temperature is 2-6 h.
In yet another exemplary embodiment of the present application, there is provided an isomerization reaction including: introducing a phenolic compound, toluene and the catalyst into a fixed bed reactor for reaction; the phenolic compound has the following general structure:
wherein R is 1 、R 2 Independently C 1 ～C 5 Alkyl or H.
The isomerization reaction using the catalyst has high selectivity, high conversion rate of reaction raw materials and fewer byproducts; and the catalyst has long service life, is not easy to deactivate and can be recycled.
In order to allow the reactants to react sufficiently and avoid excessive byproducts, in some embodiments, the mass ratio of phenolic compound to toluene is 9:1 to 7:3; preferably, the phenolic compound is o-cresol or 2, 6-dimethylphenol. Since the isomerization reaction is a continuous reaction, the catalyst is filled once, and the catalyst is preferably filled in an amount of 50g to 60g.
The catalyst can effectively reduce energy consumption and improve production efficiency. For example, in some embodiments, the catalyst of the present application is used to increase the mass space velocity of the reactants at the same temperature, preferably the mass space velocity of the phenolic compound is from 0.4 to 6hr -1 Or 1-20 hr -1 The method comprises the steps of carrying out a first treatment on the surface of the Under the condition that other conditions are the same, the catalyst can effectively reduce the reaction temperature, improve the production efficiency and avoid the generation of high-boiling byproducts, and the reaction temperature is preferably 330-350 ℃ or 280-310 ℃.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
The catalyst was prepared as follows:
(1) The active components are loaded by adopting an isovolumetric impregnation method: the aqueous solution containing 10g of aluminum nitrate is firstly loaded to 50g of HZSM-5 molecular sieve (the pore diameter of the molecular sieve is 2nm, the pore volume is 0.25mL/g, and the surface area is 450 m) 2 And/g) obtaining a molecular sieve loaded with aluminum nitrate; then 4.6g of phosphoric acid aqueous solution is loaded on the molecular sieve loaded with aluminum nitrate to obtainTo an aluminum phosphate loaded molecular sieve;
(2) Drying the molecular sieve loaded with aluminum phosphate at 120 ℃ for 3 hours, and calcining the molecular sieve at 500 ℃ for 2 hours to obtain a carrier 1 loaded with active components, wherein the mass content of the active components is 5.4% of that of the HZSM-5 molecular sieve;
(3) Mixing the carrier 1 loaded with the active components and 25g of 30% silica sol uniformly, extruding the mixture, naturally airing the mixture, drying the mixture at 120 ℃ for 3 hours, calcining the mixture at 500 ℃ for 3 hours, and dispersing silica formed by the silica sol after calcining on the carrier 1 to obtain the catalyst Cat-1.
The o-cresol isomerisation reaction is as follows:
the reaction of preparing m-cresol and p-cresol by isomerizing o-cresol on a fixed bed reactor is carried out by using the catalyst Cat-1. The reaction conditions are as follows: the catalyst loading is 50g, the o-cresol and toluene (the mass ratio of the o-cresol to the toluene is 4:1) are preheated at 330 ℃, and react in a fixed bed under the action of the catalyst, the reaction temperature is 330 ℃, the pressure is normal pressure, and the mass airspeed of the o-cresol is 0.4hr -1 . The reaction results are shown in Table 1.
The 2, 6-xylenol isomerization reaction is as follows:
the reaction for preparing mixed xylenol by isomerizing 2, 6-xylenol is carried out on a fixed bed reactor, using the catalyst Cat-1 described above. The reaction conditions are as follows: the catalyst loading is 50g,2, 6-dimethylphenol and benzene (mass ratio of 4:1) are preheated at 280 ℃, reacted in a fixed bed under the action of the catalyst, the reaction temperature is 280 ℃, the pressure is normal pressure, and the mass space velocity of 2, 6-dimethylphenol is 1.6hr -1 . The reaction results are shown in Table 2.
Example 2
In the difference from example 1, in the step (1), an aqueous solution containing 7g of ammonium phosphate was used instead of an aqueous solution containing 4.6g of phosphoric acid, to obtain a catalyst Cat-2. Catalyst Cat-2 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 3
(1) The active components are loaded by adopting an isovolumetric impregnation method: loading 5g of an aqueous solution containing ammonium molybdate onto 50g of an HZSM-5 molecular sieve to obtain an ammonium molybdate loaded molecular sieve; (2) Drying the molecular sieve loaded with ammonium molybdate at 120 ℃ for 3 hours, and then performing first calcination at 550 ℃ for 2 hours to obtain a carrier 3 loaded with active components; wherein the mass content of the active component is 7.4% of that of the HZSM-5 molecular sieve.
(3) Mixing the carrier 3 loaded with the active components and 25g of 30% silica sol uniformly, extruding strips, naturally airing, drying at 120 ℃ for 3 hours, and calcining at 550 ℃ for 4 hours to obtain the catalyst Cat-3.
Catalyst Cat-3 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 4
Unlike example 3, in step (1), ammonium molybdate was replaced with silicotungstic acid to obtain catalyst Cat-4.
Catalyst Cat-4 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 5
Unlike example 1, in step (1), an aqueous solution of ferric nitrate was used instead of an aqueous solution of aluminum nitrate; an aqueous solution containing 7g of ammonium phosphate was used in place of the aqueous solution containing 4.6g of phosphoric acid to obtain catalyst Cat-5.
Catalyst Cat-5 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 6
Unlike example 1, in step (1), an aqueous solution containing 8.28g of ferric sulfate was used instead of an aqueous solution containing 10g of aluminum nitrate; an aqueous solution containing 7g of ammonium phosphate was used in place of the aqueous solution containing 4.6g of phosphoric acid to obtain catalyst Cat-6.
Catalyst Cat-6 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 7
Unlike example 1, in step (1), an aqueous solution containing 5g of aluminum nitrate was used instead of an aqueous solution containing 10g of aluminum nitrate; the aqueous solution containing 2.3g of phosphoric acid is used for replacing the aqueous solution containing 4.6g of phosphoric acid, and the obtained carrier 7 loaded with the active component has the mass content of 3% of HZSM-5 molecular sieve, so as to obtain the catalyst Cat-7.
The catalyst Cat-7 is used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the o-cresol isomerization reaction temperature and the preheating temperature are 340 ℃, and the 2, 6-xylenol isomerization reaction temperature and the preheating temperature are 285 ℃ respectively.
Example 8
Unlike example 1, in step (1), 27.78g of aluminum nitrate was used instead of 10g of aluminum nitrate; the active component-supporting carrier 8 obtained by replacing 4.6g of phosphoric acid with 12.78g of phosphoric acid has a mass content of 15% of that of the HZSM-5 molecular sieve.
Catalyst Cat-8 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the mass space velocity of the o-cresol in the o-cresol isomerization reaction was 1.3hr -1 The mass space velocity of 2, 6-dimethylphenol in the 2, 6-xylenol isomerization reaction is 5.6hr -1 The other conditions were the same as in example 1.
Example 9
Unlike example 1, in step (1), 1.85g of aluminum nitrate was used instead of 10g of aluminum nitrate; the active component-loaded molecular sieve catalyst 9 was obtained by replacing 4.6g of phosphoric acid with 0.85g of phosphoric acid, wherein the mass content of the active component was 1% of that of the HZSM-5 molecular sieve.
Catalyst Cat-9 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 10
Unlike example 1, in step (1), 35g of aluminum nitrate was used instead of 10g of aluminum nitrate; the active component-supporting carrier 10 was obtained by replacing 4.6g of phosphoric acid with 16.1g of phosphoric acid, wherein the mass content of the active component was 18.9% of that of the HZSM-5 molecular sieve. The catalyst Cat-10 is obtained.
Catalyst Cat-10 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 11
Unlike example 1, in step (2), the molecular sieve loaded with aluminum phosphate was subjected to first calcination at 400 ℃ for 4 hours to obtain the active component-loaded carrier 11, wherein the mass content of the active component is 5.4% of that of the HZSM-5 molecular sieve; in the step (3), the carrier 11 loaded with the active components and 25g of 30% silica sol are uniformly mixed, extruded and naturally dried, dried for 3 hours at 120 ℃, and then calcined for 6 hours at 400 ℃ to obtain the catalyst Cat-11.
Catalyst Cat-11 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 12
Unlike example 1, in step (2), the molecular sieve loaded with aluminum phosphate was subjected to first calcination at 600 ℃ for 1 hour to obtain the active component-loaded carrier 12, wherein the mass content of the active component is 5.4% of that of the HZSM-5 molecular sieve;
in the step (3), the carrier 12 loaded with the active components and 25g of 30% silica sol are uniformly mixed, extruded and naturally dried, dried for 3 hours at 120 ℃, and then calcined for 2 hours at 600 ℃ to obtain the catalyst Cat-12.
Catalyst Cat-12 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Example 13
Unlike example 1, the preheating temperature and the reaction temperature of the o-cresol isomerization reaction were 340℃and the mass space velocity was 1.0hr -1 。
Example 14
Unlike example 1, the preheating temperature and the reaction temperature of the o-cresol isomerization reaction were 350℃and the mass space velocity was 1.8hr -1 。
Example 15
Unlike example 1, the preheating temperature and the reaction temperature for the o-cresol isomerization reaction were 360℃and the mass space velocity was 6hr -1 。
Example 16
Unlike example 1, the preheating temperature and the preheating temperature of the 2, 6-xylenol isomerization reactionThe reaction temperature is 310 ℃, and the mass space velocity is 12hr -1 。
Example 17
Unlike example 1, the preheating temperature and the reaction temperature of the 2, 6-xylenol isomerization reaction were 320℃and the mass space velocity was 20hr -1 。
Example 18
Unlike example 1, in the o-cresol isomerization reaction, the space velocity of o-cresol was 1.0hr -1 The method comprises the steps of carrying out a first treatment on the surface of the In the isomerization reaction of 2, 6-xylenol, the mass space velocity of 2, 6-dimethylphenol is 2.0hr -1 。
Example 19
(1) Firstly, loading active components by adopting an isovolumetric impregnation method: loading 5g of aqueous solution containing aluminum nitrate onto 50g of HZSM-5 molecular sieve to obtain a molecular sieve loaded with aluminum nitrate; then loading 2.3g of phosphoric acid and 2.5g of ammonium molybdate into the molecular sieve loaded with aluminum nitrate to obtain the molecular sieve loaded with aluminum phosphate and ammonium molybdate;
(2) Drying the molecular sieve loaded with aluminum phosphate and ammonium molybdate at 120 ℃ for 3 hours, and then performing first calcination at 500 ℃ for 2 hours to obtain a carrier 20 loaded with active components, wherein the mass content of the active components is 7.70% of that of the HZSM-5 molecular sieve;
(3) Mixing the molecular sieve catalyst 19 and 25g 30% silica sol uniformly, extruding strips, naturally airing, drying at 120 ℃ for 3 hours, and calcining at 500 ℃ for 3 hours to obtain the catalyst Cat-19.
Catalyst Cat-19 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the procedure of which was the same as in example 1.
Comparative example 1
(1) Loading 10g of aqueous solution containing aluminum nitrate onto 50g of HZSM-5 molecular sieve by adopting an isovolumetric impregnation method to obtain the molecular sieve loaded with aluminum nitrate;
(2) Drying the molecular sieve loaded with aluminum nitrate at 120 ℃ for 3 hours, and then performing first calcination at 500 ℃ for 2 hours to obtain a molecular sieve catalyst D1 loaded with active components;
(3) Uniformly mixing D1 and 25g of 30% silica sol, extruding, naturally airing, drying at 120 ℃ for 3 hours, and calcining at 500 ℃ for 3 hours to obtain the catalyst Cat D1.
The o-cresol isomerisation reaction is as follows:
the reaction of m-cresol and p-cresol was carried out in a fixed bed reactor by isomerizing o-cresol to prepare m-cresol and p-cresol, and the catalyst Cat D1 was used. The reaction conditions are as follows: the catalyst loading is 50g, the o-cresol and toluene (mass ratio of 4:1) are preheated at 330 ℃, and react in a fixed bed under the action of the catalyst, the reaction temperature is 330 ℃, the pressure is normal pressure, and the mass airspeed of the o-cresol is 0.4hr -1 . The reaction results are shown in Table 1.
The 2, 6-xylenol isomerization reaction is as follows:
the reaction for preparing mixed xylenol by isomerizing 2, 6-xylenol is carried out on a fixed bed reactor, using the catalyst Cat D1 described above. The reaction conditions are as follows: the catalyst loading is 50g,2, 6-dimethylphenol and benzene (the mass ratio of 2, 6-dimethylphenol to benzene is 4:1) are preheated at 310 ℃, and react in a fixed bed under the action of the catalyst, wherein the reaction temperature is 310 ℃, the pressure is normal pressure, and the mass space velocity of 2, 6-dimethylphenol is 1.6hr -1 . The reaction results are shown in Table 2.
Comparative example 2
Unlike comparative example 1 in which the number of the rolls was not limited,
the catalyst was prepared as follows:
(1) Firstly, loading 5g of ammonium phosphate-containing aqueous solution onto 50g of HZSM-5 molecular sieve by adopting an isovolumetric impregnation method to obtain ammonium phosphate-loaded molecular sieve;
(2) Drying the molecular sieve loaded with ammonium phosphate at 120 ℃ for 3 hours, and calcining the molecular sieve at 500 ℃ for 2 hours to obtain a molecular sieve catalyst D2 loaded with active components;
(3) Uniformly mixing the molecular sieve catalyst D2 and 25g of 30% silica sol, extruding, naturally airing, drying at 120 ℃ for 3 hours, and calcining at 500 ℃ for 3 hours to obtain the catalyst Cat-D2.
Catalyst Cat-D2 was used for the o-cresol isomerization reaction and the 2, 6-xylenol isomerization reaction, the reaction procedure was the same as comparative example 1.
Comparative example 3
Untreated HZSM-5 molecular sieve was used as catalyst.
The mass space velocity of the o-cresol in the o-cresol isomerization reaction is 0.4hr -1 Preheating and reacting at 330 ℃.
The mass space velocity of 2, 6-dimethylphenol in the 2, 6-xylenol isomerization reaction is 2hr -1 Preheating and reaction temperature 310 ℃.
Comparative example 4
The catalyst Cat-1 of example 1 was used to catalyze the carbon octaarene isomerization reaction. The catalyst loading was 100g, the feed was 15% ethylbenzene and 85% meta-xylene, the hydrogen pressure was 0.5MPa, the flow rate was 70mL/min, the reaction temperature was 360℃and the light oil molar ratio was 2.0, the mass space velocity was 4.5hr -1 . The ethylbenzene conversion was 4.3%, the C8 loss was 0.35% and the xylene isomerization was 2.1%.
TABLE 1
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TABLE 2
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As can be seen from tables 1 and 2, the catalysts prepared in the present application can use higher mass space velocity and lower reaction temperature, and compared with the catalysts prepared in comparative examples 1-3, the catalysts in examples 1-19 can increase the conversion rate of the reaction when the reaction temperature is the same, indicating that the catalysts in examples have higher activity, better selectivity and longer service life.
According to examples 1-19 and comparative example 4, the catalysts of the present application have higher activity and selectivity in the isomerization reaction of phenolic compounds and are less effective in catalyzing the isomerization reaction of C8 aromatic hydrocarbons, indicating that the catalysts of the present application are specific for the reaction of phenolic compounds.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the catalyst provided by the application can effectively improve the pore structure and the reaction site of the carrier through loading the active components so as to solve the problems of low catalyst activity, poor selectivity and short service life. Under the effect of ion exchange, because different metals have different electron donating capacities, metal elements in the active component can replace metals in the carrier framework, so that acid sites in the catalyst are changed, and the activity of the catalyst is improved. The phosphorus element in the metal phosphate and the polyatoms in the heteropoly acid are dispersed in the carrier framework, so that the pore channel structure of the catalyst can be improved, and the selectivity of the catalyst is improved; and the carbon deposition resistance of the catalyst can be improved, so that the activity and stability of the catalyst are improved, and the service life of the catalyst is prolonged.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. An isomerization reaction, characterized in that the isomerization reaction comprises:
introducing a phenolic compound, toluene and a catalyst into a fixed bed reactor for reaction; the phenolic compound has the following general structure:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 、R 2 Independently C 1 ~C 5 Alkyl of (a);
the catalyst comprises a carrier, silicon dioxide and an active component;
wherein the carrier is a molecular sieve; the carrier is selected from any one or more of HZSM-5, MCM-22, MCM-41 and SAPO-11 molecular sieves;
the active component is an oxide formed by metal phosphate and/or heteropolyacid; the metal phosphate is aluminum phosphate, and the heteropolyacid is ammonium molybdate;
the silica and the active component are dispersed on the carrier.
2. The isomerization reaction according to claim 1, wherein the mass content of the active component is 3 to 15% of the carrier, and the mass content of the silica is 3 to 15% of the carrier.
3. The isomerization reaction according to claim 1, wherein the carrier has a pore volume of 0.2 to 0.7mL/g, a pore diameter of 1.5 to 5nm, and a specific surface area of 300 to 600m 2 /g。
4. The isomerization reaction according to claim 1, wherein the carrier has a pore volume of 0.25 to 0.5mL/g, a pore diameter of 2.0 to 5.0nm, and a specific surface area of 400 to 500m 2 /g。
5. The isomerization reaction of any one of claims 1 to 4, wherein the catalyst is prepared by a process comprising:
carrying out a first calcination reaction on the carrier loaded with the active compound to obtain a carrier loaded with the active component; the active compound is an aluminum phosphate precursor and/or an ammonium molybdate precursor;
mixing the carrier loaded with the active components with an adhesive and performing a second calcination reaction to obtain the catalyst; the binder is a silica precursor.
6. The isomerization reaction of claim 5, wherein the binder is a silica sol.
7. An isomerisation reaction according to claim 5, characterized in that,
when the active compound is the aluminum phosphate precursor, the carrier loaded with the active compound is prepared by the following method:
loading an aqueous metal salt solution, phosphoric acid and/or ammonium phosphate solution onto a carrier to obtain the carrier loaded with the active compound; wherein the metal salt is aluminum nitrate and/or aluminum sulfate;
and when the active compound is the ammonium molybdate precursor, loading the ammonium molybdate precursor aqueous solution on the carrier to obtain the carrier loaded with the active compound.
8. An isomerisation reaction according to claim 5, characterized in that,
the temperature of the first calcination reaction is 400-600 ℃, and the time of the first calcination reaction is 1-4 hours; the temperature of the second calcination reaction is 400-600 ℃, and the time of the second calcination reaction is 2-6 h.
9. The isomerization reaction according to any one of claims 1 to 4, characterized in that the mass ratio of the phenolic compound and toluene is 9:1 to 7:3.
10. The isomerization reaction of any one of claims 1 to 4, wherein the phenolic compound is 2, 6-dimethylphenol.
11. The isomerization reaction according to any one of claims 1 to 4, characterized in that the mass space velocity of the phenolic compound is 0.4 to 6h -1 Or 1-20 h -1 。
12. The isomerization reaction according to any one of claims 1 to 4, characterized in that the temperature of the reaction is 330 to 350 ℃ or 280 to 310 ℃.
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| EP0317911A2 (en) * | 1987-11-27 | 1989-05-31 | BASF Aktiengesellschaft | Process for the preparation of phenyl acetaldehydes |
| CN103316710A (en) * | 2013-07-11 | 2013-09-25 | 中科合成油内蒙古有限公司 | Hydroisomerization/cracking catalyst, and preparation method and application thereof |
| CN104923293A (en) * | 2015-06-17 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst |
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| CN107008477A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of catalyst, its preparation method and the method for preparing cyclohexyl benzene |
| CN107737605A (en) * | 2017-09-30 | 2018-02-27 | 宝鸡文理学院 | A kind of catalyst of DI-tert-butylphenol compounds of 4 methyl of selectivity synthesis 2,6 and its application |
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| EP0317911A2 (en) * | 1987-11-27 | 1989-05-31 | BASF Aktiengesellschaft | Process for the preparation of phenyl acetaldehydes |
| CN103316710A (en) * | 2013-07-11 | 2013-09-25 | 中科合成油内蒙古有限公司 | Hydroisomerization/cracking catalyst, and preparation method and application thereof |
| CN104923293A (en) * | 2015-06-17 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst |
| CN106944143A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | heteropoly acid ammonium type catalyst and its preparation method |
| CN107008477A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of catalyst, its preparation method and the method for preparing cyclohexyl benzene |
| CN107737605A (en) * | 2017-09-30 | 2018-02-27 | 宝鸡文理学院 | A kind of catalyst of DI-tert-butylphenol compounds of 4 methyl of selectivity synthesis 2,6 and its application |
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