CN112439401B - Hydrogenolysis catalyst, preparation method and application thereof in preparation of isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol - Google Patents
Hydrogenolysis catalyst, preparation method and application thereof in preparation of isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol Download PDFInfo
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- CN112439401B CN112439401B CN201910810948.6A CN201910810948A CN112439401B CN 112439401 B CN112439401 B CN 112439401B CN 201910810948 A CN201910810948 A CN 201910810948A CN 112439401 B CN112439401 B CN 112439401B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 53
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 67
- 238000001125 extrusion Methods 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000004115 Sodium Silicate Substances 0.000 claims description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 15
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000007580 dry-mixing Methods 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 9
- 244000060011 Cocos nucifera Species 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 9
- 229910001948 sodium oxide Inorganic materials 0.000 description 9
- 238000004846 x-ray emission Methods 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910017813 Cu—Cr Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 palladium ions Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/63—Platinum group metals with rare earths or actinides
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a hydrogenolysis catalyst, a preparation method and application thereof in the hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol to prepare isopropylbenzene, mainly solving the problem that the activity of the catalyst is reduced due to the loss of active components during the long-period operation of the hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol, inhibiting the generation of reaction byproducts and simultaneously improving the liquid resistance of the catalyst 2 O 3 、Na 2 O、SiO 2 ‑Al 2 O 3 The activated carbon can be used for the industrial production of the isopropylbenzene prepared by the hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a hydrogenolysis catalyst, a preparation method and application thereof in preparation of isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol.
Background
Propylene Oxide (PO) is an important organic chemical intermediate, and is mainly used as a raw material for producing polyurethane, namely polyether polyol. The current industrial processes for producing PO are mainly chlorohydrin process, co-oxidation process (PO/styrene monomer process, PO/tert-butanol process, PO/methyl tert-butyl ether process), cumene hydroperoxide process (CHP process) and hydrogen peroxide oxidation process (HPPO process). The new PO producing process developed by Sumitomo chemical includes three steps of cumene oxidation, propylene epoxidation and alpha, alpha-dimethyl benzyl alcohol hydrogenolysis. The process has high conversion rate and high selectivity, the product is only PO, and the process is not influenced by the price fluctuation of the by-product styrene and can bring more stable economic benefits for manufacturers. However, the hydrogenolysis process of the alpha, alpha-dimethylbenzyl alcohol adopts a Cu-Cr catalyst, which seriously pollutes the environment.
U.S. Pat. No. 6,139 (US) patent 6646139 reports a process for preparing cumene by hydrogenolysis of α, α -dimethylbenzyl alcohol, in which Cu-Cr oxide is used as catalyst, the conversion rate of α, α -dimethylbenzyl alcohol can reach 100.0%, and the selectivity of cumene is more than 97.5%. However, the catalyst in the method has the defects of easy carbon deposition, easy high-temperature loss of Cu, pollution of Cr to the environment and the like, and in addition, the service life of the catalyst and the content of the byproduct isopropylcyclohexane are not mentioned.
Chinese patent CN101735004 reports that Pd or Pd-Pt metal bifunctional catalyst is adopted to catalyze alpha, alpha-dimethyl benzyl alcohol for hydrogenolysis to prepare isopropyl benzene at the temperature of 80-160 ℃ and the pressure of 0.1-2.0 MPa, in the method, alkali washing is needed before the reaction of raw material alpha, alpha-dimethyl benzyl alcohol, more waste liquid is generated, the conversion rate is less than or equal to 99.5 percent, the selectivity of isopropyl benzene is more than or equal to 99.5 percent, hydrogenation metal components in the catalyst are loaded by adopting an impregnation method or an ion exchange method, the loading rate is low, the manufacturing cost is high, and the problems that the system temperature runaway is easily caused at the initial reaction stage due to overhigh activity exist.
Chinese patent CN104151129 reports a method for preparing isopropylbenzene from alpha-methylstyrene by using AMS selective hydrogenation catalyst, which is composed of Pd/Ca/K/Mg/Ba and Al 2 O 3 The alpha-methyl styrene is used as a carrier, the conversion rate of the alpha-methyl styrene can reach 100 percent, the byproduct isopropyl cyclohexane can reach 0ppm, but the selectivity of isopropyl benzene is only over 96 percent, the strength of the carrier is not high, and the service life of the catalyst is limited.
Chinese patent CN1257138C proposes to use H 2 The method of reducing the Cu catalyst with the CO mixed gas is not disclosed in the patent because the catalyst used is still a Cu-Cr catalyst.
Chinese patent CN1616383A proposes that noble metal Pd is used as a catalyst and H is used 2 Or organic matter is used as hydrogen source, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 96 percent and the selectivity of isopropyl benzene is more than 99 percent at the temperature of 30-100 ℃, and the reaction is carried out in a batch reaction kettle to realize continuous reactionThe reaction is difficult to continue.
Chinese patent CN1555348A proposes to use a Cu-based catalyst and hydrogen with CO content less than 5% as hydrogen source, which can prevent the activity reduction caused by hydrogen pressure reduction and catalyst poisoning, and can effectively utilize all the contents in the reaction vessel, but the catalyst still has poor stability.
Chinese patent CN104230642A describes a Pd catalyst prepared by an impregnation method, and H is used as the catalyst 2 The catalyst is a hydrogen source, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 98%, the selectivity of cumene is more than 95%, and the catalyst has the risks of uneven distribution of active components and insufficient stability at the temperature of 30-100 ℃.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a hydrogenolysis catalyst and a preparation method thereof. The hydrogenolysis catalyst prepared by the invention can be applied to the hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol to prepare the isopropylbenzene, effectively solves the problem of activity reduction caused by the loss of active components of the catalyst in the long-period operation process of the hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol, inhibits the generation of reaction byproducts, and simultaneously improves the liquid resistance of the catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a hydrogenolysis catalyst, which comprises the following components by the total mass of 100 percent of the catalyst:
a) the Pd content is 0.5-3.0%, preferably 0.5-2.0%;
b)Y 2 O 3 the content is 0.5-3.0%, preferably 1.0-2.0%;
c)Na 2 the content of O is 1.5-13.0%, preferably 2.0-10.0%;
d)SiO 2 -Al 2 O 3 the content of the activated carbon is 85-98.0%, preferably 90.0-95.0%.
In the catalyst of the present invention, preferably, the catalyst is a catalyst for improving catalytic activity of a catalyst for promoting activity of a catalyst for cell of a present inventionComponent d) SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio range of the activated carbon is 0.3-8.0: 1.0-12: 1, preferably in the range of 2.0 to 5.0: 1.0-4.0: 1.
the invention also provides a preparation method of the hydrogenolysis catalyst, which can be used for preparing the hydrogenolysis catalyst and comprises the following steps:
mixing a carbon source, an aluminum source, sodium silicate, a palladium source, an yttrium source, an extrusion aid and water, kneading to form a wet uniform plastic body, extruding, molding, drying and roasting to obtain the catalyst for preparing the isopropylbenzene by hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol.
In the preparation method, the mass ratio of the palladium source, the aluminum source, the sodium silicate and the carbon source is 0.05-6.0: 1.0-15.0: 1.0-27.3: 1, preferably 1 to 5: 2-10: 2-20: 1;
the mass ratio of the yttrium source to the palladium source is 0.1-4.5: 1, preferably 0.5 to 3.0: 1.
in the preparation method, the palladium source is an ammonia water solution of palladium chloride, wherein the mass concentration of palladium element is 15-25%, preferably 20%; the ammonia water concentration for preparing the ammonia water solution of palladium chloride is 25-28 wt%.
The yttrium source is selected from one or two of yttrium nitrate and yttrium chloride. The metal palladium is a main active component of the catalyst, excessive hydrogenation of benzene rings is easily caused by too high content of the metal palladium, the yield of products is reduced, on the contrary, the content is too low, the activity of the catalyst is relatively low, the catalyst is inactivated relatively quickly, and the introduction of yttrium auxiliary agent can promote the dispersion of the palladium and improve the catalytic activity.
The carbon source is selected from activated carbon well known in the art, and can be coconut shell carbon, coal carbon, wood carbon and the like, the granularity of the carbon source is 200-1000 meshes, and the iodine value is 800-1000. The active carbon is a porous material, the rich pore channel structure of the active carbon is beneficial to improving the activity of the catalyst, and the active carbon has excellent adsorption capacity and is beneficial to the hydrogenolysis reaction.
The aluminum source is a precursor of alumina, is selected from the group consisting of boehmite, pseudoboehmite, SB powder and the like, preferably pseudoboehmite, has a particle size of below 200 meshes and a specific surface area of 200 to up to 200 ℃500m 2 The pore volume is 0.3 to 0.6 ml/g.
The sodium silicate is a sodium silicate aqueous solution, the solid content is more than or equal to 40 wt%, the preferred weight percentage is 40 wt%, and the modulus is 1.5-3.0, and the preferred weight percentage is 2.5-3.0. Sodium silicate, commonly known as water glass, is used as a raw material of the binder and provides an auxiliary agent Na + When the temperature is increased (80 ℃) in the roasting process, water molecules are rearranged and have catalytic action on condensation between adjacent silanol groups, the temperature is further heated to be more than 120-130 ℃, residual water molecules promote the silanol groups to condense, and Si-OH bonds are mutually dehydrated and associated to form Si-O-Si bonds, a three-dimensional curing structure system with excellent water resistance can be formed after the three-dimensional curing structure system is cured at high temperature, meanwhile, sodium and palladium ions in the raw materials are in a closed state of a three-dimensional structure, the loss of active components such as palladium and auxiliary agent sodium in the long-period operation process of the catalyst can be effectively prevented, and the liquid resistance is obviously enhanced.
The extrusion aid is sesbania powder preferably, and the added extrusion aid accounts for 1-8% of the total mass of the raw materials.
In the preparation method of the invention, the mixing and selecting method comprises the following steps: firstly, dry-mixing a carbon source, an aluminum source and an extrusion aid, and then mixing sodium silicate, a palladium source, an yttrium source and water (preferably deionized water); the amount of the water is not specifically required, so that the raw materials can form a plastic blank as a reference, and in some embodiments of the invention, the amount of the water is 10-30% of the total mass of the raw materials; the dry mixing is carried out, the rotating speed of a motor is 10-80 r/min, and the time is 30-50 min;
in the preparation method of the invention, the kneading is carried out in a kneader; the kneading is carried out at the motor rotating speed of 10-80 r/min for 10-30 min.
In the preparation method, the extrusion molding is carried out by the selected method comprising the following steps: extruding and molding the prepared uniform plastic body in a strip extruding machine, wherein the diameter of the extruded strip is 1-5 mm; the cross section of the extrusion die can be cylindrical, clover and the like, the extrusion speed is 20rpm, and the extrusion pressure is 50-200N.
In the preparation method, the drying is preferably carried out in the air, and the drying temperature is not more than 80 ℃, and is preferably 60-80 ℃; the drying time is 1-24 h, preferably 4-12 h.
In the preparation method of the invention, the roasting and selecting method comprises the following steps: and (3) carrying out temperature-raising roasting on the dried and formed material in an air atmosphere, wherein the roasting conditions are as follows: roasting at 200-400 ℃ for 3-10 hours at a heating rate of 10-100 ℃/hour.
Meanwhile, the invention also provides the application of the catalyst in the preparation of isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol. The method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol takes the alpha, alpha-dimethyl benzyl alcohol as a starting material and performs hydrogenolysis reaction under the action of the catalyst or the catalyst prepared by the method to prepare the isopropylbenzene.
In the above method, the hydrogenolysis reaction is preferably carried out in the presence of a solvent, preferably cumene, in a mass ratio of the solvent to α, α -dimethylbenzyl alcohol in the range of 1: 2 to 4.
In the method, the hydrogenolysis reaction is carried out at the pressure of 1-2 MPa (gauge pressure), the temperature of 140-160 ℃ and H 2 The volume ratio of the/DMPC (alpha, alpha-dimethyl benzyl alcohol) is 300-500: 1, and the liquid hourly space velocity is 1-3 h -1 。
Preferably, the catalyst of the present invention comprises a reduction activation treatment before use.
In a preferred embodiment, the method for reductive activation of a catalyst according to the present invention comprises: preferably, the temperature of the reactor is increased to 200-230 ℃, the temperature is kept constant for 1-2H to remove the physical water adsorbed by the catalyst, and then H with the volume fraction not more than 10v percent is introduced 2 For example (5 v% + -2 v%) H 2 The catalyst is pre-reduced for at least 0.5h, such as 1h, 1.5h or 2h, the proportion of the hydrogen in the hydrogen and nitrogen mixed gas is gradually increased, such as gradually increased to 10 v%, 20 v%, 50 v% and 100%, the temperature of a hot spot of a catalyst bed layer in the process is controlled not to exceed 260 ℃, finally the catalyst is reduced for 2-5 h, such as 3 or 4h, in the reduction activation process, the gas volume space velocity is kept for 300-1000 h -1 And obtaining the activated catalyst.
In the method, the conversion rate of the raw material alpha, alpha-dimethyl benzyl alcohol is more than 99 percent; the selectivity of the isopropyl benzene is more than 99 percent; the catalyst has stable service life up to over 1000 hr, high strength and no obvious loss of active components.
The invention has the beneficial effects that:
the preparation process of the catalyst provided by the invention adopts an integrated forming method, sodium silicate is used as a binder, and the binder is mixed with the impregnation liquid. The components of the alumina, the silicon oxide and the active carbon are mainly used as composite carriers, and the hardness, the liquid resistance and the like of the catalyst are obviously improved while the activity of the catalyst is considered. In addition, the addition of the Y element in the catalyst composition attracts the Pd element to form a metal bond due to the electronegativity of the Y element, so that the aggregation of the palladium element can be effectively reduced, the dispersion degree of palladium is improved, and further the sintering resistance, the activity and the long-period stability of the catalyst are improved.
The catalyst is used in the reaction of preparing the isopropylbenzene by hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol, solves the problems of activity reduction caused by loss of active components of the catalyst in the long-period operation process and inhibition of generation of reaction byproducts, and has the advantages of good stability of the catalyst, long service life, high conversion rate of raw materials, high selectivity of products and the like.
Detailed Description
The advantageous effects of the present invention will be described below by way of specific examples. It will be appreciated by those skilled in the art that the examples are only intended to illustrate the invention and are not intended to limit the scope of the invention. In the examples, the means used are conventional in the art unless otherwise specified.
First, the main raw material sources in the example:
coconut shell charcoal with particle size of 200-1000 mesh and iodine value of 800-1000, purchased from Lossen corporation
Pseudo-boehmite with the granularity of less than 200 meshes and the specific surface area of 200-500 m 2 The pore volume is 0.3-0.6 ml/g, and the material is purchased from Shandong aluminum industry Co., Ltd;
SB powder, available from Zibozehao catalysis technologies, Inc.;
the preparation method of the ammonia water solution of palladium chloride comprises the steps of adding palladium chloride into ammonia water with the concentration of 25-28 wt%, and then adding deionized water to completely dissolve the palladium chloride and dilute the palladium element content of the palladium chloride to the mass concentration of 20%.
Other raw materials are all common commercial products and the reagents are all analytically pure, unless otherwise specified.
Secondly, the product analysis method in the embodiment:
the side pressure strength of the catalyst was measured by a particle strength tester, and the side pressure strength of the catalyst after 40-grain reaction was measured and the average value was taken.
The elemental content of the catalyst was determined by X-ray fluorescence spectroscopy (XRF).
The mole number of dimethylbenzyl alcohol contained in the hydrogenolysis reaction raw material, the mole number of generated cumene and the mole number of dimethylbenzyl alcohol remained in the reaction solution are calculated after being analyzed by an Agilent 7820A gas chromatograph, and the test conditions comprise: adopts DB-5 chromatographic column and FID detector, the vaporizing chamber temperature is 260 deg.C, the detector temperature is 260 deg.C, and the carrier gas is high-purity N 2 The flow rate was 30 ml/min.
Conversion of dimethylbenzyl alcohol (1-mole of dimethylbenzyl alcohol remaining in reaction solution/mole of dimethylbenzyl alcohol contained in raw material) × 100%;
cumene selectivity-100% moles of cumene formed/moles dimethylbenzyl alcohol converted.
Example 1:
a preparation method of a hydrogenolysis catalyst comprises the following steps:
1) firstly, 70.6g of pseudo-boehmite, 12.5g of coconut shell carbon and 3.0g of sesbania powder are weighed and mixed in a mixer in a dry mode, the rotating speed of a motor is 15r/min, the dry mixing time is 30min, then 26g of deionized water, 69.3g of sodium silicate aqueous solution (the solid content is 40 wt%, the modulus is about 2.7), 0.87g of yttrium chloride and 2.5g of palladium chloride aqueous ammonia solution (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a kneader to be kneaded, the kneading time is 20min, and the rotating speed of the motor is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 70N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally heating to 400 ℃ at the speed of 60 ℃/h in a muffle furnace for roasting for 4h to obtain the catalyst A.
The hydrogenolysis catalyst prepared in example 1 has an active component Pd content of 0.5 wt% determined by XRF, and other components with the mass percentage content as follows: y is 2 O 3 About 0.5% of sodium oxide, about 6.5% of sodium oxide, and the balance of SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio of the activated carbon is about 1.6: 4.8: 1.
example 2
A preparation method of a hydrogenolysis catalyst comprises the following steps:
1) firstly weighing 70.6g of SB powder, 10.0g of coconut shell carbon and 3g of sesbania powder, carrying out dry mixing in a mixer at the motor speed of 15r/min for 30min, then mixing 20g of deionized water, 69.4g of sodium silicate aqueous solution (with the solid content of 40 wt% and the modulus of about 2.7), 1.69g of yttrium nitrate and 15g of palladium chloride ammonia aqueous solution (with the mass concentration of palladium element of 20 wt%), adding the solution into a kneader for kneading for 20min at the motor speed of 15r/min, and obtaining wet dough.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 80N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally heating to 400 ℃ at the speed of 60 ℃/h in a muffle furnace for roasting for 4h to obtain the catalyst B.
The hydrogenolysis catalyst prepared in example 2 has an active component Pd element content of 3 wt% as determined by XRF, and other components in percentage by mass: y is 2 O 3 The content is about 0.5%, and the sodium oxide is about 6%.5 percent, and the rest is SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio of the activated carbon is about 2.0: 6.0: 1.
example 3
A preparation method of a hydrogenolysis catalyst comprises the following steps:
1) firstly, 35.3g of pseudo-boehmite, 27.0g of coconut shell carbon and 3g of sesbania powder are weighed and mixed in a mixer in a dry mode, the rotating speed of a motor is 15r/min, the dry mixing time is 30min, then 22g of deionized water, 5.2g of yttrium chloride, 97.1g of sodium silicate aqueous solution (the solid content is 40 wt%, the modulus is about 2.7) and 15g of palladium chloride aqueous ammonia solution (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a kneader to be kneaded, the kneading time is 20min, and the rotating speed of the motor is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 70N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally heating to 350 ℃ at the speed of 60 ℃/h in a muffle furnace for roasting for 4h to obtain the catalyst C.
The hydrogenolysis catalyst prepared in example 3 had a composition by weight percent as determined by XRF: the active component Pd element content is 3 wt%, and the other components comprise the following components in percentage by mass: y is 2 O 3 The content of sodium oxide is about 3 percent, the content of sodium oxide is about 9 percent, and the rest is SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio of the activated carbon is about 1.03: 1.11: 1.
comparative example 1
1) Firstly, 58.8g of pseudo-boehmite and 3.0g of sesbania powder are weighed and mixed in a mixer, the rotating speed of a motor is 15r/min, the dry mixing time is 30min, then 42.5g of deionized water, 10.2g of yttrium nitrate, 114.5g of sodium silicate aqueous solution (the solid content is 40 wt%, the modulus is about 2.7) and 15g of palladium chloride ammonia aqueous solution (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a kneader to be kneaded, the kneading time is 20min, and the rotating speed of the motor is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 90N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally roasting in a muffle furnace at 300 ℃ for 4h to obtain the catalyst D.
The hydrogenolysis catalyst prepared in comparative example 1 had the following composition by weight percent as determined by XRF:
the active component Pd element content is 3 wt%, and the other components comprise the following components in percentage by mass: y is 2 O 3 About 3% of sodium oxide, about 11% of sodium oxide, and the balance of SiO 2 -Al 2 O 3 And is present in an amount of about 50% alumina and 33% silica.
Comparative example 2
1) Firstly, 46.6g of coconut shell charcoal and 2.5g of sesbania powder are weighed and mixed in a mixer in a dry mode, the motor speed is 15r/min, the dry mixing time is 30min, then 138.8g of sodium silicate aqueous solution (the solid content is 40 wt%, and the modulus ratio is 2.7) and 2.5g of palladium chloride ammonia aqueous solution (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a kneader to be kneaded, the kneading time is 20min, and the motor speed is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 100N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally roasting in a muffle furnace at 300 ℃ for 4h to obtain a catalyst E.
The hydrogenolysis catalyst prepared in comparative example 2 had a composition, as determined by XRF, of, by weight percent: the Pd element content of the active component is 0.5 wt%, and the other components comprise the following components in percentage by mass: sodium oxide about 13%, the balance being SiO 2 -activated carbon, SiO 2 Mass ratio to activated carbon is about 0.86: 1.
comparative example 3
1) Firstly, 47.1g of pseudo-boehmite, 15.3g of coconut shell carbon and 2.5g of sesbania powder are weighed and mixed in a mixer in a dry mode, the rotating speed of a motor is 15r/min, the dry mixing time is 30min, then 25g of deionized water, 104g of sodium silicate aqueous solution (the solid content is 40 wt%, the modulus is about 2.7) and 25g of palladium chloride ammonia aqueous solution (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a mixing and kneading machine for kneading, the kneading time is 20min, and the rotating speed of the motor is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, extrusion pressure of 75N, extrusion speed of 20rpm, and an extrusion grinding tool is cylindrical and has a diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally roasting in a muffle furnace at 300 ℃ for 4h to obtain the catalyst F.
The hydrogenolysis catalyst prepared in the comparative example 3 comprises the active component Pd 5 wt% determined by XRF, and other components with the mass percentage: sodium oxide about 9.7%, the balance being SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio of the activated carbon is about 2.0: 2.6: 1.
comparative example 4
1) Firstly, 58.8g of pseudo-boehmite, 8.8g of coconut shell carbon and 2.5g of sesbania powder are weighed and mixed in a mixer in a dry mode, the rotating speed of a motor is 15r/min, the dry mixing time is 30min, then 100g of ammonia type silica sol (the solid content is 40 percent, the modulus is about 2.7), 1.73g of yttrium chloride and 2.5g of ammonia water solution of palladium chloride (the mass concentration of palladium element is 20 wt%) are mixed, the solution is added into a kneader to be kneaded, the kneading time is 20min, and the rotating speed of the motor is 15r/min, so that wet dough is obtained.
3) Putting the wet material mass obtained in the step 2) into a double-screw extruder for extrusion molding, wherein the extrusion conditions are room temperature, the extrusion pressure is 65N, the extrusion speed is 20rpm, and the extrusion grinding tool is cylindrical and has the diameter of 2 mm;
4) and 3) rapidly drying the strip-shaped wet base blank obtained in the step 3) in a drying furnace at 80 ℃ for 8h, and finally roasting in a muffle furnace at 300 ℃ for 4h to obtain the catalyst G.
The hydrogenolysis catalyst prepared in comparative example 4 had the following composition by weight percent as determined by XRF: the Pd element content of the active component is 0.5 wt%, and the other components comprise the following components in percentage by mass: y is 2 O 3 The content is about 1 percent, and the rest component is SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio of the activated carbon is about 3.4: 5.7: 1.
examples 4 to 6
In the industrial process of the catalyst prepared in the above examples 1-3 and used for the hydrogenolysis synthesis of isopropyl benzene by alpha, alpha-dimethyl benzyl alcohol, the catalyst is reduced and activated before use by the following method: firstly, raising the temperature of a reactor to 200-230 ℃, dehydrating for 1.5h, then introducing a mixed gas of hydrogen (5 v%) and nitrogen for pre-reduction for 0.5h, such as 1h, then gradually increasing the proportion of hydrogen in the mixed gas of hydrogen and nitrogen to 10 v%, 20 v%, 50 v% and 100%, simultaneously controlling the temperature of a hot spot of a catalyst bed layer not to exceed 260 ℃, finally reducing for 3h under a pure hydrogen atmosphere, and keeping the gas volume space velocity for 300-1000 h in the reduction activation process -1 。
In the reaction process, the raw materials comprise (by mass percent) 75.0 percent of isopropyl benzene and 25.0 percent of alpha, alpha-dimethyl benzyl alcohol, and in a fixed bed reactor, the reaction pressure is 2MPa (gauge pressure), and H is 2 Volume ratio of benzyl alcohol 250: 1, the evaluation was carried out for 1000 hours under the reaction conditions that the space velocity of the raw material volume was 1.5/hour, and the reaction results are shown in Table 1. Comparative examples 5 to 8: the catalyst prepared in comparative examples 1 to 4 was used in the same manner as in examples 4 to 6, and the reaction results are shown in Table 1.
TABLE 1 evaluation table of the initial reaction and the activity after 1000h reaction for preparing isopropylbenzene by benzyl alcohol hydrogenolysis
As the catalyst does not contain Cr element, the problem of environmental pollution is avoided, and as can be seen from the table 1, the conversion rate of alpha, alpha-dimethyl benzyl alcohol is more than 99.0 percent and the selectivity of cumene is more than 99.0 percent under the conditions that the temperature of alpha, alpha-dimethyl benzyl alcohol is less than or equal to 160 ℃ and the pressure of 2MPa, the technology obtains good reaction results when being used for the process of synthesizing cumene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, the catalyst prepared in the embodiment 1 is continuously operated for 1000 hours, the conversion rate of benzyl alcohol is more than 99 percent, the selectivity of cumene is more than 99 percent, and the strength of the catalyst after reaction is good without the defects of pulverization, incompleteness and the like.
TABLE 2 comparison of strength before and after 1000h reaction of catalyst
| Catalyst and process for preparing same | Reaction temperature/. degree.C | Catalyst Strength (N/pellet) before reaction | Catalyst Strength after reaction (N/pellet) |
| A | 150 | 56 | 41 |
| B | 150 | 60 | 45 |
| C | 150 | 58 | 46 |
| D | 150 | 55 | 10 |
| E | 150 | 62 | 20 |
| F | 150 | 60 | 35 |
| G | 150 | 55 | 35 |
The catalysts of the examples and comparative examples were subjected to elemental analysis after 1000 hours of reaction, and the results are shown in Table 3:
TABLE 3 comparison table of Pd and Na element analysis of 1000h catalyst reaction
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (15)
1. A hydrogenolysis catalyst which comprises the following components in an amount of 100% by mass based on the total mass of the catalyst:
a) the Pd content is 0.5-3.0%;
b)Y 2 O 3 the content is 0.5-3.0%;
c)Na 2 the content of O is 1.5-13%;
d)SiO 2 -Al 2 O 3 -activated carbon content 85-98.0%;
the hydrogenolysis catalyst is prepared by mixing and kneading a carbon source, an aluminum source, sodium silicate, a palladium source, an yttrium source, an extrusion aid and water into a wet uniform plastic body, and then extruding, forming, drying and roasting.
2. The hydrogenolysis catalyst of claim 1 comprising the following components in 100% by weight of the total catalyst mass:
a) the Pd content is 0.5-2.0%;
b)Y 2 O 3 the content is 1.0-2.0%;
c)Na 2 the content of O is 2.0-10.0%;
d)SiO 2 -Al 2 O 3 -90.0-95.0% of activated carbon.
3. Hydrogenolysis catalyst according to claim 1, characterized in that the component d) SiO 2 -Al 2 O 3 -activated carbon, SiO 2 With Al 2 O 3 The mass ratio range of the activated carbon is 0.3-8.0: 1.0-12: 1.
4. the hydrogenolysis catalyst of claim 3 wherein the SiO is 2 With Al 2 O 3 The mass ratio range of the activated carbon is 2.0-5.0: 1.0-4.0: 1.
5. a method of preparing a hydrogenolysis catalyst as claimed in any one of claims 1-4 comprising the steps of:
mixing a carbon source, an aluminum source, sodium silicate, a palladium source, an yttrium source, an extrusion aid and water, kneading to form a wet uniform plastic body, extruding, molding, drying and roasting to obtain the catalyst for preparing the isopropylbenzene by hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol.
6. The preparation method according to claim 5, wherein the palladium source is an ammonia solution of palladium chloride, wherein the mass concentration of palladium element is 15-25%; and/or
The yttrium source is selected from one or two of yttrium nitrate and yttrium chloride; and/or
The carbon source is selected from activated carbon, the granularity of the activated carbon is 200-1000 meshes, and the iodine value of the activated carbon is 800-1000; and/or
The aluminum source is selected from the group consisting of burymite, pseudo-boehmite and SB powder, the particle size is below 200 meshes, and the specific surface area is 200-500 m 2 The pore volume is 0.3-0.6 ml/g; and/or
The sodium silicate is a sodium silicate aqueous solution, the solid content is more than or equal to 40 wt%, and the modulus is 1.5-3.0; and/or
The extrusion aid is sesbania powder, and the added extrusion aid accounts for 1-8% of the total mass of the raw materials; and/or
The mass ratio of the palladium source to the aluminum source to the sodium silicate to the carbon source is 0.05-6.0: 1.0-15.0: 1.0-27.3: 1; and/or
The mass ratio of the yttrium source to the palladium source is 0.1-4.5: 1.
7. the method according to claim 6, wherein the palladium source has a palladium element concentration of 20% by mass; and/or
The carbon source is selected from coconut shell carbon, coal-made carbon or wood carbon; and/or
The aluminum source is pseudo-boehmite; and/or
The mass ratio of the palladium source to the aluminum source to the sodium silicate to the carbon source is 1-5: 2-10: 2-20: 1; and/or
The mass ratio of the yttrium source to the palladium source is 0.5-3.0: 1.
8. the method of manufacturing according to claim 5, wherein the mixing method comprises: firstly, dry-mixing a carbon source, an aluminum source and an extrusion aid, and then mixing sodium silicate, a palladium source, an yttrium source and water.
9. The preparation method according to claim 8, wherein the dry mixing is carried out at a motor speed of 10-80 r/min for 30-50 min.
10. The production method according to claim 5,
the kneading is carried out in a kneader; the rotating speed of the motor is 10-80 r/min, and the time is 10-30 min; and/or
The extruded strips are formed, and the diameter of the extruded strips is 1-5 mm; the extrusion speed is 20rpm, and the extrusion pressure is 50-200N; and/or
The drying is carried out in the air, the drying temperature is not more than 80 ℃, and the drying time is 1-24 h.
11. The preparation method according to claim 10, wherein the drying temperature is 60 to 80 ℃ and the drying time is 4 to 12 hours.
12. The method of claim 5, wherein the firing method comprises: and (3) carrying out temperature-raising roasting on the dried and formed material in an air atmosphere, wherein the roasting conditions are as follows: roasting at 200-400 ℃ for 3-10 hours at a heating rate of 10-100 ℃/hour.
13. A process for producing cumene by hydrogenolysis of α, α -dimethylbenzyl alcohol, which comprises using α, α -dimethylbenzyl alcohol as a starting material, and subjecting the starting material to hydrogenolysis reaction with the catalyst according to any one of claims 1 to 4 or the catalyst produced by the process according to any one of claims 5 to 12.
14. The method according to claim 13, wherein the hydrogenolysis reaction is carried out at a pressure of 1 to 2MPa gauge and a temperature of 140 to 160 ℃ H 2 The volume ratio of DMPC is 100-300: 1, and the liquid hourly space velocity is 1-3 h -1 。
15. The method of claim 13, wherein the catalyst comprises a reductive activation treatment prior to use.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735004A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for producing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN102040482A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing alpha, alpha-dimethyl benzyl alcohol by hydrogenating hydrogen dioxide isopropyl benzene |
| CN104230642A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Alpha, alpha-dimethyl-benzyl carbinol direct hydrogenolysis method for preparing isopropyl benzene |
| CN104710277A (en) * | 2013-12-17 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparation of low carbon alcohol by hydrogenolysis of sugar and sugar alcohol |
| RU2565764C1 (en) * | 2014-08-08 | 2015-10-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Method of producing phenol and acetone |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735004A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Method for producing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN102040482A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing alpha, alpha-dimethyl benzyl alcohol by hydrogenating hydrogen dioxide isopropyl benzene |
| CN104230642A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Alpha, alpha-dimethyl-benzyl carbinol direct hydrogenolysis method for preparing isopropyl benzene |
| CN104710277A (en) * | 2013-12-17 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparation of low carbon alcohol by hydrogenolysis of sugar and sugar alcohol |
| RU2565764C1 (en) * | 2014-08-08 | 2015-10-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Method of producing phenol and acetone |
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