CN108686712B - Modified alpha-alumina carrier and preparation method thereof, silver catalyst and application - Google Patents
Modified alpha-alumina carrier and preparation method thereof, silver catalyst and application Download PDFInfo
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- CN108686712B CN108686712B CN201710218015.9A CN201710218015A CN108686712B CN 108686712 B CN108686712 B CN 108686712B CN 201710218015 A CN201710218015 A CN 201710218015A CN 108686712 B CN108686712 B CN 108686712B
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- Prior art keywords
- alumina
- alpha
- carrier
- alumina carrier
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 239000004332 silver Substances 0.000 title claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 80
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 19
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052702 rhenium Inorganic materials 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 150000004682 monohydrates Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- YONLFQNRGZXBBF-ZIAGYGMSSA-N (2r,3r)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-ZIAGYGMSSA-N 0.000 claims description 2
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 10
- -1 small molecule compounds Chemical class 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
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- 230000008901 benefit Effects 0.000 description 2
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
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- 238000004375 physisorption Methods 0.000 description 2
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- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
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- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
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- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B01J35/612—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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 relates to the field of olefin epoxidation reaction, and provides a modified alpha-alumina carrier, a preparation method thereof, a silver catalyst and application thereof, wherein the modified alpha-alumina carrier comprises a molded alpha-alumina carrier and mesoporous alumina growing on the molded alpha-alumina carrier; the crushing strength of the modified alpha-alumina carrier is 55-220N, and the specific surface area is 1.30-2.5m2The pore volume is 0.40-0.80mL/g, and the water absorption rate is not lower than 42%; the pore size of the mesoporous alumina is 2-200 nm. The invention enlarges the pore canal of the carrier, and compared with the carrier prepared by the prior art, the modified alpha-alumina carrier can improve the dispersibility of the active component of the catalyst on the carrier. The silver catalyst prepared by the modified alpha-alumina carrier shows good activity and higher selectivity in the process of producing ethylene oxide by oxidizing ethylene.
Description
Technical Field
The invention relates to the field of olefin epoxidation reaction, and particularly provides a modified alpha-alumina carrier, a preparation method of the modified alpha-alumina carrier, the modified alpha-alumina carrier prepared by the method, a silver catalyst, and application of the modified alpha-alumina carrier or the silver catalyst in production of ethylene oxide by ethylene oxidation.
Background
Under the action of the silver catalyst, ethylene is oxidized to mainly generate ethylene oxide, and byproducts of carbon dioxide, water and the like are generated at the same time, wherein the activity, the selectivity and the stability are main performance indexes of the silver catalyst. The activity refers to the reaction temperature required when the ethylene oxide production process reaches a certain reaction load, and the lower the reaction temperature is, the higher the activity of the catalyst is; selectivity refers to the ratio of moles of ethylene converted to ethylene oxide in the reaction to the total reacted moles of ethylene; stability is expressed as the rate of decline of activity and selectivity, the smaller the rate of decline, the better the stability of the catalyst. The silver catalyst with high activity, high selectivity and good stability is used in the process of producing ethylene oxide by oxidizing ethylene, so that the economic benefit can be greatly improved, and the preparation of the silver catalyst with high activity, high selectivity and good stability is the main direction of research on the silver catalyst. The performance of the silver catalyst is not only related to the composition of the catalyst and the preparation method, but also related to the performance of the carrier used in the catalyst and the preparation method.
The preparation method of the silver catalyst mainly comprises the preparation of a porous carrier (such as alumina) and the two processes of applying an active component and an auxiliary agent to the carrier. The carrier is generally alpha-alumina with small specific surface area. The alumina has more than ten crystal forms, and is commonly alpha, gamma, theta, eta, delta and the like, and in the crystal phases, the alpha phase is a stable phase and directly influences the performance of the silver catalyst.
The carrier needs to provide a certain surface for loading the active component and uniformly dispersing the active component thereon, which puts certain requirements on the pore structure of the carrier. The pores of the alumina carrier can be classified into three types: (1) primary particle inter-grain pores are mainly dehydration pores of alumina raw material grains and are basically gaps between parallel plate surfaces with the size of 1-2 nm; (2) the pores among the secondary particles of the alumina raw material are changed along with the escape of moisture and the change of a crystal phase during calcination and are pores more than tens of nanometers; and (3) defective pores and macropores generated when the pore-forming agent and the support are formed.
The silver catalyst carrier should not only have high strength, but also provide a suitable specific surface and pore structure. The formed carrier is treated to modify the surface of the carrier, improve the dispersion condition of the catalytic active component silver, change the acidity and alkalinity of the surface of the carrier, and modulate the electronic condition of the surface of the metallic silver and the absorption and desorption conditions of reaction species, thereby improving the catalytic performance of the silver catalyst. There have been some studies reported in this regard.
Japanese patent JP2002136868 reports a method for preparing an alumina carrier: firstly, forming a carrier raw material, roasting at the temperature of 500-2000 ℃ to form a carrier precursor with the main component of alumina, treating the obtained precursor by adopting a hydrofluoric acid solution with the concentration of 0.1-15%, and roasting at the temperature of 1000-2000 ℃ for a plurality of hours to form a carrier finished product, wherein the silver catalyst prepared from the obtained carrier has excellent performance.
German patent DE2933950 reports a process for purifying silver catalyst supports, which states that pure α -alumina should be used as support material, and that without this purity of alumina, commercially available normal α -alumina can be purified: the wet alpha alumina was boiled with about an equal amount of 1 wt% NaOH solution for 30min and then washed with deionized water until the pH of the wet alpha alumina was below 8. The patent recognizes that the carrier can also be obtained by other methods such as boiling the carrier with about an equal amount of a1 wt% hydrofluoric acid solution for 10min and then washing with water until the pH is not less than 5. The activity and service life (stability) of the silver catalyst containing the alkali metal promoter prepared by the carrier obtained by the method are obviously improved, but the selectivity is only about 81.7 percent, and the processing process is complicated.
U.S. Pat. No. 3, 4786743A also describes a silver catalyst made from a carrier whose surface has been treated with an acid having a pKa of ≦ 3 and containing a step-like structure, which has good thermal stability, activity and selectivity, but the highest selectivity is only around 80%.
The above patent documents refer to methods for treating the alumina carrier, which are direct treatments on the surface of the molded alpha-alumina carrier, and these methods have limited activity improvement effect on the silver catalyst and have insignificant improvement effect on selectivity. Therefore, there is a problem in that research and development of a method capable of increasing the activity and selectivity of a silver catalyst to a greater extent are still required.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a modified alpha-alumina carrier which enables a silver catalyst to meet high activity and simultaneously has higher selectivity and a preparation method thereof, a silver catalyst comprising the modified alpha-alumina carrier, and application of the modified alpha-alumina carrier or the silver catalyst in ethylene oxidation production of ethylene oxide.
The inventor of the invention finds that the activity improvement effect on the silver catalyst is limited and the improvement effect on the selectivity is not large by only directly treating the surface of the formed alpha-alumina carrier. In order to improve the performance of the alpha-alumina carrier, the inventors have made extensive studies on the alpha-alumina carrier, and found that a silver catalyst with better selectivity can be prepared based on the carrier by growing mesoporous alumina on the surface of the alpha-alumina carrier. The present invention has been made based on the above findings.
According to a first aspect of the present invention there is provided a modified alpha-alumina support comprising a shaped alpha-alumina support and mesoporous alumina grown thereon; the crushing strength of the modified alpha-alumina carrier is 55-220N, and the specific surface area is 1.30-2.5m2The pore volume is 0.40-0.80mL/g, and the water absorption rate is not lower than 42%; the pore size of the mesoporous alumina is 2-200nm, preferably 30-100 nm.
According to a second aspect of the present invention, there is provided a process for the preparation of a modified α -alumina support, the process comprising: and mixing the formed alpha-alumina carrier with the mesoporous alumina precursor mixture, and reacting, drying and roasting to grow mesoporous alumina on the formed alpha-alumina carrier so as to prepare the modified alpha-alumina carrier.
According to a third aspect of the present invention there is provided a modified alpha-alumina support prepared by the above method.
According to a fourth aspect of the present invention, there is provided a silver catalyst comprising:
component a, the modified alpha-alumina carrier;
component b, silver;
component c, an alkali metal and/or an alkaline earth metal;
component d, rhenium and optionally a co-adjuvant therefor;
optional component e: an organic amine.
According to a fifth aspect of the present invention there is provided the use of a modified alpha alumina support as described above or a silver catalyst as described above in the production of ethylene oxide by the oxidation of ethylene.
The mesoporous macroporous alumina grows on the surface of the alpha-alumina carrier, so that the pore channels of the carrier are increased. The silver catalyst prepared by the modified alpha-alumina carrier shows good activity and higher selectivity in the process of producing ethylene oxide by oxidizing ethylene.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention there is provided a modified alpha-alumina support,the modified alpha-alumina carrier comprises a molded alpha-alumina carrier and mesoporous alumina growing on the molded alpha-alumina carrier; the crushing strength of the modified alpha-alumina carrier is 55-220N, and the specific surface area is 1.30-2.5m2The pore volume is 0.40-0.80mL/g, and the water absorption is not less than 42%.
Preferably, the modified alpha-alumina carrier has a crushing strength of 90-140N and a specific surface area of 1.30-2.0m2The pore volume is 0.50-0.55mL/g, and the water absorption is not less than 50%.
More preferably, the specific surface area of the modified alpha-alumina carrier is 1.30-1.5m2/g。
The modified alpha-alumina is particularly suitable for being used as a carrier of a silver catalyst for ethylene epoxidation reaction. The macroporous alumina attached to the surface of the molded alpha-alumina carrier can increase the specific surface of the carrier, reduce the fluidity of silver particles, improve the sintering resistance of a silver catalyst, improve the selectivity of the catalyst and prolong the service life of the catalyst.
The mesoporous alumina has a regular or irregular pore channel structure, and the pore size is 2-200 nm. The aperture size of the mesoporous alumina is preferably 30-100nm, so that the activity and selectivity of the silver catalyst can be further improved.
In the present invention, the kind of the mesoporous alumina may be selected conventionally in the art, for example, one or more of acidic alumina, basic alumina and neutral alumina. Preferably, the mesoporous alumina is alkaline alumina and/or neutral alumina.
According to a second aspect of the present invention, there is provided a process for the preparation of a modified α -alumina support, the process comprising: and mixing the formed alpha-alumina carrier with the mesoporous alumina precursor mixture, and reacting, drying and roasting to grow mesoporous alumina on the formed alpha-alumina carrier so as to prepare the modified alpha-alumina carrier.
In the present invention, the shaped α -alumina support may be prepared according to a conventional method in the art. According to a preferred embodiment, the shaped alpha-alumina support is prepared by: mixing an alumina raw material, a binder and a proper amount of water, and optionally adding an auxiliary agent to obtain a precursor mixture of the alpha-alumina carrier; then, the precursor mixture is kneaded, shaped, dried, and fired.
The alumina source refers to an aluminum source which can be completely converted into alpha-alumina after being calcined, and includes but is not limited to hydrated alumina and/or transition phase alumina. According to a preferred embodiment, the alumina starting materials are alpha-alumina trihydrate and pseudo-alumina monohydrate. Typically, the amount of alpha-alumina trihydrate is from 50 to 90 wt% and the amount of pseudo-alumina monohydrate is from 10 to 50 wt%, based on the total weight of the alumina feedstock.
Additionally, the particle size of the alumina feedstock is conventionally selected, for example, the alpha-alumina trihydrate may be 50 to 500 mesh and the pseudo-alumina monohydrate may be greater than 200 mesh.
The binder can generate alumina sol with alumina raw materials, and the components are bound together to form paste which can be extruded and formed. For example, the binder may be mixed with pseudo-hydrated alumina as an alumina sol, and thus, the pseudo-hydrated alumina, the binder, and water may be provided directly in the form of an alumina sol. The binder may be selected from acids, such as at least one of nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid, preferably nitric acid.
The binder and water may be added separately or in the form of an aqueous binder solution, which may be added in an amount of 15 to 60 wt%, preferably 15 to 45 wt%, more preferably 15 to 35 wt%, and still more preferably 15 to 25 wt%, based on the total weight of the precursor mixture. In the aqueous binder solution, the weight ratio of the binder to water may be 1: 1.25-10, and preferably the weight ratio of the binder to water is 1: 4-5. In the case of separate addition, the addition amounts of the binder and water also satisfy the above ranges.
The addition of the auxiliary agent can improve the pore structure and the mechanical strength of the alpha-alumina carrier. The auxiliary agent is preferably one or more of silicon, silicon-containing compound and alkaline earth metal compound, and the silicon-containing compound is SiO2. The assistant may be used in an amount of 0 to 5 parts by weight with respect to 100 parts by weight of the alumina raw material.
In order to mix the components of the alpha-alumina carrier precursor mixture uniformly, the alpha-alumina carrier precursor mixture is kneaded in a kneader, and the kneading time can be 5-90 min. After the α -alumina carrier precursor mixture is sufficiently kneaded, the carrier is shaped (formed), which may be performed in a forming machine. The shaped alpha-alumina support may be in a shape conventional in the art, including, but not limited to, a ring shape, a sphere shape, a column shape, or a porous column shape, specifically, for example, a honeycomb-shaped cylindrical particle having seven, five, or three holes with an outer diameter of 7 to 9mm and a honeycomb pore diameter of 1 to 3mm, a single-hole annular particle having an outer diameter of 7 to 9mm and an inner diameter of 3 to 6mm, and the like.
Drying the formed product after the precursor mixture is formed, wherein the drying can be carried out at 80-130 ℃, the water content in the formed product is controlled to be below 10 percent, and the drying time is determined according to the water content; typically the drying time may be from 1 to 24 hours.
In order to obtain a shaped alpha-alumina carrier having suitable characteristics, the present invention calcines the dried shaped article. The roasting comprises the processes of temperature programming and constant-temperature roasting, wherein the temperature of the constant-temperature roasting can be 1000-1600 ℃, and the temperature of the constant-temperature roasting is preferably 1100-1500 ℃; the constant-temperature roasting time can be 2-24 h.
According to a specific embodiment, the shaped α -alumina support is prepared by the following method:
step A, mixing the alpha-alumina trihydrate, pseudo-monohydrate alumina and optional auxiliary agents to prepare a solid mixture;
step B, adding a binder aqueous solution into the solid mixture to obtain an alpha-alumina carrier precursor mixture;
and step C, kneading, molding, drying and roasting the alpha-alumina carrier precursor mixture to obtain the molded alpha-alumina carrier.
In the present invention, the concept of the mesoporous alumina precursor mixture is well known in the art, and refers to a mixture of various raw materials for preparing mesoporous alumina.
According to one embodiment, the mesoporous alumina precursor mixture comprises a template, an aluminum source, and water.
The template can be one or more of a surfactant, other water-soluble polymers different from the surfactant and organic small molecule compounds. Preferably, the template is at least one selected from the group consisting of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, P123, polyethylene glycol, polyacrylamide, oleic acid monoglyceride, acrylamide, glucose, sucrose, dibenzoyl-L-tartaric acid and ethylene glycol, and more preferably, the template is at least one selected from the group consisting of P123, polyethylene glycol, polyacrylamide and sucrose.
The aluminum source refers to an organic aluminum salt and/or an inorganic aluminum salt, preferably at least one selected from the group consisting of aluminum isopropoxide, aluminum isobutoxide, aluminum nitrate, aluminum sulfate and sodium aluminate, more preferably aluminum isopropoxide and/or aluminum nitrate.
Typically, the weight ratio of the template, the source of aluminium and the water is from 1: 0.5 to 10: 2 to 30.
In this embodiment, the weight ratio of the shaped alpha-alumina support to the mesoporous alumina precursor mixture (based on the total amount of the template, the aluminum source and the water) is 1: 5-30, preferably 1: 5-25.
Preferably, the mesoporous alumina precursor mixture further comprises a pH adjuster and/or a precipitant. The pH regulator is selected from nitric acid and ammonia water, and is used for preparing acidic or alkaline mesoporous alumina respectively, and the precipitant is selected from ammonium carbonate and urea. The amounts of the pH regulator and the precipitant are well known in the art and will not be described herein.
According to one embodiment, the process for preparing modified alpha-alumina comprises the steps of:
1) mixing the template, an aluminum source and water, and adding a pH regulator and an optional precipitator after the aluminum source is dissolved;
2) mixing the product obtained in step 1) with the formed alpha-alumina carrier in a hydrothermal reaction kettle (such as a stainless steel reaction kettle with a polytetrafluoroethylene lining), and carrying out hydrothermal treatment for 0.5-24h at 20-250 ℃ (preferably 20-150 ℃);
3) drying and roasting the product obtained in the step 2). Preferably, the product is filtered off with suction before this drying to remove the excess liquid phase.
In addition, when the template is selected from the group consisting of polyacrylamide, the method for preparing the modified α -alumina comprises the steps of:
1) mixing the aluminum source, water, acrylamide and an initiator, and adding the formed alpha-alumina carrier and an optional precipitator after the aluminum source is dissolved;
2) after the solution obtained in the step 1) is transparent, heating at 50-90 ℃ for 60-120min to initiate acrylamide polymerization to obtain polyacrylamide wet gel;
3) and drying and roasting the polyacrylamide wet gel.
The initiator is a conventional choice for acrylamide polymerization, and is selected, for example, from water-soluble peroxides, preferably ammonium persulfate; the weight ratio of the acrylamide monomer to the initiator is usually 1: 0.01-0.5.
Mixing the formed alpha-alumina carrier and the mesoporous alumina precursor mixture, and after reaction, drying at 50-130 ℃ for 10-50 h; the roasting can be carried out at 400-700 ℃ for 1-12 h.
According to a third aspect of the present invention there is provided a modified alpha-alumina support prepared by the above method. The prepared modified alpha-alumina carrier has the structure and physical parameters of the modified alpha-alumina carrier in the first aspect of the invention, and is not described in detail herein.
According to a fourth aspect of the present invention, there is provided a silver catalyst comprising:
component a, the above-mentioned modified alpha-alumina carrier;
component b, silver;
component c, an alkali metal and/or an alkaline earth metal;
component d, rhenium and optionally co-adjuvants thereof;
optional component e: an organic amine.
In the silver catalyst, components c and d are both promoters of the silver catalyst. Components b to d refer to the corresponding elements present in the silver catalyst.
The alkali metal is at least one selected from lithium, sodium, potassium, rubidium and cesium; the alkaline earth metal is selected from at least one of calcium, magnesium, strontium and barium.
In the present invention, the silver catalyst may be prepared in a conventional manner, for example by applying (coating or impregnating) a silver-containing compound, an organic amine, an alkali metal promoter, an alkaline earth metal promoter, a rhenium-containing promoter and optionally a co-promoter thereof to the modified alpha-alumina support.
The silver-containing compound may be any silver-containing compound suitable for preparing a silver catalyst for ethylene oxide production, such as one or more of silver oxalate, silver oxide and silver nitrate.
The organic amine may be any organic amine compound suitable for preparing a silver catalyst for ethylene oxide production as long as the organic amine compound is capable of forming a silver amine complex with a silver compound, for example, one or more selected from the group consisting of pyridine, butylamine, ethylenediamine, 1, 3-propylenediamine, ethanolamine and triethylamine. Preferably, the organic amine is ethylenediamine and/or ethanolamine.
The alkali metal auxiliary agent is selected from compounds corresponding to alkali metals (lithium, sodium, potassium, rubidium or cesium); for example, one or more selected from the group consisting of nitrates, sulfates and hydroxides of the alkali metals.
Preferably, the alkali metal assistant is one or more of lithium sulfate, cesium sulfate and cesium nitrate.
In the present invention, the content of the alkali metal element in the finally prepared silver catalyst is usually 0 to 2000ppm, preferably 5 to 1500ppm, based on the total weight of the silver catalyst.
The alkaline earth metal auxiliary agent is selected from compounds corresponding to alkaline earth metals (magnesium, calcium, strontium or barium); for example, one or more selected from the group consisting of oxides, oxalates, sulfates, acetates, and nitrates of the alkaline earth metals. The alkaline earth metal promoter is preferably selected from barium and/or strontium compounds, more preferably from barium acetate and/or strontium acetate.
In the present invention, the content of the alkaline earth metal element in the finally prepared silver catalyst is usually 0 to 2000ppm based on the total weight of the silver catalyst.
In the present invention, the rhenium promoter and optionally the rhenium co-promoter added during the preparation of the silver catalyst, in addition to the alkali metal and alkaline earth metal promoters mentioned above, can further improve the activity, selectivity and stability of the silver catalyst.
The rhenium-containing auxiliary agent can be selected from one or more of elementary rhenium, rhenium oxide, perrhenic acid and perrhenate, is preferably selected from perrhenic acid and perrhenate, and is more preferably selected from at least one of perrhenic acid, cesium perrhenate and ammonium perrhenate.
In the present invention, the rhenium element content in the finally obtained silver catalyst is usually 5 to 1500ppm, preferably 10 to 1000ppm, based on the total weight of the silver catalyst.
The rhenium co-promoter can be any transition metal simple substance in the periodic table of elements, boron or a compound corresponding to the transition metal simple substance, and the rhenium co-promoter can be one or more of a chromium simple substance, a molybdenum simple substance, a tungsten simple substance, a boron simple substance, a chromium metal compound, a molybdenum metal compound, a tungsten metal compound and a boron compound.
In the present invention, the rhenium co-promoter content of the finally prepared silver catalyst is generally from 0 to 1000ppm, based on the total weight of the silver catalyst.
In addition, the above auxiliaries may be applied to the alumina support before, simultaneously with, or after impregnation with silver, or may be impregnated on the support after the silver compound is reduced.
According to one embodiment, the silver catalyst is prepared by:
1) impregnating the modified alpha-alumina carrier with a solution containing sufficient amounts of a silver compound, an organic amine, an alkali metal auxiliary agent, a rhenium-containing auxiliary agent and optionally a co-auxiliary agent;
2) filtering off the impregnation solution and drying the impregnated carrier; and
3) activating the impregnated carrier in an oxygen-containing mixed gas to produce the silver catalyst.
In the step 1), the silver compound (e.g., silver oxalate) may be dissolved in an aqueous solution of an organic amine (e.g., ethylenediamine and/or ethanolamine) to generate a silver-amine complex, and then the silver-amine complex and the alkali metal and other additives are mixed to prepare the immersion liquid;
in the step 3), the activation aims to carry out thermal decomposition on the product to prepare the finished product of the silver catalyst. Wherein the activation can be carried out in air flow or nitrogen-oxygen mixed gas with oxygen content not more than 21 v% (such as oxygen content of 8.0 v%), the temperature of the activation is generally 180-700 ℃, preferably 200-500 ℃, and the time of the activation can be 20 seconds to 120 minutes, preferably 1-60 minutes.
According to a more specific embodiment, the silver catalyst is prepared by the following method:
firstly, reacting a silver nitrate aqueous solution with an ammonium oxalate or oxalic acid aqueous solution to precipitate a silver oxalate precipitate, filtering, washing with deionized water until no nitrate ions exist, then dissolving the silver oxalate into an organic amine aqueous solution, and adding the other additives (an alkali metal additive and/or an alkaline earth metal additive, a rhenium metal additive and an optional rhenium co-additive) to prepare a dipping mixed solution;
then, the above modified α -alumina support is impregnated with the impregnation mixed solution, drained, and activated in the air flow or nitrogen-oxygen mixed gas to perform thermal decomposition.
In this embodiment, silver oxide may be used instead of silver nitrate, or silver oxalate may be directly complexed with an organic amine without leaching, followed by impregnation of the support.
In the present invention, the amount of the silver compound used in the impregnation process is such that the content of silver element in the finally prepared silver catalyst is 1 to 30 wt%, preferably 5 to 26 wt%, based on the total weight of the silver catalyst.
According to a fifth aspect of the present invention, there is provided the use of a modified α -alumina support as described above or said silver catalyst in the production of ethylene oxide by the oxidation of ethylene. The silver catalyst is particularly suitable for the process for producing ethylene oxide by oxidizing ethylene, and shows good activity and selectivity.
The term "optional" or "optionally" as used herein means either with or without, and with or without the addition of.
The term "water" as used herein refers to one or more of deionized water, distilled water and ultrapure water, unless otherwise specified or indicated.
The term "rhenium co-promoter" as used in the present invention is also referred to as "rhenium co-promoter" or rhenium co-promoter.
The molecular formula of the term "alumina" described in the present invention is Al2O3。
In order that the present invention may be more readily understood, the present invention will now be described in further detail with reference to the following examples, which are intended to be illustrative only and not to limit the scope of the invention.
The detection method of the physical properties of the modified alpha-alumina carrier comprises the following steps:
the specific surface area of the support is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.
The term "water absorption" as used in the present invention refers to the volume of saturated adsorbed water per unit mass of the carrier, in mL/g. The determination method comprises the following steps: first, a certain amount of carrier (assuming its mass m) is weighed1) Boiling in boiling water for 1 hr, taking out the carrier, standing on wet gauze with moderate water content to remove excessive water on the surface of the carrier, and weighing the mass of the carrier after water adsorption (assuming that the mass is m)2) The water absorption of the carrier was calculated by the following formula.
Where ρ isWater (W)Is the density of water at the measurement temperature under atmospheric pressure.
The evaluation method of the performance of the silver catalyst in the invention is as follows:
various silver catalysts involved in the present invention were tested for their initial activity and selectivity using a laboratory microreactor (hereinafter referred to as "microreaction") evaluation device. The reactor used in the microreaction evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reaction tube was placed in a heating mantle. The filling volume of the catalyst is 1mL, and the lower part of the catalyst is provided with an inert filler, so that a catalyst bed layer is positioned in a constant temperature area of a heating sleeve.
The measurement conditions for the activity and selectivity of the catalyst used in the present invention are shown in table 1:
TABLE 1 determination of catalyst Activity and selectivity
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The measurement results were corrected for volume shrinkage and the selectivity S was calculated as follows:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2The carbon dioxide concentration difference between the outlet gas and the inlet gas of the reactor is determined, and the average of more than 10 groups of test data is taken as the test result of the day.
Preparation example 1
This preparation example is used to illustrate a shaped α -alumina support and a method for preparing the same.
Mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g of the mixture is put into a mixer to be uniformly mixed, the mixture is transferred into a kneader, 90mL of dilute nitric acid (nitric acid: water: 1: 5, weight ratio) is added, and the mixture is kneaded into paste which can be extruded and formed. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. The green body was then placed in an electric furnace and allowed to rise from room temperature to 1250 ℃ over a period of about 18 hours and held at that temperature for 4 hours to yield white shaped alpha-A12O3Sample of the support, denoted supportD1, the relevant physical property data of this support are shown in table 2.
Examples 1-3 are provided to illustrate the modified alpha-alumina of the present invention and the method of preparing the same.
Example 1
At room temperature, 15g of sucrose, 4.28g P123 g of aluminum isopropoxide and 50g of water are mixed, poured into a 250mL three-necked flask, and stirred while controlling the water bath temperature at 60 ℃ until the aluminum isopropoxide is dissolved. And (3) dropwise adding 10 wt% of nitric acid solution into the solution, adjusting the pH value of the system to be 5, and then pouring the obtained sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining. 10g of the molded α -alumina carrier prepared in preparation example 1 was put into a reaction vessel, aged at room temperature for 10 hours in the hydrothermal reaction vessel, and after aging, the open reaction vessel was put into an oven to be dried at 60 ℃ for 48 hours. And finally, placing the obtained solid in a muffle furnace, heating to 550 ℃, roasting, and keeping the temperature for 4 hours to obtain an alpha-alumina carrier (namely, the modified alpha-alumina carrier) with the acid mesoporous alumina growing thereon, wherein the obtained product is marked as a carrier C1, and relevant physical property data of the carrier C1 are shown in Table 2.
Example 2
4.58g of polyethylene glycol was dissolved in 70mL of deionized water, stirred until clear, and 14.3g of Al (NO) was added3)3·9H2And O. Under the condition of vigorous stirring, the solution and 0.5mol/L ammonium carbonate solution are mixed in parallel flow, and after the parallel flow feeding is finished, the pH value of the mixed solution is adjusted to 9 by using an ammonia water solution. The mixed solution was transferred to a stainless steel autoclave lined with polytetrafluoroethylene. 10g of the carrier D1 prepared in preparation example 1 is taken and put into a reaction kettle, the carrier D1 is reacted for 24 hours at 100 ℃ in the hydrothermal reaction kettle, the carrier D1 is filtered and dried for 48 hours at 80 ℃, the obtained solid is put into a muffle furnace to be heated to 550 ℃ for roasting, the temperature is kept constant for 4 hours, the obtained product is an alpha-alumina carrier growing with alkaline mesoporous alumina, the carrier C2 is marked, and the relevant physical property data is shown in Table 2.
Example 3
8.0g of aluminum nitrate was dissolved in 45mL of distilled water with stirring at room temperature, and 2.1g of acrylamide and 0.8g of ammonium persulfate were further added. After stirring for 30min, 2.8g of urea was added. 10g of the support D1 prepared in preparation example 1 was taken in, and after the solution was clear and transparent, it was heated in an oven at 60 ℃ for 90min to initiate polymerization of acrylamide. After the polymerization was completed, the obtained wet gel was dried in an oven at 80 ℃ for 48 hours. The polymer is put in a muffle furnace and heated to 550 ℃ for roasting, and the temperature is kept constant for 4 hours, so that the obtained product is an alpha-alumina carrier (namely, the modified alpha-alumina carrier) growing with neutral mesoporous alumina, and is marked as a carrier C3, and related physical property data of the product are shown in Table 2.
TABLE 2 physical Properties of the vectors
Injecting: the pore size distribution refers to the range of pore size distribution of pure mesoporous alumina synthesized without the support of preparation example 1.
As can be seen by comparing the data in Table 2, the alpha-alumina carrier of the mesoporous and macroporous alumina grows larger pore channels of the carrier and improves the specific surface area of the alpha-alumina carrier.
Examples 4 to 6 and comparative example 1
700g of silver nitrate was dissolved in 750mL of deionized water. 325g of ammonium oxalate was dissolved in 250mL of 50 ℃ deionized water. The two solutions were mixed under vigorous stirring to form a white silver oxalate precipitate. Aging for more than 30 minutes, filtering, washing the precipitate with deionized water until nitrate ions are removed to obtain a silver oxalate paste containing about 60 wt% silver and about 15 wt% water.
300g of ethylenediamine and 485g of deionized water were added to a stirred glass flask. The prepared silver oxalate paste was slowly added to the mixed solution with stirring, the temperature was kept below 45 ℃ to completely dissolve the silver oxalate, 4.2g of cesium sulfate and 0.2g of ammonium perrhenate were added, and deionized water was added to make the total mass of the solution to 2000g to prepare a dipping mixed solution. The addition amount of the silver oxalate ensures that the impregnation mixed solution contains 23 to 25 weight percent of silver.
50g of each of the carrier samples of examples 1 to 3 and preparation example 1 was taken and placed in a vessel capable of being evacuated. Vacuumizing to vacuum degree above 10mmHg, adding 100g of the prepared impregnation mixed solution into each part of the carrier, and immersing the carrier for 30 min. The excess solution is leached away. The impregnated carrier was heated in an air stream at 275 deg.C for 10min and cooled to produce the ethylene oxide silver catalysts, which were designated as silver catalysts of examples 4-6 and comparative example 1, respectively.
Analyzing the silver content of the prepared catalyst, wherein the content is calculated by metal elements; the activity and selectivity of the catalyst samples were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
TABLE 3 silver catalyst test results for ethylene oxide production
Injecting: selectively taking the accumulated EO yield to 400T/M3Average value in catalyst.
As can be seen from comparison of the data in table 3, after the mesoporous alumina of the present invention is grown on the α -alumina support, the selectivity of the silver catalyst is significantly improved, and particularly, compared with a catalyst in which the support is not modified, the selectivity is improved by 1.5 to 3%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (16)
1. A modified alpha-alumina carrier is characterized in that the modified alpha-alumina carrier comprises a molded alpha-alumina carrier and mesoporous alumina growing on the molded alpha-alumina carrier; the crushing strength of the modified alpha-alumina carrier is 55-220N, and the specific surface area is 1.30-2.5m2The pore volume is 0.40-0.80mL/g, and the water absorption rate is not lower than 42%; the pore size of the mesoporous alumina is 2-200 nm.
2. The modified α -alumina support of claim 1, wherein the mesoporous and macroporous alumina has a pore size of 30-100 nm.
3. A method for preparing a modified α -alumina support according to claim 1 or 2, comprising: and mixing the formed alpha-alumina carrier with the mesoporous alumina precursor mixture, and reacting, drying and roasting to grow mesoporous alumina on the formed alpha-alumina so as to prepare the modified alpha-alumina carrier.
4. The preparation method of claim 3, wherein the mesoporous alumina precursor mixture comprises a template, an aluminum source, and water.
5. The preparation method of claim 4, wherein the weight ratio of the template, the aluminum source and the water is 1: 0.5-10: 2-30.
6. The preparation method according to claim 4, wherein the weight ratio of the formed alpha-alumina carrier to the mesoporous alumina precursor mixture is 1: 5-30.
7. The preparation method according to claim 4, wherein the template is selected from at least one of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, P123, polyethylene glycol, polyacrylamide, oleic acid monoglyceride, acrylamide, glucose, sucrose, dibenzoyl-L-tartaric acid, and ethylene glycol; the aluminum source is selected from at least one of aluminum isopropoxide, aluminum isobutanolate, aluminum nitrate, aluminum sulfate and sodium aluminate.
8. The preparation method according to claim 4, wherein the mesoporous alumina precursor mixture further comprises a pH adjusting agent and/or a precipitating agent.
9. The method of manufacturing of claim 8, wherein the method comprises the steps of:
1) mixing the template, an aluminum source and water, and adding a pH regulator and an optional precipitator after the aluminum source is dissolved;
2) mixing the product obtained in the step 1) with the formed alpha-alumina carrier in a hydrothermal reaction kettle, and carrying out hydrothermal treatment at the temperature of 20-250 ℃ for 0.5-24 h;
3) drying and roasting the product obtained in the step 2).
10. The method of manufacturing of claim 8, wherein the method comprises the steps of:
1) mixing the aluminum source, water, acrylamide and an initiator, and adding the formed alpha-alumina carrier and an optional precipitator after the aluminum source is dissolved;
2) after the solution obtained in the step 1) is transparent, heating at 50-90 ℃ for 60-120min to initiate acrylamide polymerization to obtain polyacrylamide wet gel;
3) and drying and roasting the polyacrylamide wet gel.
11. The preparation method according to claim 3, wherein the shaped α -alumina support is prepared by: mixing an alumina raw material, a binder and water, optionally adding an auxiliary agent to obtain an alpha-alumina carrier precursor mixture, and kneading, molding, drying and roasting the alpha-alumina carrier precursor mixture.
12. The production method according to claim 11, wherein the alumina raw materials are alpha-alumina trihydrate and pseudo-alumina monohydrate.
13. The production method according to any one of claims 3, 9 and 10, wherein the drying temperature is 50 to 130 ℃, and the drying time is 10 to 50 hours; the roasting temperature is 400-700 ℃, and the roasting time is 1-12 h.
14. A modified α -alumina support prepared by the process of any one of claims 3 to 13.
15. A silver catalyst, comprising:
component a, a modified α -alumina support according to claim 1 or 14;
component b, silver;
component c, an alkali metal and/or an alkaline earth metal;
component d, rhenium and optionally a co-promoter therefor.
16. Use of a modified alpha-alumina support as claimed in claim 1 or claim 14, or a silver catalyst as claimed in claim 15, in an ethylene epoxidation reaction.
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| EP0150238A1 (en) * | 1982-07-06 | 1985-08-07 | The Dow Chemical Company | Alumina catalyst supports containing barium salts |
| CN1044416A (en) * | 1989-01-24 | 1990-08-08 | 日本触媒化学工业株式会社 | Produce oxyethane catalyzer and method for making thereof |
| CN102553589A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Alumina support, preparation method of alumina support, silver catalyst prepared by alumina support, and use of silver catalyst |
| CN103357440A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN104148040A (en) * | 2014-07-24 | 2014-11-19 | 华东师范大学 | Aluminum matrix-mesoporous alumina composite material and preparation method and application of aluminum matrix-mesoporous alumina composite material |
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| EP0150238A1 (en) * | 1982-07-06 | 1985-08-07 | The Dow Chemical Company | Alumina catalyst supports containing barium salts |
| CN1044416A (en) * | 1989-01-24 | 1990-08-08 | 日本触媒化学工业株式会社 | Produce oxyethane catalyzer and method for making thereof |
| CN102553589A (en) * | 2010-12-29 | 2012-07-11 | 中国石油化工股份有限公司 | Alumina support, preparation method of alumina support, silver catalyst prepared by alumina support, and use of silver catalyst |
| CN103357440A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
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