CN114436728A - Method for preparing isopropylbenzene by using alpha, alpha dimethyl benzyl alcohol and application - Google Patents
Method for preparing isopropylbenzene by using alpha, alpha dimethyl benzyl alcohol and application Download PDFInfo
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- CN114436728A CN114436728A CN202011116359.7A CN202011116359A CN114436728A CN 114436728 A CN114436728 A CN 114436728A CN 202011116359 A CN202011116359 A CN 202011116359A CN 114436728 A CN114436728 A CN 114436728A
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- alpha
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- cumene
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 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 79
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 34
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 99
- 229910052763 palladium Inorganic materials 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052717 sulfur Inorganic materials 0.000 claims description 33
- 239000011593 sulfur Substances 0.000 claims description 33
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 241000510672 Cuminum Species 0.000 claims description 18
- 235000007129 Cuminum cyminum Nutrition 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 29
- -1 benzene free radical Chemical class 0.000 abstract description 17
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 abstract description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 6
- 235000019445 benzyl alcohol Nutrition 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 67
- 239000012018 catalyst precursor Substances 0.000 description 56
- 238000005984 hydrogenation reaction Methods 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 238000011156 evaluation Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- 229920001021 polysulfide Polymers 0.000 description 13
- 239000005077 polysulfide Substances 0.000 description 13
- 150000008117 polysulfides Polymers 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 11
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000007327 hydrogenolysis reaction Methods 0.000 description 9
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical class CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 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 2
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 230000003081 coactivator Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/20—Sulfiding
-
- 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
- B01J37/28—Phosphorising
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- 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
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- 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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/182—Phosphorus; Compounds thereof with silicon
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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)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing isopropyl benzene by utilizing alpha, alpha-dimethyl benzyl alcohol and application thereof, wherein the method comprises the following steps: in the presence of a catalyst and hydrogen, reacting a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol and cumyl benzene to obtain cumyl benzene, wherein the cumyl benzene is contained in the hydrocarbon material, the weight percentage of the cumyl benzene is x%, and when x% is less than or equal to 0.1%, the reaction temperature is controlled to be 180-220 ℃; when the concentration is 0.1% < x% < 0.5%, controlling the reaction temperature between (200+ x 100) and 250 ℃; when 0.5% < x%, the reaction temperature was controlled between (220+ x 80) and 320 ℃. Different conditions are selected according to different content of the cumyl benzene in the raw material, so that the cumyl benzene generates a cumyl benzene free radical and methyl styrene, and the cumyl benzene free radical generated in the conversion of the benzyl alcohol is quenched in time. The method can be widely applied to the production of cumene and propylene oxide from alpha, alpha-dimethyl benzyl alcohol.
Description
Technical Field
The invention belongs to the field of cumene preparation, particularly relates to cumene preparation by utilizing alpha, alpha-dimethyl benzyl alcohol, and particularly relates to cumene preparation by hydrogenolysis of a hydrocarbon byproduct containing alpha, alpha-dimethyl benzyl alcohol generated in propylene oxide production.
Background
Propylene Oxide (PO) is the third largest propylene derivative besides polypropylene and acrylonitrile, and is an important basic organic chemical raw material. Currently, there are four main processes for PO production: a chlorohydrin method, a PO/SM method for co-production of styrene and a PO/TBA method for co-production of tert-butyl alcohol, a hydrogen peroxide direct oxidation method (HPPO method) and a cumene oxidation method (CHP method).
The chlorohydrin method has serious pollution, and the development of the PO production technology mainly focuses on the research and development of a green environment-friendly new process. Wherein, the co-oxidation method is influenced by the market of co-products, and the potential safety hazard of the HPPO process is higher.
In the technology for producing propylene oxide by the CHP method, a large amount of byproducts containing alpha, alpha-dimethyl benzyl alcohol (DMBA) are generated in the propylene epoxidation process, and cumene is generated by hydrogenolysis reaction and participates in the reaction cycle again. This by-product, which contains α, α -dimethylbenzyl alcohol (DMBA), also contains a small amount of cumyl benzene (the product on the right in formula 3), which is produced by dimerization of two cumyl benzenes, thereby causing an increase in the unit consumption of cumyl benzene.
The specific reaction process is shown in equations (1), (2), (3) and (4).
The U.S. Pat. No. 4, 7442843, 2 provides a process for increasing the yield of cumene, which adopts a palladium-based catalyst, produces cumene through hydrogenolysis or dehydration hydrogenation by using alpha, alpha-dimethylbenzyl alcohol and hydrogen as raw materials, and uses hydrogen containing 0.1-10% of CO, thereby obviously increasing the conversion rate of dimethylbenzyl alcohol and the selectivity of cumene. Chinese patent CN101733093A reports that using alumina or zeolite to support metal Pd or a mixture of Pd and Pt as a reaction, under the condition of reaction temperature below 160 ℃, the conversion rate of α, α -dimethylbenzyl alcohol is more than 99.5%, and the selectivity of cumene is more than 99.5%, under the reaction conditions of the patent, the Pd catalyst is very easy to cause cumene to generate over-hydrogenated isopropylcyclohexane at the initial stage, and the stronger acidity of the carrier in the patent can obviously cause the polymerization of methylstyrene as an intermediate product in dehydration of α, α -dimethylbenzyl alcohol, and the patent does not mention the technical problem of catalyst stability. Chinese patent CN104230640A proposes to adopt Pd/SiO2The catalyst can realize 100 percent conversion of alpha, alpha-dimethyl benzyl alcohol under the condition of reaction temperature of 180 ℃, but the selectivity of isopropyl benzene is lower than 98.5 percent.
In the prior art, more has appeared to be the improvement of the hydrogenolysis activity of α, α -dimethylbenzyl alcohol and the selectivity of cumene by improving the process or catalyst, thereby increasing the yield of cumene. And the technical problem of how to reduce the formation of cumene in the hydrogenolysis reaction process or how to further reduce the unit consumption of cumene in the propylene oxide production technology, especially the cumene impurity control or conversion existing in the epoxidation product, is less involved.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for preparing isopropylbenzene by using alpha, alpha-dimethyl benzyl alcohol, in particular to a method for preparing isopropylbenzene by using alpha, alpha-dimethyl benzyl alcohol containing isopropylbenzene impurities, aiming at different contents of the isopropylbenzene impurities in raw materials, different reaction conditions are selected and thermodynamic control is carried out, so that the isopropylbenzene generates a free radical and alpha-methyl styrene, the alpha-methyl styrene and the alpha-methyl styrene are respectively hydrogenated to generate the isopropylbenzene, and simultaneously, the isopropylbenzene free radical possibly generated in the process of converting the benzyl alcohol is timely quenched to generate the isopropylbenzene, thereby reducing the unit consumption of the isopropylbenzene.
One of the objects of the present invention is to provide a method for preparing cumene using α, α -dimethylbenzyl alcohol, comprising: in the presence of a catalyst and hydrogen, reacting a hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol to obtain cumene, wherein the hydrocarbon material contains the cumin, and the weight percentage of the cumin is x%, wherein when x% is less than or equal to 0.1%, the reaction temperature is controlled to be 180-220 ℃; when the concentration is 0.1% < x% < 0.5%, controlling the reaction temperature between (200+ x 100) and 250 ℃; when 0.5% < x% (preferably 0.5% < x ≦ 1%), the reaction temperature was controlled between (220+ x 80) and 320 ℃.
The inventor finds that when the temperature for preparing the cumin is regulated and controlled by the method, the cumin contained in the raw material can be decomposed into the cumin, and the cumin generated in the hydrogenolysis process can be inhibited, so that the cumin product is almost free from the cumin (only 1-10 ppm).
In a preferred embodiment, the catalyst comprises a carrier, metallic palladium, an optional co-metal and an optional non-metallic promoter, wherein the metallic palladium, the optional co-metal and the optional non-metallic promoter are supported on the carrier.
Among them, the source of the metallic palladium is not particularly limited, and examples thereof include, but are not limited to, at least one of palladium chloride, palladium nitrate, chloropalladic acid, and the like.
In a further preferred embodiment, the support is selected from at least one of silica, alumina and activated carbon (preferably alumina); and/or the auxiliary metal is selected from at least one of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, and/or the nonmetal auxiliary agent is selected from sulfur and/or phosphorus.
Among them, the source of the promoter metal is not particularly limited, and examples thereof include, but are not limited to, at least one of a promoter metal chloride, an active promoter metal nitrate compound, an active promoter metal acetate compound, and the like. The sulfur is derived from sulfur-containing organics such as, but not limited to, at least one of tertiary nonyl polysulfide, tertiary butyl polysulfide, dimethyl disulfide, and the like. The source of phosphorus is not particularly limited, but is preferably, but not limited to, at least one of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate, and the like.
The inventor finds that after the carrier is modified by phosphorus, the hydrogenation activity and stability of the catalyst can be obviously improved. Especially, when the coactivator component (coactivator metal) is introduced into the catalyst, the method has obvious technical effect on improving the conversion rate of alpha, alpha-dimethylbenzyl and the selectivity of cumene.
In a preferred embodiment, the content of the metal palladium is 0.06 g/L-30 g/L, the content of the auxiliary metal is 0.0006 g/L-1.0 g/L, and the content of the nonmetal auxiliary agent is 10 g/L-100 g/L based on 1L of the carrier.
In a further preferred embodiment, the metallic palladium is contained in an amount of 0.5 to 20g/L, the co-metal is contained in an amount of 0.01 to 1.0g/L, the phosphorus is contained in an amount of 2 to 100g/L (preferably 5 to 80g/L), and the sulfur is contained in an amount of 0.0001 to 3g/L (preferably 0.01 to 1g/L, preferably 0.05 to 0.2g/L), based on 1L of the support.
Wherein the content of the metal palladium is calculated by the content of palladium element therein, the content of the auxiliary metal is calculated by the content of auxiliary metal element, the content of phosphorus is calculated by the content of phosphorus element, and the content of sulfur is calculated by the content of sulfur element therein.
The sulfur-containing organic matter is preferentially adsorbed to the low-coordination unsaturated active center on the surface of the catalyst to form a local poisoning phenomenon of an unstable active center on the catalyst, so that the local overheating of the catalyst caused by high initial activity of the catalyst can be well inhibited, the growth of metal crystal grains and the over hydrogenation of cumene to isopropylcyclohexane are avoided, the generation of the cumene can be effectively controlled, and the selectivity of the cumene is increased while the operation stability of the catalyst is obviously improved.
In a preferred embodiment, the non-metallic adjuvant optionally further comprises silica;
wherein, the silicon dioxide modification (especially the modified alumina carrier matrix) can improve the activity and stability of the catalyst. When only silicon dioxide is used as a carrier substrate, because the action between the active component and the carrier is weak, Pd grains are easy to aggregate and grow at the reaction temperature, and the stability of the catalyst is not facilitated, an alumina carrier substrate is preferably used.
In a further preferred embodiment, the silica content is 6 to 300g/L (preferably 20 to 200g/L) based on 1L of the support. Wherein the content of the silica is calculated by the content of the molecules.
Wherein, after the modification by silicon, the aperture of the catalyst is enlarged, and the diffusion speed of reactants and products is improved, thereby improving the conversion rate and the selectivity. In addition, it has been found that the silicon-containing catalyst has better hydrogenolysis activity and is also beneficial to accelerating the hydrogenolysis reaction rate.
In a preferred embodiment, the catalyst is prepared by:
optional step 1, mixing the carrier and an optional phosphorus-containing compound (preferably an aqueous solution of the phosphorus-containing compound) matrix, drying and roasting to obtain a phosphorus-containing carrier I;
optional step 2: mixing the carrier or the carrier I with the aqueous solution of silica gel, drying and roasting to obtain the carrier II containing phosphorus and/or silicon.
Step 3, adding the carrier, the carrier I or the carrier II into a solution containing a palladium compound and an optional auxiliary metal compound, drying and roasting to obtain an oxidation state catalyst precursor I;
step 4, adding the oxidation state catalyst precursor I into a solution containing a sulfur compound, and drying to obtain an oxidation state catalyst precursor II;
and 5, carrying out reduction treatment on the oxidation state catalyst precursor I or the oxidation state catalyst precursor II to obtain the catalyst.
In the preparation of the catalyst of the present inventionThe following drying was carried out as follows: drying at 60-200 ℃ for 4-36 hours, preferably at 80-150 ℃ for 6-12 hours, and more preferably at 110 ℃ for 8 hours; and/or the roasting temperature is 400-700 ℃, preferably, the roasting temperature is 400-500 ℃; and/or, carrying out reduction treatment by using hydrogen, preferably, the reduction temperature is 40-300 ℃, preferably 200-300 ℃, and more preferably 250 ℃; the volume space velocity of the hydrogen is 50-500 h-1Preferably 80 to 150 hours-1More preferably 100h-1。
In the presence of a supported palladium catalyst, the catalytic process for preparing the isopropylbenzene by hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol is realized by the catalyst at higher temperature. The hydrogenation method of the invention effectively controls the generation of heavy components such as cumyl benzene and methyl styrene polymer, increases the conversion rate of alpha, alpha-dimethyl benzyl alcohol, increases the yield of cumyl benzene while obviously improving the operation stability of the catalyst, and reduces the unit consumption of cumyl benzene for producing propylene oxide.
In a preferred embodiment, the reaction pressure is controlled to be 1.0 to 5.0MPa, preferably 2.0 to 3.0 MPa.
In a preferred embodiment, the liquid phase volume space velocity is controlled to be 1.0-30 h in the reaction-1Preferably 8 to 20 hours-1。
In a preferred embodiment, the molar ratio of hydrogen to α, α -dimethylbenzyl alcohol in the reaction is greater than 4, preferably greater than 5.
In a preferred embodiment, in the reaction, a liquid phase circulation process is adopted, and the circulation ratio is 1-10, preferably 3-8.
In a preferred embodiment, the hydrocarbon feed containing α, α -dimethylbenzyl alcohol further contains cumene.
In a further preferred embodiment, the hydrocarbon material containing the α, α -dimethylbenzyl alcohol contains 10 to 90 wt% of α, α -dimethylbenzyl alcohol, 10 to 89 wt% of cumene, and 0 to 1 wt% of cumin.
Wherein, the content of the cumyl benzene is preferably 0.01 to 1 wt%, for example, 0.01 to 0.1 wt%, 0.1 to 0.5 wt%, 0.5 to 1 wt%, 0.1 to 1 wt%.
In a further preferred embodiment, the weight ratio of α, α -dimethylbenzyl alcohol to the cumene is (0.2 to 4):1, preferably (1 to 4): 1.
In a preferred embodiment, the hydrocarbon material containing α, α -dimethylbenzyl alcohol further optionally contains acetophenone, methylstyrene, n-propylbenzene, n-butylbenzene, etc.
Wherein, the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol can be selected from tower bottoms after the separation of propylene oxide in the process of preparing the propylene oxide by the cumene hydroperoxide method or can be obtained by reducing the cumene hydroperoxide.
In a preferred embodiment, the hydrocarbon material contains cumyl benzene with the weight percentage of x%, wherein when x% is less than or equal to 0.1%, the reaction temperature is controlled between 200 ℃ and 220 ℃ (preferably without 220 ℃); when the concentration of x is more than 0.1% and less than or equal to 0.5%, controlling the reaction temperature to be 220-240 ℃; when the concentration is 0.5% < x% (preferably 0.5% < x% < 1%), the reaction temperature is controlled to 240-300 ℃ (preferably 240 ℃ is not included).
In a further preferred embodiment, the hydrocarbon material contains cumyl benzene, the weight percentage of which is x%, wherein when x is less than or equal to 0.1%, the temperature of a catalyst bed layer is controlled to be 200-210 ℃; when the concentration of x is more than 0.1% and less than or equal to 0.5%, controlling the temperature of a catalyst bed layer to be 220-230 ℃; when the concentration is 0.5% < x% (preferably 0.5% < x% < 1%), controlling the temperature of the catalyst bed layer at 270-300 ℃.
When the cumene concentration in the raw material is higher than 1%, cumene may be added to the raw material to a diluted concentration of 0.1% or less, 0.1% or less and 0.5% or less and 1% or 0.5% or less and 0.1% or less and 0.5% or less and 1% or less, and the raw material may be diluted to 0.1% or less and 0.1% or less and 1% or less.
According to the method, the temperature of a catalyst bed is controlled according to the content of cumene-in-benzene in the raw material, under a proper working condition, the content of cumene-in-benzene in a hydrogenation product is less than 100ppm, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 99.6%, the selectivity of cumene is more than 99.7%, and the catalyst continuously and stably operates for 200 hours, so that a better technical effect is obtained, and the method has wide industrial utilization value.
The second object of the present invention is to provide the use of the process according to the first object of the present invention for the preparation of propylene oxide.
The invention also aims to provide a preparation method of propylene oxide, which comprises the following steps:
1) cumene hydroperoxide is obtained by cumene oxidation;
2) under the existence of a solid catalyst, cumene hydroperoxide reacts with excessive propylene to obtain propylene oxide and alpha, alpha-dimethyl benzyl alcohol;
3) rectifying and separating propylene oxide to obtain a hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol;
4) the hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol is treated by the method which is one of the purposes of the invention to obtain the isopropyl benzene, and the isopropyl benzene is recycled to the step 1).
In the preparation process of the propylene oxide, cumene hydroperoxide exists, the cumene generates free radicals under the action of the peroxide, and the cumene is easily generated, and the reaction is inclined to be quenched by the free radicals to generate the cumene through thermodynamic control in the step 4).
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a specific catalyst to carry out reaction, and simultaneously skillfully regulates and controls the reaction temperature according to the content of the cumyl benzene in the raw material, thereby not only realizing energy saving, but also ensuring the yield of the product under the combined action of the catalyst and the reaction temperature;
(2) under the proper working condition, the content of the cumin in the hydrogenation product is less than 100ppm, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 99.6 percent, the selectivity of the cumin is more than 99.7 percent, and the catalyst continuously and stably runs for 200 hours, thereby obtaining better technical effect and having wide industrial utilization value.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the technical solution formed by the combination does not depart from the idea of the present invention, and the technical solution formed by the combination is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The content of cumene in the hydrogenation product (ppm) ═ W1 t
Alpha, alpha-dimethylbenzyl alcohol conversion (%) - (W)2 0-W2 t)/W2 0×100％；
Cumene selectivity (%) - (W)3 t-W3 0)/M2/(W2 0-W2 t)/M1]×100％
W1 0: the raw material contains cumene in percentage by mass; w1 tThe quality of cumene in the hydrogenation product;
W2 0: the mass of α, α -dimethylbenzyl alcohol in the raw material; w2 t: the mass of α, α -dimethylbenzyl alcohol in the hydrogenation product;
W3 0: the mass of cumene in the starting material; w3 t: the mass of cumene in the hydrogenation product;
M1is the molar molecular weight of the alpha, alpha-dimethylbenzyl alcohol; m2Is the molar molecular weight of cumene.
[ example 1 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II for 4 hours by using hydrogen, wherein the reduction temperature is 250 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol having the composition shown in table 1 was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 210 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
[ example 2 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 2, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 230 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
[ example 3 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladate-copper nitrate aqueous solution containing 3.0 g of palladium and 1.0g of copper, and the mixture is dried at 110 ℃ for 8 hours and roasted at 500 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II.
Reducing the catalyst precursor II for 4 hours by using hydrogen, wherein the reduction temperature is 250 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 2, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 230 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
[ example 4 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 3, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 280 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
[ example 5 ] A method for producing a polycarbonate
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I. The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II.
Before the catalystReducing the body II with hydrogen for 4 hours at the reduction temperature of 250 ℃ and the hydrogen volume space velocity of 100 hours-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing alpha, alpha-dimethylbenzyl alcohol was carried out in a continuous manner, the composition of the hydrocarbon feed containing cumene if it came out of the reactor being shown in table 4.
The operating conditions are as follows:
reaction temperature: 300 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 4.
[ example 6 ]
The procedure of example 3 was repeated except that: the catalyst further comprises silica.
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier containing P.
Mixing the P-containing catalyst carrier 1L with SiO2600 g of silica gel water solution with the mass concentration of 5 percent are mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
mixing 1 liter of the carrier containing P/Si with 2000 g of chloropalladate-copper nitrate aqueous solution containing 3.0 g of palladium and 1.0g of copper, drying at 110 ℃ for 8 hours, and roasting at 500 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst. The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 2, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 230 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
[ example 7 ]
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 5 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier containing P.
Mixing the P-containing catalyst carrier 1L with SiO2200g of silica gel water solution with the mass concentration of 5 percent are mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
1 liter of the carrier containing P/Si is mixed with 2000 g of chloropalladate-copper nitrate aqueous solution containing 5.0 g of palladium and 0.05g of copper, and the mixture is dried at 110 ℃ for 8 hours and roasted at 500 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.01g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 1, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 200 deg.C
Reaction pressure: 1.6MPa
Volume airspeed of fresh oil of raw material: 2.2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 6
The content of the cumin in the hydrogenation product is less than 100ppm, the conversion rate of alpha, alpha-dimethyl benzyl alcohol is more than 99.6 percent, and the selectivity of the cumin in the product is more than 99.7 percent.
[ example 8 ]
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 40 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier containing P.
Mixing the P-containing catalyst carrier 1L with SiO2600 g of silica gel aqueous solution with the mass concentration of 20 percent are mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
1 liter of the carrier containing P/Si is mixed with 2000 g of chloropalladate-copper nitrate aqueous solution containing 1.0g of palladium and 0.5g of copper, and the mixture is dried at 110 ℃ for 8 hours and roasted at 500 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I is mixed with 1000 g polysulfide-cyclohexane solution containing 0.1 g sulfur, and dried at 40 ℃ for 8 hours to prepare the sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 2, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 220 deg.C
Reaction pressure: 2.8MPa raw material fresh oil volume space velocity: 2.5h-1
Liquid phase circulation ratio: 5
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 6
The content of the cumin in the hydrogenation product is less than 100ppm, the conversion rate of alpha, alpha-dimethyl benzyl alcohol is more than 99.6 percent, and the selectivity of the cumin in the product is more than 99.7 percent.
[ example 9 ]
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 60 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier containing P.
Mixing the P-containing catalyst carrier 1L with SiO2600 g of 10% silica gel aqueous solution are mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
1 liter of the carrier containing P/Si is mixed with 2000 g of chloropalladate-copper nitrate aqueous solution containing 10.0 g of palladium and 0.01g of copper, and the mixture is dried at 110 ℃ for 8 hours and roasted at 500 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.5g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II for 4 hours by using hydrogen, wherein the reduction temperature is 250 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 3, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 270 deg.C
Reaction pressure: 3.0MPa
Volume airspeed of fresh oil of raw material: 2.8h-1
Liquid phase circulation ratio: 6
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 10
The content of the cumin in the hydrogenation product is less than 100ppm, the conversion rate of alpha, alpha-dimethyl benzyl alcohol is more than 99.6 percent, and the selectivity of the cumin in the product is more than 99.7 percent.
Comparative example 1
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 1, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 160 ℃ C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
Comparative example 2
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II.
Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 2, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 200 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
Comparative example 3
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L catalyst precursor I and sulfur containing 0.2g polysulfide cyclohexane solution 1000 g mixture, through 40 degrees C drying for 8 hours, prepared by sulfur modified palladium catalyst precursor II.
Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain the palladium-based catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 3, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 220 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 6.
Comparative example 4
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladite acid aqueous solution containing 3.0 g of palladium, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
The 1L of catalyst precursor I is mixed with 1000 g of polysulfide-cyclohexane solution containing 0.2g of sulfur, and the mixture is dried for 8 hours at 40 ℃ to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen at 250 deg.c for 4 hr and hydrogen volume space velocity of 100 hr-1To obtain palladiumA base catalyst.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor packed with the catalyst prepared above and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol, the composition of which is shown in table 4, was carried out in a continuous manner.
The operating conditions were as follows:
reaction temperature: 220 deg.C
Reaction pressure: 2.0MPa
Volume airspeed of fresh oil of raw material: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluations are shown in table 4.
TABLE 1
| Raw Material composition 1 | The weight percentage is w% |
| Isopropyl benzene | 46.3 |
| N-propylbenzene | 0.12 |
| Methyl styrene | 0.13 |
| Acetophenone | 0.82 |
| Alpha, alpha-dimethylbenzyl alcohol | 52.6 |
| And isopropyl benzene | 0.06 |
TABLE 2
| Raw Material composition 1 | The weight percentage is w% |
| Isopropyl benzene | 45.9 |
| N-propyl benzene | 0.12 |
| Methyl styrene | 0.13 |
| Acetophenone | 0.82 |
| Alpha, alpha-dimethylbenzyl alcohol | 52.7 |
| And isopropyl benzene | 0.33 |
TABLE 3
| Raw Material composition 2 | The weight percentage is w% |
| Isopropyl benzene | 45.8 |
| N-propylbenzene | 0.12 |
| Methyl styrene | 0.13 |
| Acetophenone | 0.82 |
| Alpha, alpha-dimethylbenzyl alcohol | 52.5 |
| And isopropyl benzene | 0.63 |
TABLE 4
| Raw Material composition 2 | The weight percentage is w% |
| Isopropyl benzene | 45.7 |
| Positive propyleneBenzene and its derivatives | 0.12 |
| Methyl styrene | 0.13 |
| Acetophenone | 0.81 |
| Alpha, alpha-dimethylbenzyl alcohol | 52.3 |
| And isopropyl benzene | 0.92 |
TABLE 5
TABLE 6
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (12)
1. A method for preparing cumene from α, α -dimethylbenzyl alcohol, comprising: in the presence of a catalyst and hydrogen, reacting a hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol to obtain cumene, wherein the hydrocarbon material contains the cumene, and the weight percentage of the cumene is x%, wherein when x% is less than or equal to 0.1%, the reaction temperature is controlled to be 180-220 ℃; when the concentration is 0.1% < x% < 0.5%, controlling the reaction temperature between (200+ x 100) and 250 ℃; when 0.5% < x, the reaction temperature was controlled between (220+ x 80) and 320 ℃.
2. The method of claim 1,
controlling the reaction pressure to be 1.0-5.0 MPa, preferably 2.0-3.0 MPa; and/or
Controlling the liquid phase volume space velocity to be 1.0-30 h-1Preferably 8 to 20 hours-1。
3. The method of claim 1,
a liquid phase circulation process is adopted, the circulation ratio is 1-10, and 3-8 is preferred; and/or
The molar ratio of hydrogen to α, α -dimethylbenzyl alcohol is greater than 4, preferably greater than 5.
4. The method of claim 1, wherein the catalyst comprises a support, metallic palladium, an optional co-metal, and an optional non-metallic promoter, wherein the metallic palladium, the optional co-metal, and the optional non-metallic promoter are supported on the support.
5. The method of claim 4,
the carrier is selected from at least one of silicon oxide, aluminum oxide and activated carbon (preferably aluminum oxide); and/or
The auxiliary metal is at least one of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, and/or
The non-metallic additive is selected from sulfur and/or phosphorus.
6. The method according to claim 5, wherein the content of the metallic palladium is 0.06-30 g/L, the content of the co-metal is 0.0006-1.0 g/L, and the content of the non-metallic auxiliary agent is 10-100 g/L based on 1L of the carrier; preferably, based on 1L of the carrier, the content of the metal palladium is 0.5 g/L-20 g/L, the content of the auxiliary metal is 0.01 g/L-1.0 g/L, the content of the phosphorus is 2 g/L-100 g/L, and the content of the sulfur is 0.0001 g/L-3 g/L.
7. The method of claim 5, wherein the non-metallic additive optionally further comprises silica; preferably, the content of the silicon dioxide is 6-300 g/L, preferably 20-200 g/L based on 1L of the carrier, wherein the content of the silicon dioxide is calculated by the content of molecules of the silicon dioxide.
8. The method according to any one of claims 1 to 7, wherein the hydrocarbon material contains cumyl benzene in an amount of x% by weight,
when x% is less than or equal to 0.1%, controlling the reaction temperature to be 200-220 ℃, and preferably 200-210 ℃;
when the concentration of x is more than 0.1% and less than or equal to 0.5%, controlling the reaction temperature to be 220-240 ℃, and preferably 220-230 ℃;
when the concentration is 0.5% < x%, the reaction temperature is controlled to be 240-300 ℃, preferably 270-300 ℃.
9. The method according to claim 8, wherein the hydrocarbon material containing α, α -dimethylbenzyl alcohol further contains cumene, and preferably, the hydrocarbon material containing α, α -dimethylbenzyl alcohol contains 10 to 90 wt% of α, α -dimethylbenzyl alcohol, 10 to 89 wt% of cumene, and 0 to 1 wt% of cumin.
10. The method according to claim 8, wherein the weight ratio of α, α dimethylbenzyl alcohol to cumene is (0.2-4): 1, preferably (1-4): 1.
11. Use of the process according to any one of claims 1 to 10 in the production of propylene oxide.
12. A method for preparing propylene oxide comprises the following steps:
1) cumene hydroperoxide is obtained by cumene oxidation;
2) under the existence of a solid catalyst, cumene hydroperoxide reacts with excessive propylene to obtain propylene oxide and alpha, alpha-dimethyl benzyl alcohol;
3) rectifying and separating propylene oxide to obtain a hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol;
4) processing a hydrocarbon material containing α, α -dimethylbenzyl alcohol by the method of any one of claims 1 to 10 to obtain cumene, which is recycled to step 1).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1496344A (en) * | 2001-03-14 | 2004-05-12 | ס�ѻ�ѧ��ҵ��ʽ���� | Method for recovering cumene |
| US20060217566A1 (en) * | 2003-09-25 | 2006-09-28 | Tetsuo Suzuki | Process for producing cumene and process for propylene oxide production including the production process |
| CN101733093A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst for preparing isopropylbenzene by catalytic hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN104230640A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Alpha, alpha-dimethylbenzyl alcohol hydrogenolysis method for preparing isopropyl benzene |
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|---|---|---|---|---|
| CN1496344A (en) * | 2001-03-14 | 2004-05-12 | ס�ѻ�ѧ��ҵ��ʽ���� | Method for recovering cumene |
| US20060217566A1 (en) * | 2003-09-25 | 2006-09-28 | Tetsuo Suzuki | Process for producing cumene and process for propylene oxide production including the production process |
| CN101733093A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | Catalyst for preparing isopropylbenzene by catalytic hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN104230640A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Alpha, alpha-dimethylbenzyl alcohol hydrogenolysis method for preparing isopropyl benzene |
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| HERMAN PINES ETC.: "Phenyl Migratian during Decomposition of Peroxides in Aldylbenzenes", J AM CHEM SOC, vol. 82, pages 2921 - 2925 * |
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