CN114192162B - Dimethylbenzyl alcohol hydrogenolysis catalyst and preparation method and application thereof - Google Patents
Dimethylbenzyl alcohol hydrogenolysis catalyst and preparation method and application thereof Download PDFInfo
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- CN114192162B CN114192162B CN202111522871.6A CN202111522871A CN114192162B CN 114192162 B CN114192162 B CN 114192162B CN 202111522871 A CN202111522871 A CN 202111522871A CN 114192162 B CN114192162 B CN 114192162B
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- mixed solution
- catalyst
- containing compound
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- dimethylbenzyl alcohol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 227
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 138
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 28
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims description 156
- 238000000034 method Methods 0.000 claims description 96
- 239000000843 powder Substances 0.000 claims description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 51
- 238000001125 extrusion Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 36
- 150000002736 metal compounds Chemical class 0.000 claims description 35
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- 239000004202 carbamide Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 28
- 239000011812 mixed powder Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 20
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 17
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 claims description 3
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 claims description 2
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 claims description 2
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 239000002344 surface layer Substances 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000009467 reduction Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 241000219782 Sesbania Species 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000004846 x-ray emission Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- GQVVQDJHRQBZNG-UHFFFAOYSA-N benzyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC1=CC=CC=C1 GQVVQDJHRQBZNG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 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 1
- 229910002061 Ni-Cr-Al alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Chemical class CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Chemical class C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical class [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- B01J35/394—
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/60—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a dimethylbenzyl alcohol hydrogenolysis catalyst and a preparation method and application thereof, wherein active components of the dimethylbenzyl alcohol hydrogenolysis catalyst comprise Pd, ru, cu and Ni, pd and Ru in the active components are highly dispersed on the surface layer of the catalyst, which is favorable for inhibiting side reactions such as excessive hydrogenation, and dimethylbenzyl alcohol diffused into a pore canal of the catalyst can undergo hydrogenolysis reaction under the catalysis of Cu and Ni to generate isopropylbenzene, but is difficult to further hydrogenate to generate isopropyl cyclohexane as a byproduct; the carrier of the dimethylbenzyl alcohol hydrogenolysis catalyst comprises ZnO and SiO 2 And Al 2 O 3 The composite carrier of the catalyst is favorable for obtaining the high-efficiency hydrogenolysis catalyst with highly dispersed active components, reliable strength and moderate acidity; the catalyst for hydrogenolysis of dimethyl benzyl alcohol has the advantages of high dispersity of active components, smooth catalyst pore channels and the like, and has excellent activity and selectivity when being used for preparing isopropylbenzene through hydrogenolysis of dimethyl benzyl alcohol.
Description
Technical Field
The invention relates to the technical field of hydrogenolysis catalysts, in particular to a dimethyl benzyl alcohol hydrogenolysis catalyst and a preparation method and application thereof.
Background
Industrial Propylene Oxide (PO) production methods mainly include chlorohydrin method, hydrogen peroxide direct oxidation method, and co-oxidation method (Halcon method). The chlorohydrin method is a main route for producing PO at present, and the process has serious problems of equipment corrosion, environmental pollution and the like. The direct oxidation route of hydrogen peroxide suffers from economic impact due to the high cost of raw materials. The co-oxidation process is a reaction of an organic peroxide with propylene to form propylene oxide. The traditional isobutane co-oxidation method and ethylbenzene co-oxidation method avoid serious pollution to the environment caused by a chlorohydrin method with high investment and long flow, but a large amount of byproducts are co-produced in the PO production process, and the PO production cost is greatly influenced by the fluctuation of the price of the co-produced products.
The cumene co-oxidation method (PO-CHP process) comprises three core reactions of cumene peroxidation, propylene epoxidation and dimethylbenzyl alcohol hydrogenolysis and related separation processes, wherein cumene hydroperoxide is taken as an oxygen source, the coproduced dimethylbenzyl alcohol is subjected to hydrogenolysis to generate cumene, and the cumene is returned to a peroxidation unit to react to obtain the cumene hydroperoxide, so that the recycling of the cumene is realized. Compared with other processes, the cumene co-oxidation method has the advantages of very high conversion rate and selectivity, short process route, less equipment investment, no coupling product, more stable economic benefit and the like.
The dimethylbenzyl alcohol hydrogenolysis reaction is one of the core reactions of the PO-CHP process. The dimethylbenzyl alcohol hydrogenolysis catalyst mainly includes platinum-palladium noble metal catalyst, nickel catalyst, copper catalyst, etc., and is reported in many patents.
U.S. Pat. No. 3,182 discloses a method for preparing isopropylbenzene by vapor phase hydrogenolysis of α, α -dimethylbenzyl alcohol using Ni-Cr-Al 2 O 3 The catalyst contains Cr, and has serious environmental pollution problems in the processes of catalyst preparation, use and recovery treatment.
Patent CN1308273C discloses a method for preparing isopropylbenzene by catalytic hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, which adopts 2wt% Pd-C catalyst, has high catalyst cost, needs to introduce halogenated aromatic hydrocarbon, sodium formate, formic acid, indole and other substances during reaction, and increases separation difficulty and cost.
Patent CN104230640A discloses a method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, which adopts Mg/Ca/Ba modified Pd-Ni/SiO 2 The selectivity of the catalyst for the hydrogenolysis reaction to produce the isopropylbenzene is generally less than 98.5 percent, the catalyst cost is high and the selectivity is low.
Patent CN104874406 discloses a Pt-loaded hydrogenolysis catalyst, which uses phenolic resin-based activated carbon as a carrier, and has the advantages of complex catalyst preparation process, large preparation difficulty, obviously reduced catalyst selectivity after 300h operation and poor catalyst stability.
Patent CN1257138C proposes to use H 2 In the method of reducing Cu catalyst with CO gas mixture, the catalyst is still Cu-Cr catalyst, and the catalyst stability index is not disclosed in the patent.
Patent CN101992098 discloses a Cu-Zn-Al catalyst for preparing isopropylbenzene by hydrogenolysis of dimethylbenzyl alcohol, and the patent adopts airspeed of 1.5h -1 The space velocity is low and the patent does not disclose the state of the catalyst after use and the strength of the catalyst.
Patent CN112569930A discloses a preparation method of isopropylbenzene and the obtained isopropylbenzene, wherein Pd and a carbon-containing precursor are loaded on an alumina carrier, the residual carbon content after roasting is less than 1.5%, the Pd loading amount is 0.5%, and the catalyst cost is higher. Furthermore, the patent does not mention the method of molding the catalyst and the state of the catalyst particles after the reaction.
The conventional noble metal catalyst has the defects of high catalyst cost, easiness in causing aromatic ring saturation, poor selectivity of isopropylbenzene and the like when being used for hydrogenolysis reaction of dimethylbenzyl alcohol; nickel-based and copper-based catalysts have the disadvantages of low activity, poor selectivity, easy sintering, poor liquid repellency of the catalyst, and the like.
At present, the catalyst prepared by the prior art has the problems of high load, low activity, poor selectivity, poor high-temperature stability, poor liquid resistance and serious environmental pollution of noble metal Pt/Pd and the like when being used for preparing isopropylbenzene by catalytic hydrogenolysis of dimethylbenzyl alcohol. Therefore, it is significant to develop a hydrogenolysis catalyst having excellent hydrogenolysis reaction performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a dimethylbenzyl alcohol hydrogenolysis catalyst and a preparation method and application thereof, wherein active components of the dimethylbenzyl alcohol hydrogenolysis catalyst comprise Pd, ru, cu and Ni, pd and Ru in the active components are highly dispersed on the surface layer of the catalyst, which is favorable for inhibiting side reactions such as excessive hydrogenation, and dimethylbenzyl alcohol diffused into a pore canal of the catalyst can undergo hydrogenolysis reaction under the catalysis of Cu and Ni to generate isopropylbenzene, but is difficult to further hydrogenate to generate byproduct isopropyl cyclohexane; the carrier of the dimethylbenzyl alcohol hydrogenolysis catalyst comprises ZnO and SiO 2 And Al 2 O 3 The composite carrier of the catalyst is favorable for obtaining the high-efficiency hydrogenolysis catalyst with highly dispersed active components, reliable strength and moderate acidity; the catalyst for hydrogenolysis of dimethyl benzyl alcohol has the advantages of high dispersity of active components, smooth catalyst pore channels and the like, and has excellent activity and selectivity when being used for preparing isopropylbenzene by hydrogenolysis of dimethyl benzyl alcohol, and has good liquid resistance and high stability.
One of the purposes of the invention is to provide a dimethylbenzyl alcohol hydrogenolysis catalyst, which comprises the following components in percentage by weight based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and calculated on inorganic oxide:
The active components of the dimethylbenzyl alcohol hydrogenolysis catalyst comprise Pd, ru, cu and Ni, the Pd and Ru in the active components are highly dispersed on the surface layer of the catalyst, which is favorable for inhibiting side reactions such as excessive hydrogenation, and the dimethylbenzyl alcohol diffused into a pore canal of the catalyst can undergo hydrogenolysis reaction under the catalysis of Cu and Ni to generate isopropylbenzene, but is difficult to further hydrogenate to generate isopropyl cyclohexane as a byproduct; the carrier of the dimethylbenzyl alcohol hydrogenolysis catalyst comprises ZnO and SiO 2 And Al 2 O 3 Is beneficial to obtaining the composite carrier of (2)High-efficiency hydrogenolysis catalyst with high dispersion of active components, reliable strength and moderate acidity.
The dimethylbenzyl alcohol hydrogenolysis catalyst includes PdO 0.01 to 0.3wt%, for example, 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, or 0.3wt%, etc., based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and on the inorganic oxide basis, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The dimethylbenzyl alcohol hydrogenolysis catalyst comprises RuO in an amount of 100wt% based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and calculated as inorganic oxide 2 0.05 to 0.8wt%, for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt% or 0.8wt%, etc., but are not limited to the recited values, and other non-recited values within the above ranges are equally applicable.
The dimethylbenzyl alcohol hydrogenolysis catalyst comprises CuO 15.0 to 25.0wt%, such as 15.0wt%, 17.0wt%, 19.0wt%, 20.0wt%, 21.0wt%, 23.0wt%, 25.0wt%, etc., based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and on inorganic oxide, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The dimethylbenzyl alcohol hydrogenolysis catalyst comprises ZnO 15.0-25.0wt%, such as 15.0wt%, 17.0wt%, 19.0wt%, 20.0wt%, 21.0wt%, 23.0wt% or 25.0wt%, etc., based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and on inorganic oxide, but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
The dimethylbenzyl alcohol hydrogenolysis catalyst comprises NiO 2.0-10.0wt%, such as 2.0wt%, 4.0wt%, 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, or 10.0wt%, etc., based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst and on the inorganic oxide basis, but is not limited to the recited values, and other non-recited values within the above ranges are equally applicable.
Hydrogenolysis catalysis with dimethylbenzyl alcohol The total weight of the catalyst is 100wt% and the dimethylbenzyl alcohol hydrogenolysis catalyst comprises Al based on inorganic oxide 2 O 3 15.0 to 40.0wt%, for example 15.0wt%, 20.0wt%, 25.0wt%, 30.0wt%, 35.0wt% or 40.0wt%, etc., but are not limited to the values recited, and other values not recited in the above ranges are equally applicable.
The dimethylbenzyl alcohol hydrogenolysis catalyst comprises SiO, based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst taken as 100wt% and calculated on inorganic oxide 2 20.0 to 45.0wt%, for example, 20.0wt%, 25.0wt%, 30.0wt%, 35.0wt%, 40.0wt% or 45.0wt%, etc., but are not limited to the recited values, and other non-recited values within the above ranges are equally applicable.
As a preferable technical scheme of the invention, in the dimethylbenzyl alcohol hydrogenolysis catalyst, the molar ratio of Pd to Ru is 1 (1-10), the molar ratio of Cu to Zn is 1 (0.5-1.0), and the molar ratio of Cu to Ni is 1 (0.1-0.5).
In the catalyst for hydrogenolysis of dimethylbenzyl alcohol, the molar ratio of Pd to Ru is 1 (1-10), when the Pd content is higher and the Ru content is lower, the catalyst cost is higher, excessive hydrogenation is serious, and when the Pd content is lower and the Ru content is higher, the catalyst activity is insufficient; the molar ratio of Cu to Zn is 1 (0.5-1.0), the molar ratio of Cu to Ni is 1 (0.1-0.5), when the Cu content is higher, the dispersity of Cu is poor, the catalyst activity is affected, and when the Cu content is lower, the catalyst activity is insufficient; proper Zn content is introduced into the catalyst, so that the dispersity of Cu can be obviously improved; the catalyst activity is high but the selectivity is poor when the Ni content is high, and the catalyst activity is low when the Ni content is low. Thus, suitable amounts of Pd, ru, cu, ni and Zn are advantageous for obtaining highly active and selective hydrogenolysis catalysts.
As a preferred embodiment of the present invention, the dimethylbenzyl alcohol hydrogenolysis catalyst has a hollow ring shape, an outer diameter of 3 to 5mm, for example, 3mm, 3.5mm, 4mm, 4.5mm, 5mm, etc., an inner diameter of 1 to 3mm, for example, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, etc., and a length of 3 to 8mm, for example, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, etc., but is not limited to the recited values, and other non-recited values within the above-recited values are equally applicable.
The dimethyl benzyl alcohol hydrogenolysis catalyst is hollow annular, so that the mass transfer performance of the catalyst can be improved, the occurrence of side reactions is reduced, and the catalyst has lower bed pressure drop.
The second object of the present invention is to provide a method for preparing the catalyst for hydrogenolysis of dimethylbenzyl alcohol, which comprises the following steps:
(1) Preparing a mixed solution 1 of a copper-containing compound, a zinc-containing compound and a nickel-containing compound; adding silica sol into urea aqueous solution to obtain mixed solution 2; adding an aminosilane coupling agent into the nano silicon dioxide alcohol solution to obtain a mixed solution 3; preparing a mixed solution 4 of a palladium-containing compound and a ruthenium-containing compound;
(2) Adding the mixed solution 1 into the mixed solution 2, sequentially stirring, evaporating to dryness and roasting, and mixing the obtained composite metal compound with alumina powder and an extrusion aid to obtain mixed powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), and sequentially mixing, extruding, forming, drying and roasting to obtain the dimethylbenzyl alcohol hydrogenolysis catalyst;
wherein, the steps (2) and (3) are not in sequence.
The preparation method of the invention firstly prepares the composite metal compound containing copper, zinc and nickel, and then mixes the composite metal compound with alumina powder and extrusion aid to obtain mixed powder, so that the active components Cu and Ni can be uniformly dispersed in the composite metal compound containing ZnO and SiO 2 And Al 2 O 3 The dimethyl benzyl alcohol diffused into the catalyst pore canal can generate hydrogenolysis reaction under the catalysis of Cu and Ni to generate isopropylbenzene, but the isopropylcyclohexane is difficult to generate by-product through further hydrogenation; then, the impregnating solution (mixed solution 5) containing Pd and Ru and the mixed powder are sequentially mixed, extruded, molded, dried and roasted, so that Pd and Ru in the active components are highly dispersed on the surface layer of the catalyst, and side reactions such as excessive hydrogenation and the like are favorably inhibited.
In addition, the preparation method of the invention focuses on limiting the preparation process of the mixed solution 5, namely, adding 4 drops of the mixed solution of the palladium-containing compound and the ruthenium-containing compound into the nano silicon dioxide alcohol solution (mixed solution 3) containing the aminosilane coupling agent, and adopting the nano silicon dioxide alcohol solution is beneficial to the high dispersion of palladium and ruthenium.
Furthermore, the preparation method of the invention is used for SiO in composite carriers 2 Two sources are arranged, namely, the silica sol in the mixed solution 2 and the nano silicon dioxide alcohol solution in the mixed solution 3, and SiO is introduced in the form of alkaline silica sol 2 Occupying SiO in the catalyst 2 The silica sol in the mixed solution 2 can promote the dispersion of Cu, zn and Ni, the nano silica alcohol solution in the mixed solution 3 can improve the dispersion degree of Pd and Ru, and the two components complement each other, thereby being beneficial to improving the activity of the hydrogenolysis catalyst.
As a preferred embodiment of the present invention, in the mixed solution 1 of step (1), the copper-containing compound includes copper formate and/or copper acetate.
Preferably, in the mixed solution 1 of step (1), the zinc-containing compound includes zinc formate and/or zinc acetate.
Preferably, in the mixed solution 1 of step (1), the nickel-containing compound includes nickel formate and/or nickel acetate.
Preferably, in the mixed solution 1 of the step (1), the molar concentration of the metal ions is 1.0 to 2.0mol/L, for example, 1.0mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L, 1.7mol/L, 1.9mol/L, or 2.0mol/L, etc., but not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
According to the invention, the formate and/or acetate of metal is used as raw materials in the mixed solution 1, so that the slurry obtained by the reaction of the metal salt in the subsequent mixed solution 1 and urea in the mixed solution 2 can be directly evaporated to dryness and baked without washing; in addition, formate and/or acetate can be decomposed by heating in the roasting process, so that the porosity of the dimethylbenzyl alcohol hydrogenolysis catalyst can be improved, and the mass transfer performance of the dimethylbenzyl alcohol hydrogenolysis catalyst can be improved.
Preferably, the mass concentration of the urea aqueous solution in step (1) is 15-30wt%, such as 15wt%, 18wt%, 20wt%, 23wt%, 25wt%, 26wt%, 28wt%, 30wt%, etc., but is not limited to the recited values, and other non-recited values within the above-mentioned range of values are equally applicable.
Preferably, the silica sol in step (1) is an alkaline silica sol.
Preferably, the SiO of the alkaline silica sol 2 The content is 30 to 40wt%, for example 30wt%, 31wt%, 33wt%, 35wt%, 38wt% or 40wt%, etc., the particle diameter is 20 to 40nm, for example 20nm, 25nm, 30nm, 35nm or 40nm, etc., and the pH is 8.0 to 10.0, for example 8.0, 8.5, 9.0, 9.5 or 10.0, etc., but not limited to the values recited above, and other values not recited in the above-mentioned numerical ranges are equally applicable.
Preferably, in the nanosilica alcoholic solution of step (1), siO 2 The content is 15 to 20wt%, for example 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%, etc., and the particle diameter is 15 to 30nm, for example 15nm, 18nm, 20nm, 23nm, 25nm, 28nm or 30nm, etc., but not limited to the values recited, and other values not recited in the above-mentioned ranges are equally applicable.
The preparation method adopts the alcohol solution of nano silicon dioxide, which is beneficial to the high dispersion of Pd and Ru; further defining SiO in nanosilicon alcohol solution 2 The content is 15-20wt%, and SiO in the nano silicon dioxide alcohol solution is avoided 2 When the content is too high, the dispersion of Pd and Ru is unfavorable, and SiO can be avoided 2 If the content is too low, the catalyst may be formed adversely, possibly resulting in a formed catalyst having a low strength.
Preferably, the alcoholic solvent of the nanosilica alcoholic solution of step (1) comprises any one or a combination of at least two of methanol, ethanol or propanol, typical but non-limiting examples of which include: a combination of methanol and ethanol, a combination of methanol and propanol, or a combination of ethanol and propanol, etc.
As a preferred embodiment of the present invention, the aminosilane coupling agent in step (1) includes any one or a combination of at least two of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, aminomethyl trimethoxysilane, and aminomethyl triethoxysilane, and typical but non-limiting examples of the combination include: a combination of gamma-aminopropyl trimethoxysilane and gamma-aminopropyl triethoxysilane, a combination of gamma-aminopropyl triethoxysilane and phenylmethyl trimethoxysilane, or a combination of phenylmethyl trimethoxysilane and phenylmethyl triethoxysilane, and the like.
Preferably, in the preparation process of the mixed solution 3 in the step (1), the mass ratio of the aminosilane coupling agent to the nano silica alcohol solution is controlled to be 1 (20-50), for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, etc., but not limited to the listed values, and other non-listed values in the above-mentioned value range are equally applicable.
According to the preparation method, the aminosilane coupling agent is added, so that the dispersity of Pd and Ru can be improved, the hydrogenolysis reaction activity of dimethylbenzyl alcohol can be improved, adverse substances such as water generated by reaction can be weakened to a certain extent, the damage to active components and carriers can be reduced, and the stability of the catalyst can be improved; the mass ratio of the aminosilane coupling agent to the nano silicon dioxide alcohol solution is further limited to be 1 (20-50), so that the effect of improving the dispersity of Pd and Ru can not be achieved when the addition amount of the aminosilane coupling agent is too small, and the problem of being unfavorable for the diffusion of raw materials and products when the addition amount of the aminosilane coupling agent is too large can be avoided.
Preferably, in the mixed solution 4 of step (1), the palladium-containing compound includes palladium acetylacetonate.
Preferably, in the mixed solution 4 of step (1), the ruthenium-containing compound includes ruthenium acetylacetonate.
According to the preparation method, palladium acetylacetonate and ruthenium acetylacetonate are used as palladium sources and ruthenium sources respectively, and compared with palladium chloride/palladium nitrate and ruthenium chloride/ruthenium nitrate, the method is more beneficial to improving the dispersity of Pd and Ru, and further improves the reactivity of the dimethylbenzyl alcohol hydrogenolysis catalyst.
Preferably, the solvent of the mixed solution 4 of step (1) comprises any one or a combination of at least two of benzene, toluene or chloroform, typical but non-limiting examples of which include: benzene and toluene, toluene and chloroform, or benzene and chloroform, etc.
In the preferred embodiment of the present invention, in the step (2), the ratio of the number of moles of the metal ions in the mixed solution 1 to the number of moles of the urea in the mixed solution 2 is controlled to be 1 (2.0-3.0), for example, 1:2.0, 1:2.2, 1:2.4, 1:2.5, 1:2.7, 1:2.9 or 1:3.0, but not limited to the above-mentioned values, and other non-listed values in the above-mentioned value range are equally applicable.
The preparation method limits the dosage of urea, which not only can avoid the disadvantage of improving the porosity of the catalyst when the urea amount is too small, but also can avoid the problem that the bulk density of the catalyst is smaller and the number of active sites on the catalyst per unit volume is lower when the urea amount is too large.
Preferably, the evaporating temperature in the step (2) is 80 to 100 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or the like, but the evaporating temperature is not limited to the values listed, and other values not listed in the above-mentioned value range are equally applicable.
Preferably, the drying time in step (2) is 4-24 hours, for example, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours or 24 hours, etc., but the method is not limited to the recited values, and other non-recited values in the above range are equally applicable.
Preferably, the temperature of the calcination in the step (2) is 250 to 400 ℃, for example 250 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃, 400 ℃ or the like, but the method is not limited to the listed values, and other non-listed values in the above-mentioned value range are equally applicable.
Preferably, the time of the calcination in step (2) is 2-8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, etc., but is not limited to the recited values, and other non-recited values within the above range are equally applicable.
In a preferred embodiment of the present invention, the alumina powder in the step (2) has a particle size of 80 to 150 mesh, for example, 80 mesh, 90 mesh, 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh or 150 mesh, but the present invention is not limited to the above-mentioned values, and other non-mentioned values in the above-mentioned value ranges are equally applicable.
According to the preparation method, the alumina powder with proper granularity is added, so that not only can the problem that the alumina is not easy to disperse when the alumina powder is too coarse, but also the problem that the diffusion performance of the formed catalyst is not good when the alumina powder is too fine can be avoided.
Preferably, the alumina powder in step (2) is used in an amount of 15 to 40wt%, for example 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, etc., based on the sum of the mass of the composite metal compound and the mass of the alumina powder, but is not limited to the recited values, and other non-recited values within the above-mentioned ranges are equally applicable.
According to the preparation method disclosed by the invention, the alumina powder with proper content is added, so that proper acidity can be provided for the catalyst, the defect of insufficient catalyst activity caused by fewer acid sites can be avoided, and the dehydration polymerization of dimethyl benzyl alcohol caused by excessive acid sites can be avoided, so that the selectivity of the catalyst is further influenced.
Preferably, the extrusion aid in step (2) comprises sesbania powder.
Preferably, the extrusion aid in step (2) is used in an amount of 2-5wt%, such as 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, based on the sum of the composite metal compound and the alumina powder, but is not limited to the recited values, and other non-recited values within the above ranges are equally applicable.
As a preferred technical scheme of the present invention, the process conditions of extrusion molding in the step (4) include: and fully kneading various materials used for molding, and performing extrusion molding by adopting an F-26 double-screw extruder at room temperature.
Preferably, the extrusion pressure of the extrusion molding is 100-200N, for example 100N, 120N, 150N, 180N or 200N, and the screw rotation speed is 10-50r/min, for example 10r/min, 20r/min, 30r/min, 40r/min or 50r/min, etc., but not limited to the values listed, and other values not listed in the above-mentioned value ranges are equally applicable.
Preferably, the temperature of the drying in the step (4) is 100 to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ or the like, but the drying is not limited to the listed values, and other non-listed values in the above-mentioned value range are equally applicable.
Preferably, the drying time in step (4) is 4-12 hours, such as 4 hours, 8 hours, 12 hours, 16 hours, 20 hours or 24 hours, etc., but is not limited to the recited values, and other non-recited values within the above range are equally applicable.
Preferably, the temperature of the calcination in the step (4) is 300 to 450 ℃, for example 300 ℃, 330 ℃, 350 ℃, 380 ℃, 400 ℃, 430 ℃ or 450 ℃, etc., but is not limited to the listed values, and other non-listed values within the above-mentioned range are equally applicable.
Preferably, the time of the calcination in step (4) is 2-8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, etc., but is not limited to the recited values, and other non-recited values within the above range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Preparing a solution:
preparing a mixed solution 1 of a copper-containing compound, a zinc-containing compound and a nickel-containing compound; wherein the copper-containing compound comprises copper formate and/or copper acetate, the zinc-containing compound comprises zinc formate and/or zinc acetate, and the nickel-containing compound comprises nickel formate and/or nickel acetate; the molar concentration of metal ions in the mixed solution 1 is 1.0-2.0mol/L;
adding alkaline silica sol into urea aqueous solution with the mass concentration of 15-30wt% to obtain mixed solution 2; wherein the SiO of the alkaline silica sol 2 The content is 30-40wt%, the particle size is 20-40nm, and the pH is 8.0-10.0;
adding an aminosilane coupling agent into the nano silicon dioxide alcohol solution, and controlling the mass ratio of the aminosilane coupling agent to the nano silicon dioxide alcohol solution to be 1 (20-50) to obtain a mixed solution 3; wherein, in the nano silicon dioxide alcohol solution, siO 2 The content is 15-20wt% and the particle size is 15-30nm; the alcohol solvent of the nano silicon dioxide alcohol solution comprises any one or a combination of at least two of methanol, ethanol and propanol; the aminosilane coupleThe coupling agent comprises any one or a combination of at least two of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, aniline methyl trimethoxy silane and aniline methyl triethoxy silane;
preparing a mixed solution 4 of a palladium-containing compound and a ruthenium-containing compound; wherein the palladium-containing compound comprises palladium acetylacetonate, the ruthenium-containing compound comprises ruthenium acetylacetonate, and the solvent of the mixed solution 4 comprises any one or a combination of at least two of benzene, toluene or chloroform;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, controlling the ratio of the mole number of metal ions in the mixed solution 1 to the mole number of urea in the mixed solution 2 to be 1 (2.0-3.0), evaporating the mixed solution to dryness at 80-100 ℃ for 4-24 hours, roasting the mixed solution at 250-400 ℃ for 2-8 hours, and mixing the obtained composite metal compound with alumina powder with the particle size of 80-150 meshes and an extrusion aid to obtain mixed powder; wherein the amount of the alumina powder is 15-40wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 2-5wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 100-200N, controlling the screw rotation speed to be 10-50r/min, firstly drying at 100-120 ℃ for 4-12h, and then roasting at 300-450 ℃ for 2-8h to obtain the dimethylbenzyl alcohol hydrogenolysis catalyst;
wherein, the steps (2) and (3) are not in sequence.
The invention also aims to provide an application of the dimethylbenzyl alcohol hydrogenolysis catalyst, wherein the dimethylbenzyl alcohol hydrogenolysis catalyst prepared by one of the purposes or the second preparation method is applied to the reaction of preparing isopropylbenzene by the hydrogenolysis of dimethylbenzyl alcohol, and the specific process can be referred to CN104230642B.
Compared with the prior art, the invention has at least the following beneficial effects:
the catalyst for hydrogenolysis of dimethyl benzyl alcohol has the advantages of high dispersity of active components, smooth catalyst pore channels and the like, and has excellent activity and selectivity when being used for preparing isopropylbenzene by hydrogenolysis of dimethyl benzyl alcohol, and has good liquid resistance and high stability.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
< source of raw materials >
Cumene, purchased from Shanghai Ala Biochemical technologies Co., ltd;
dimethyl benzyl alcohol, purchased from tAN_SNhite chemical industry development limited;
sodium silica sol available from Linyan Kohn silicon products Co., ltd;
palladium acetylacetonate, available from Shanghai Ala Biochemical technologies Co., ltd;
ruthenium acetylacetonate, available from Shanghai Ala Biochemical technologies Co., ltd;
copper formate, available from Shanghai Ala Biochemical technologies Co., ltd;
zinc formate, available from Shanghai Ala Biochemical technologies Co., ltd;
nickel formate, available from Shanghai Ala Biochemical technologies Co., ltd;
urea, available from Shanghai Ala Biochemical technologies Co., ltd;
alcohol silica solution, xuan Chengjing r.i. new materials limited;
alumina powder, available from Shanghai Ala Biochemical technologies Co., ltd.
< test method >
1. The composition analysis of the dimethylbenzyl alcohol hydrogenolysis catalyst adopts an X-ray fluorescence spectrometer (XRF) for analysis;
2. Dimethyl benzyl alcohol conversion= (number of moles of dimethyl benzyl alcohol remaining in 1-reaction solution/number of moles of dimethyl benzyl alcohol contained in raw material) ×100%;
cumene selectivity = moles of cumene produced/moles of dimethylbenzyl alcohol converted 100%;
wherein the mole number of the dimethylbenzyl alcohol contained in the raw material, the mole number of the produced isopropylbenzene and the mole number of the dimethylbenzyl alcohol remained in the reaction solution are calculated after analysis by using an Agilent 7820A gas chromatograph, and the test conditions comprise: adopting DB-5 chromatographic column and FID detector, the temperature of vaporization chamber is 260 deg.C, the temperature of detector is 260 deg.C, and carrier gas is high-purity N 2 The flow rate was 30ml/min.
Example 1
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
672.4g of water is firstly added into a reaction kettle, then 96.4g of copper formate, 24.7g of nickel formate and 85.6g of zinc formate are added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
133.3g of urea were dissolved in 755.2g of water to give an aqueous urea solution, after which 78.0g of an alkaline silica sol (SiO 2 30wt% of the mixture, 30nm of particle size and 9.0 pH) and stirring the mixture sufficiently to obtain a mixed solution 2;
11.6g of gamma-aminopropyl trimethoxysilane were added to 253.5g of ethanol solution of nanosilica (SiO 2 20wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
0.5g of palladium acetylacetonate and 4.2g of ruthenium acetylacetonate are dissolved in 93.8g of benzene and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 95 ℃ for 12 hours, then roasting at 300 ℃ for 6 hours, and mixing the obtained composite metal compound with 40.0g of alumina powder with the particle size of 100 meshes and 4.3g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 27.8wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 110 ℃ for 4 hours, and then roasting at 450 ℃ for 4 hours, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst A;
Wherein, the steps (2) and (3) are not in sequence.
Catalyst a was analyzed by X-ray fluorescence spectroscopy (XRF) and had the composition (in terms of inorganic oxide): pdO 0.10wt%, ruO 2 0.70wt％，CuO 17.0wt％，NiO 5.0wt％，ZnO 18.2wt％，Al 2 O 3 20.0wt％，SiO 2 39.0wt％。
And (3) reduction of a catalyst:
catalyst A was charged into a fixed bed hydrogenation reactor with a catalyst loading of 100ml. The catalyst is reduced under the mixed gas of nitrogen and hydrogen before use, and the volume space velocity of the mixed gas is kept for 300h in the reduction process -1 Firstly, raising the temperature of a reactor to 160 ℃ and keeping the temperature for 2 hours to remove physical water adsorbed by the catalyst, and then introducing the catalyst into the reactor, wherein the volume fraction of the physical water is 5v percent H 2 The mixed gas of hydrogen and nitrogen is pre-reduced for 1h, then the proportion of the hydrogen in the mixed gas of the hydrogen and the nitrogen is gradually increased to 10v%, 20v%, 50v% and 100%, the hot spot temperature of the catalyst bed layer in the process is controlled to be not more than 250 ℃, and finally the temperature is increased to 250 ℃ for reduction for 4h under the pure hydrogen atmosphere.
Catalyst performance evaluation:
cumene solution of 25wt% dimethyl benzyl alcohol as raw material is prepared under the conditions of pressure of 2.0MPa, temperature of 150 ℃ and H 2 Alcohol mole ratio 8:1, liquid hourly space velocity 3h -1 The reaction is carried out under the condition of (2). The hydrogenolysis reaction results are shown in Table 1.
Example 2
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
672.4g of water is firstly added into a reaction kettle, then 124.8g of copper formate, 12.4g of nickel formate and 75.0g of zinc formate are added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
145.9g of urea was dissolved in 583.5g of water to obtain an aqueous urea solution, followed by addition of 83.6g of an alkaline silica sol (SiO 2 40wt% of the mixture, 40nm of particle size and 9.0 pH) and stirring thoroughly to obtain a mixed solution 2;
6.5g of gamma-aminopropyl triethoxysilane was added to 264.0g of a nano silica ethanol solution (SiO 2 20wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
0.75g of palladium acetylacetonate and 2.4g of ruthenium acetylacetonate are dissolved in 62.8g of benzene and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 99 ℃ for 12 hours, then roasting at 350 ℃ for 4 hours, and mixing the obtained composite metal compound with 30.0g of alumina powder with the particle size of 100 meshes and 4.3g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 20.8wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 110 ℃ for 8 hours, and then roasting at 400 ℃ for 4 hours, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst B;
wherein, the steps (2) and (3) are not in sequence.
Catalyst B was analyzed by X-ray fluorescence spectroscopy (XRF) and consisted of(in terms of inorganic oxide): pdO 0.15wt%, ruO 2 0.40wt％，CuO 22.0wt％，NiO 2.5wt％，ZnO 15.95wt％，Al 2 O 3 15.0wt％，SiO 2 44.0wt％。
Catalyst B was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in table 1.
Example 3
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
750.3g of water is firstly added into a reaction kettle, then 113.5g of copper formate, 39.6g of nickel formate and 78.2g of zinc formate are added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
189.3g of urea was dissolved in 441.6g of water to give an aqueous urea solution, after which 70.0g of alkaline silica sol (SiO 2 30wt% of the mixture, 30nm of particle size and 9.0 pH) and stirring the mixture sufficiently to obtain a mixed solution 2;
6.8g of aniline methyltrimethoxysilane was added to 248.0g of nano silica propanol solution (SiO 2 15wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
0.90g of palladium acetylacetonate and 1.2g of ruthenium acetylacetonate are dissolved in 41.9g of chloroform and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 95 ℃ for 12 hours, then roasting at 300 ℃ for 8 hours, and mixing the obtained composite metal compound with 50.0g of alumina powder with the particle size of 100 meshes and 4.8g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 31.2wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 110 ℃ for 12h, and then roasting at 400 ℃ for 8h, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst C;
Wherein, the steps (2) and (3) are not in sequence.
Catalyst C was analyzed by X-ray fluorescence spectroscopy (XRF) and had the composition (in terms of inorganic oxide): pdO 0.18wt%, ruO 2 0.20wt％，CuO 20.0wt％，NiO 8wt％，ZnO 16.62wt％，Al 2 O 3 25.0wt％，SiO 2 30.0wt％。
Catalyst C was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in table 1.
Example 4
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
725.4g of water is firstly added into a reaction kettle, then 141.8g of copper formate, 14.8g of nickel formate and 72.6g of zinc formate are added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
169.9g of urea was dissolved in 509.7g of water to obtain an aqueous urea solution, followed by addition of 26.3g of an alkaline silica sol (SiO 2 40wt% of the mixture, 30nm in particle size and 9.0 in pH) and stirring the mixture sufficiently to obtain a mixed solution 2;
9.4g of phenylmethyltriethoxysilane was added to 196.0g of a nanosilica ethanol solution (SiO 2 15wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
0.60g of palladium acetylacetonate and 2.7g of ruthenium acetylacetonate are dissolved in 65.8g of benzene and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 90 ℃ for 12 hours, then roasting at 400 ℃ for 4 hours, and mixing the obtained composite metal compound with 70.0g of alumina powder with the particle size of 100 meshes and 5.0g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 41.8wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 120 ℃ for 4 hours, and then roasting at 450 ℃ for 6 hours, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst D;
wherein, the steps (2) and (3) are not in sequence.
Catalyst D was analyzed by X-ray fluorescence spectroscopy (XRF), composition (as inorganic oxide): pdO 0.12wt%, ruO 2 0.45wt％，CuO 25.0wt％，NiO 3wt％，ZnO 15.43wt％，Al 2 O 3 35.0wt％，SiO 2 21.0wt％。
Catalyst D was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Example 5
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
774.6g of water is firstly added into a reaction kettle, 130.5g of copper formate, 24.7g of nickel formate and 86.1g of zinc formate are then added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
160.5g of urea was dissolved in 642.0g of water to obtain an aqueous urea solution, after which 30.7g of alkaline silica sol (SiO 2 30wt% of the mixture, 40nm in particle size and 9.0 in pH) and stirring the mixture sufficiently to obtain a mixed solution 2;
9.6g of gamma-aminopropyl are reactedThe methyltrimethoxysilane was added to 223.9g of a nanosilicon dioxide ethanol solution (SiO 2 15wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
1.0g of palladium acetylacetonate and 3.0g of ruthenium acetylacetonate are dissolved in 79.8g of benzene and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 95 ℃ for 12 hours, then roasting at 300 ℃ for 8 hours, and mixing the obtained composite metal compound with 60.0g of alumina powder with the particle size of 100 meshes and 4.9g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 37.1wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 120 ℃ for 8 hours, and then roasting at 350 ℃ for 8 hours, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst E;
Wherein, the steps (2) and (3) are not in sequence.
Catalyst E composition (in terms of inorganic oxide) was analyzed by X-ray fluorescence spectroscopy (XRF): pdO 0.2wt%, ruO 2 0.5wt％，CuO 23.0wt％，NiO 5.0wt％，ZnO 18.3wt％，Al 2 O 3 30.0wt％，SiO 2 23.0wt％。
Catalyst E was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Example 6
The embodiment provides a preparation method of a dimethyl benzyl alcohol hydrogenolysis catalyst, which comprises the following steps:
(1) Preparing a solution:
644.1g of water is firstly added into a reaction kettle, 102.1g of copper formate, 19.8g of nickel formate and 77.8g of zinc formate are then added, and the mixture is fully stirred and dissolved to obtain a mixed solution 1;
156.7g of urea was dissolved in 470.0g of water to obtain an aqueous urea solution, after which 32.2g of an alkaline silica sol (SiO 2 40wt% of the mixture, 40nm of particle size and 9.0 pH) and stirring thoroughly to obtain a mixed solution 2;
6.8g of gamma-aminopropyl triethoxysilane was added to 208.5g of a nano silica propanol solution (SiO 2 15wt% of the mixture, and the particle size is 30 nm), and fully stirring the mixture to obtain a mixed solution 3;
0.8g of palladium acetylacetonate and 1.8g of ruthenium acetylacetonate are dissolved in 51.9g of chloroform and fully stirred to obtain a mixed solution 4;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, firstly evaporating at 90 ℃ for 12 hours, then roasting at 400 ℃ for 8 hours, and mixing the obtained composite metal compound with 76.0g of alumina powder with the particle size of 100 meshes and 5.0g of sesbania powder to obtain mixed powder; wherein the amount of the alumina powder is 45.8wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 3.0wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 150N, controlling the screw rotation speed to be 30r/min, firstly drying at 100 ℃ for 12h, and then roasting at 400 ℃ for 4h, wherein the obtained dimethylbenzyl alcohol hydrogenolysis catalyst is denoted as a catalyst F;
wherein, the steps (2) and (3) are not in sequence.
The catalyst F composition (in terms of inorganic oxide) was analyzed by X-ray fluorescence spectroscopy (XRF): pdO 0.16wt%, ruO 2 0.3wt％，CuO 18.0wt％，NiO 4.0wt％，ZnO 16.54wt％，Al 2 O 3 38.0wt％，SiO 2 23.0wt％。
Catalyst F was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in table 1.
Comparative example 1
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 1, differing only in: step (1) does not use urea aqueous solution, i.e. the mixed solution 2 is alkaline silica sol (SiO 2 30wt% of the polymer, 30nm of particle size and 9.0 pH); the obtained dimethylbenzyl alcohol hydrogenolysis catalyst was designated as catalyst G.
Catalyst G was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in table 1.
Comparative example 2
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 2, differing only in: step (2) using no alumina powder, i.e., mixing the obtained composite metal compound directly with 4.3g sesbania powder to obtain mixed powder; the obtained catalyst for hydrogenolysis of dimethylbenzyl alcohol was designated as catalyst H.
Catalyst H was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Comparative example 3
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 3, differing only in: step (1) no aminosilane coupling agent (phenylmethyltrimethoxysilane) was used, i.e., mixed solution 3 was a nano-silica propanol solution (SiO 2 15wt% of the particles and 30nm of the particle size); the obtained catalyst for hydrogenolysis of dimethylbenzyl alcohol was designated as catalyst I.
Catalyst I was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Comparative example 4
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 4, differing only in: step (1) without using nanosilica ethanol solution (SiO 2 15wt% and 30nm particle size), and the alkaline silica Sol (SiO) of step (1) 2 40wt%, particle size 30nm, pH 9.0) from 26.3g to 99.8g; the obtained dimethylbenzyl alcohol hydrogenolysis catalyst was designated as catalyst J.
Catalyst J was subjected to a catalyst reduction test and catalyst performance evaluation, and specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Comparative example 5
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 5, differing only in: step (1) was carried out without palladium acetylacetonate and was substituted with an equivalent molar amount of ruthenium acetylacetonate, i.e., 1.30g of ruthenium acetylacetonate was additionally added; the obtained catalyst for hydrogenolysis of dimethylbenzyl alcohol was designated as catalyst K.
Catalyst K was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Comparative example 6
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 5, differing only in: step (1) was carried out without ruthenium acetylacetonate and replaced with an equivalent molar amount of palladium acetylacetonate, i.e. 2.30g of palladium acetylacetonate was additionally added; the obtained catalyst for hydrogenolysis of dimethylbenzyl alcohol was designated as catalyst L.
Catalyst L was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in Table 1.
Comparative example 7
This comparative example provides a method for preparing a catalyst for hydrogenolysis of dimethylbenzyl alcohol, with reference to example 6, differing only in: palladium acetylacetonate and ruthenium acetylacetonate are respectively substituted by palladium chloride and ruthenium chloride with the same molar quantity, namely, 0.46g of palladium chloride and 0.94g of ruthenium chloride are dissolved in 28.0g of water, and the mixed solution 4 is obtained by fully stirring; the obtained catalyst for hydrogenolysis of dimethylbenzyl alcohol was designated as catalyst M.
Catalyst M was subjected to catalyst reduction testing and catalyst performance evaluation, specific process conditions and procedures were as described in example 1, and hydrogenolysis reaction results are shown in table 1.
The results of the hydrogenolysis reactions corresponding to the catalysts prepared in the above examples and comparative examples are summarized in table 1 below.
TABLE 1
From table 1, the following points can be seen:
(1) The catalyst A-F obtained by the preparation method has good activity and selectivity, which shows that the catalyst for hydrogenolysis of dimethylbenzyl alcohol has high dispersity of active components and smooth catalyst pore channels, and has excellent activity and selectivity when being used for preparing isopropylbenzene by hydrogenolysis of dimethylbenzyl alcohol;
(2) Comparison of example 1 and comparative example 1 shows that the addition of urea during the preparation of the dimethylbenzyl alcohol hydrogenolysis catalyst can improve the mass transfer performance of the catalyst and increase the reactivity and selectivity;
(3) Comparison of example 2 and comparative example 2 shows that the absence of alumina powder in the preparation process of the dimethylbenzyl alcohol hydrogenolysis catalyst can result in weaker acidity of the catalyst, adverse to dimethylbenzyl alcohol conversion and lower catalyst activity;
(4) By comparing the example 3 with the comparative example 3, the addition of the aminosilane coupling agent in the preparation process of the dimethylbenzyl alcohol hydrogenolysis catalyst is helpful for improving the dispersity of noble metals, thereby improving the reaction conversion rate;
(5) By comparing example 4 with comparative example 4, it is demonstrated that the addition of nanosilica alcohol solution during the preparation of dimethylbenzyl alcohol hydrogenolysis catalyst helps to increase the hydrogenolysis reactivity of the catalyst;
(6) Comparison of example 5 and comparative examples 5 and 6 shows that the noble metal active component in the dimethylbenzyl alcohol hydrogenolysis catalyst is Ru or Pd, so that the hydrogenolysis activity is low, and excessive Pd content can promote excessive hydrogenation side reaction;
(7) By comparing example 6 with comparative example 6, it is demonstrated that noble metal palladium sources and ruthenium sources in the dimethylbenzyl alcohol hydrogenolysis catalyst are preferably palladium acetylacetonate and ruthenium acetylacetonate, which are beneficial to improving the dispersity of Pd and Ru, and further improving the reactivity of the dimethylbenzyl alcohol hydrogenolysis catalyst.
The detailed process equipment and process flow of the present invention are described by the above embodiments, but the present invention is not limited to, i.e., it does not mean that the present invention must be practiced depending on the detailed process equipment and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (35)
1. A dimethylbenzyl alcohol hydrogenolysis catalyst characterized in that it comprises, based on the total weight of the dimethylbenzyl alcohol hydrogenolysis catalyst, 100wt% and calculated as inorganic oxide, the following components:
PdO 0.01-0.3wt％；
RuO 2 0.05-0.8wt％；
CuO 15.0-25.0wt％；
ZnO 15.0-25.0wt％；
NiO 2.0-10.0wt％；
Al 2 O 3 15.0-40.0wt％；
SiO 2 20.0-45.0wt％；
the dimethylbenzyl alcohol hydrogenolysis catalyst is prepared by the following preparation method, and comprises the following steps:
(1) Preparing a mixed solution 1 of a copper-containing compound, a zinc-containing compound and a nickel-containing compound; adding silica sol into urea aqueous solution to obtain mixed solution 2; adding an aminosilane coupling agent into the nano silicon dioxide alcohol solution to obtain a mixed solution 3; preparing a mixed solution 4 of a palladium-containing compound and a ruthenium-containing compound;
(2) Adding the mixed solution 1 into the mixed solution 2, sequentially stirring, evaporating to dryness and roasting, and mixing the obtained composite metal compound with alumina powder and an extrusion aid to obtain mixed powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), and sequentially mixing, extruding, forming, drying and roasting to obtain the dimethylbenzyl alcohol hydrogenolysis catalyst;
wherein, the steps (2) and (3) are not in sequence.
2. The dimethylbenzyl alcohol hydrogenolysis catalyst according to claim 1, wherein in the dimethylbenzyl alcohol hydrogenolysis catalyst, the molar ratio of Pd to Ru is 1 (1-10), the molar ratio of Cu to Zn is 1 (0.5-1.0), and the molar ratio of Cu to Ni is 1 (0.1-0.5).
3. A dimethylbenzyl alcohol hydrogenolysis catalyst according to claim 1, characterized in that the dimethylbenzyl alcohol hydrogenolysis catalyst is hollow ring-shaped, having an outer diameter of 3-5mm, an inner diameter of 1-3mm, and a length of 3-8mm.
4. A process for preparing a dimethylbenzyl alcohol hydrogenolysis catalyst according to any one of claims 1-3, characterized in that the process comprises the steps of:
(1) Preparing a mixed solution 1 of a copper-containing compound, a zinc-containing compound and a nickel-containing compound; adding silica sol into urea aqueous solution to obtain mixed solution 2; adding an aminosilane coupling agent into the nano silicon dioxide alcohol solution to obtain a mixed solution 3; preparing a mixed solution 4 of a palladium-containing compound and a ruthenium-containing compound;
(2) Adding the mixed solution 1 into the mixed solution 2, sequentially stirring, evaporating to dryness and roasting, and mixing the obtained composite metal compound with alumina powder and an extrusion aid to obtain mixed powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), and sequentially mixing, extruding, forming, drying and roasting to obtain the dimethylbenzyl alcohol hydrogenolysis catalyst;
wherein, the steps (2) and (3) are not in sequence.
5. The method according to claim 4, wherein in the mixed solution 1 of step (1), the copper-containing compound comprises copper formate and/or copper acetate.
6. The method according to claim 4, wherein in the mixed solution 1 of step (1), the zinc-containing compound comprises zinc formate and/or zinc acetate.
7. The method according to claim 4, wherein in the mixed solution 1 of step (1), the nickel-containing compound comprises nickel formate and/or nickel acetate.
8. The method according to claim 4, wherein the molar concentration of the metal ions in the mixed solution 1 in the step (1) is 1.0 to 2.0mol/L.
9. The method according to claim 4, wherein the urea aqueous solution in step (1) has a mass concentration of 15 to 30wt%.
10. The method according to claim 4, wherein the silica sol in the step (1) is an alkaline silica sol.
11. The method according to claim 10, wherein the alkaline silica sol is SiO 2 The content is 30-40wt%, the particle size is 20-40nm, and the pH is 8.0-10.0.
12. The method of claim 4, wherein in the alcoholic solution of nanosilica in step (1), siO 2 The content is 15-20wt% and the particle size is 15-30nm.
13. The method of claim 4, wherein the alcoholic solvent of the alcoholic solution of nanosilica in step (1) comprises any one or a combination of at least two of methanol, ethanol or propanol.
14. The method according to claim 4, wherein the aminosilane coupling agent in the step (1) comprises any one or a combination of at least two of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, aminomethyl trimethoxysilane, and aminomethyl triethoxysilane.
15. The method according to claim 4, wherein the mass ratio of the aminosilane coupling agent to the nanosilica alcohol solution is controlled to be 1 (20-50) in the preparation of the mixed solution 3 in step (1).
16. The method according to claim 4, wherein in the mixed solution 4 of step (1), the palladium-containing compound comprises palladium acetylacetonate.
17. The method according to claim 4, wherein in the mixed solution 4 of step (1), the ruthenium-containing compound comprises ruthenium acetylacetonate.
18. The method according to claim 4, wherein the solvent of the mixed solution 4 in the step (1) comprises any one or a combination of at least two of benzene, toluene and chloroform.
19. The method according to claim 4, wherein in the step (2), the ratio of the number of moles of metal ions in the mixed solution 1 to the number of moles of urea in the mixed solution 2 is controlled to be 1 (2.0 to 3.0).
20. The method according to claim 4, wherein the evaporating temperature in the step (2) is 80-100 ℃.
21. The method according to claim 4, wherein the drying time in step (2) is 4 to 24 hours.
22. The method according to claim 4, wherein the baking temperature in the step (2) is 250 to 400 ℃.
23. The method according to claim 4, wherein the calcination time in the step (2) is 2 to 8 hours.
24. The method according to claim 4, wherein the alumina powder in step (2) has a particle size of 80 to 150 mesh.
25. The method according to claim 4, wherein the alumina powder in the step (2) is used in an amount of 15 to 40wt% based on the sum of the mass of the composite metal compound and the mass of the alumina powder.
26. The method of claim 4, wherein the extrusion aid in step (2) comprises sesbania powder.
27. The method according to claim 4, wherein the extrusion aid in the step (2) is used in an amount of 2 to 5wt% based on the sum of the mass of the composite metal compound and the mass of the alumina powder.
28. The method according to claim 4, wherein the extrusion molding process conditions of step (4) include: and fully kneading various materials used for molding, and performing extrusion molding by adopting an F-26 double-screw extruder at room temperature.
29. The method of claim 28, wherein the extrusion pressure of the extrusion is 100-200N and the screw speed is 10-50r/min.
30. The method according to claim 4, wherein the drying temperature in the step (4) is 100 to 120 ℃.
31. The method according to claim 4, wherein the drying time in the step (4) is 4 to 12 hours.
32. The method according to claim 4, wherein the baking temperature in the step (4) is 300 to 450 ℃.
33. The method according to claim 4, wherein the calcination time in the step (4) is 2 to 8 hours.
34. The preparation method according to claim 4, characterized in that the preparation method comprises the steps of:
(1) Preparing a solution:
preparing a mixed solution 1 of a copper-containing compound, a zinc-containing compound and a nickel-containing compound; wherein the copper-containing compound comprises copper formate and/or copper acetate, the zinc-containing compound comprises zinc formate and/or zinc acetate, and the nickel-containing compound comprises nickel formate and/or nickel acetate; the molar concentration of metal ions in the mixed solution 1 is 1.0-2.0mol/L;
adding alkaline silica sol into urea aqueous solution with the mass concentration of 15-30wt% to obtain mixed solution 2; which is a kind of In the alkaline silica sol, siO 2 The content is 30-40wt%, the particle size is 20-40nm, and the pH is 8.0-10.0;
adding an aminosilane coupling agent into the nano silicon dioxide alcohol solution, and controlling the mass ratio of the aminosilane coupling agent to the nano silicon dioxide alcohol solution to be 1 (20-50) to obtain a mixed solution 3; wherein, in the nano silicon dioxide alcohol solution, siO 2 The content is 15-20wt% and the particle size is 15-30nm; the alcohol solvent of the nano silicon dioxide alcohol solution comprises any one or a combination of at least two of methanol, ethanol and propanol; the aminosilane coupling agent comprises any one or a combination of at least two of gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, aniline methyl trimethoxy silane and aniline methyl triethoxy silane;
preparing a mixed solution 4 of a palladium-containing compound and a ruthenium-containing compound; wherein the palladium-containing compound comprises palladium acetylacetonate, the ruthenium-containing compound comprises ruthenium acetylacetonate, and the solvent of the mixed solution 4 comprises any one or a combination of at least two of benzene, toluene or chloroform;
(2) Adding the mixed solution 1 into the mixed solution 2, stirring, controlling the ratio of the mole number of metal ions in the mixed solution 1 to the mole number of urea in the mixed solution 2 to be 1 (2.0-3.0), evaporating the mixed solution to dryness at 80-100 ℃ for 4-24 hours, roasting the mixed solution at 250-400 ℃ for 2-8 hours, and mixing the obtained composite metal compound with alumina powder with the particle size of 80-150 meshes and an extrusion aid to obtain mixed powder; wherein the amount of the alumina powder is 15-40wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder, and the amount of the extrusion aid is 2-5wt% of the sum of the mass of the composite metal compound and the mass of the alumina powder;
(3) Dropwise adding the mixed solution 4 into the mixed solution 3 to obtain a mixed solution 5;
(4) Adding the mixed powder obtained in the step (2) into the mixed solution 5 obtained in the step (3), stirring, fully kneading various materials used for molding, performing extrusion molding by adopting an F-26 double-screw extruder at room temperature, controlling the extrusion pressure of the extrusion molding to be 100-200N, controlling the screw rotation speed to be 10-50r/min, firstly drying at 100-120 ℃ for 4-12h, and then roasting at 300-450 ℃ for 2-8h to obtain the dimethylbenzyl alcohol hydrogenolysis catalyst;
wherein, the steps (2) and (3) are not in sequence.
35. The application of the dimethylbenzyl alcohol hydrogenolysis catalyst is characterized in that the dimethylbenzyl alcohol hydrogenolysis catalyst prepared by any one of claims 1-3 or the dimethylbenzyl alcohol hydrogenolysis catalyst prepared by any one of claims 4-34 is applied to the reaction of preparing cumene through the hydrogenolysis of dimethylbenzyl alcohol.
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| JPS6140227A (en) * | 1984-07-31 | 1986-02-26 | Sumitomo Chem Co Ltd | Production of isobutylbenzene |
| CN102641734A (en) * | 2011-02-18 | 2012-08-22 | 中国石油化工集团公司 | Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof |
| CN109529870A (en) * | 2018-12-12 | 2019-03-29 | 万华化学集团股份有限公司 | A kind of hydrogenation of acetophenone catalyst and preparation method thereof |
| CN112517059A (en) * | 2020-12-16 | 2021-03-19 | 万华化学集团股份有限公司 | Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof |
| CN112569972A (en) * | 2019-09-29 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing isopropyl benzene and preparation and application thereof |
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| JPS6140227A (en) * | 1984-07-31 | 1986-02-26 | Sumitomo Chem Co Ltd | Production of isobutylbenzene |
| CN102641734A (en) * | 2011-02-18 | 2012-08-22 | 中国石油化工集团公司 | Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof |
| CN109529870A (en) * | 2018-12-12 | 2019-03-29 | 万华化学集团股份有限公司 | A kind of hydrogenation of acetophenone catalyst and preparation method thereof |
| CN112569972A (en) * | 2019-09-29 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing isopropyl benzene and preparation and application thereof |
| CN112517059A (en) * | 2020-12-16 | 2021-03-19 | 万华化学集团股份有限公司 | Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method thereof |
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