CN114100596A - Alpha-alumina carrier and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation - Google Patents
Alpha-alumina carrier and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation Download PDFInfo
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- CN114100596A CN114100596A CN202010886364.XA CN202010886364A CN114100596A CN 114100596 A CN114100596 A CN 114100596A CN 202010886364 A CN202010886364 A CN 202010886364A CN 114100596 A CN114100596 A CN 114100596A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 58
- 239000004332 silver Substances 0.000 title claims abstract description 58
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000008247 solid mixture Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 34
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 34
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000001050 lubricating effect Effects 0.000 claims abstract description 10
- 239000002210 silicon-based material Substances 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 27
- 239000002006 petroleum coke Substances 0.000 claims description 13
- 229910052792 caesium Inorganic materials 0.000 claims description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 229910052702 rhenium Inorganic materials 0.000 claims description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 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 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000001354 calcination Methods 0.000 abstract description 12
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 239000012752 auxiliary agent Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910052918 calcium silicate Inorganic materials 0.000 description 10
- 239000000378 calcium silicate Substances 0.000 description 10
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229940100890 silver compound Drugs 0.000 description 4
- 150000003379 silver compounds Chemical class 0.000 description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000004684 trihydrates Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-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
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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Abstract
The invention belongs to the field of silver catalysts, and relates to an alpha-alumina carrier and a preparation method thereof, a silver catalyst and a method for producing ethylene oxide by ethylene epoxidation. The method comprises the following steps: I) obtaining a solid mixture comprising: a) alpha-A1 with particle size of 10-30 mu m2O3(ii) a b) alpha-A1 with particle size of 1-3 mu m2O3(ii) a c) Low molecular weight polyvinylpyrrolidone; d) burnout of the lubricating material; e) a silicon-containing compound; f) a zirconium-containing compound; II) adding water into the solid mixture obtained in the step I) for kneading and extruding into strips for forming; III) drying the green sample obtained in step II) and calcining to obtain alpha-A12O3And (3) a carrier. Compared with the prior art, the silver catalyst prepared by the carrier provided by the invention has the advantages of high activity and selectivity for the reaction of producing ethylene oxide by oxidizing ethylene.
Description
Technical Field
The invention belongs to the field of silver catalysts, and particularly relates to a preparation method of a silver catalyst carrier for ethylene epoxidation, the silver catalyst carrier for ethylene epoxidation prepared by the method, a silver catalyst containing the carrier, and a method for producing ethylene oxide by ethylene epoxidation by using the silver catalyst.
Background
Ethylene epoxidation under the action of a silver catalyst produces mainly Ethylene Oxide (EO) and simultaneously produces carbon dioxide and water as side reactions, wherein activity, selectivity and stability are the 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.
Currently, there are three types of silver catalysts: the catalyst has high activity, good stability, initial selectivity of 80-82% and service life of 2-5 years, and is suitable for all ethylene oxide/ethylene glycol (EO/EG) production devices; the second is high-selectivity silver catalyst, the highest selectivity of the catalyst reaches over 88 percent, but the catalyst requires CO in the reaction gas of the inlet reactor2The concentration is below 1.0 percent, and the method is suitable for a newly-built EO/EG production device with relatively low space-time yield; thirdly, the catalyst is a silver catalyst with medium selectivity (the activity and the selectivity of the silver catalyst are between the activity and the selectivity of the silver catalyst), the selectivity of the catalyst can reach 83-85%, and the CO in the reaction gas at the inlet of the reactor is required to be in the range of2The concentration is below 3%. The selectivity of different catalysts can be determined according to CO in the reaction gas2The concentration and the outlet EO concentration are correspondingly adjusted, and in recent years, due to the requirements of energy consumption and environmental protection, the high-selectivity silver catalyst and the medium-selectivity silver catalyst are widely applied to industrial production and replace the original high-activity silver catalyst.
The performance of the silver catalyst is not only important in relation to the composition of the catalyst and the preparation method, but also important in relation to the performance of the carrier used by the catalyst and the preparation method. For with alpha-Al2O3As for the carrier as the main component, the carrier physical properties include compressive strength, porosity, specific surface area and pore distribution, etc., and a good catalyst carrier has excellent compressive strength, porosity and specific surface area. The higher porosity can reduce the diffusion resistance of reactants and product gas under reaction conditions; the specific surface requirement of the carrier is minimumA value to ensure that the catalytically active component is uniformly loaded onto the support; the crush strength is a measure of the physical integrity of the support and is critical to the ability of the catalyst to withstand the harsher operating conditions and to ensure a longer service life. The physical properties of the carrier have certain contradiction, and the higher porosity can reduce the compressive strength and lower the specific surface; conversely, increasing the compressive strength of the support generally reduces its porosity, while increasing the specific surface. Therefore, the balance between different physical properties is very important for the carrier.
US5384302 uses two different particle sizes of alpha-Al2O3And trihydrate and monohydrate alumina are taken as raw materials, a titanium-containing auxiliary agent, a pore-forming agent, a ceramic binder and the like are added to prepare a carrier, and the carrier has better compressive strength and porosity after being calcined at 1500 ℃, so that the catalyst prepared from the carrier has better performance. US7060651 describes a high-silicon carrier, the content of silicon oxide is above 70%, the specific surface is 0.5-3.0m2The catalyst is prepared by using at least one of metal components of platinum, palladium, silver, molybdenum, titanium, zirconium, copper and the like or oxide thereof as an active component, wherein the content of the active component is not more than 2 percent of the metal content, and the active component is immersed and loaded on a carrier at 40-200 ℃ in a solution form and then is subjected to heat treatment to obtain the catalyst which can be used for ethylene or propylene epoxidation reaction. US7825062 is prepared by taking alpha-alumina with different particle sizes as a raw material, adding an auxiliary agent containing zirconium, titanium and silicon, and roasting at the high temperature of 1400-1550 ℃ to obtain a carrier with the specific surface of 1.3-5.0 m2The pore volume is 0.25-0.8 ml/g, wherein the total pore volume is more than 80% of pores with the diameter of 0.1-10 μm, and the average pore diameter is 0.8-2 μm. CN1217233A describes that the carrier is prepared by roasting three-water alpha-alumina with different particle sizes, pseudo-one-water alumina with a certain proportion, a pore-forming agent, a fluxing agent, a mineralizer, an auxiliary agent and the like at the high temperature of 1300-1500 ℃, and the catalyst prepared by the carrier has higher selectivity. CN1634652A describes that no pore-forming agent is added in the preparation process of the carrier, and the carrier is prepared by directly roasting 50-500 meshes of alpha-alumina trihydrate, a certain proportion of pseudo-monohydrate alumina, a fluxing agent, a mineralizing agent, an auxiliary agent and the like at the high temperature of 1250-1550 ℃. CN103372466A adopts different proportions of trihydrate alpha-alumina, pseudo-monohydrate alumina, mineralizer and alkaline earth goldThe carrier is prepared by uniformly mixing compound auxiliary agent, combustible lubricating material and the like, kneading, extruding and molding and high-temperature calcining, the mineralizer can reduce the crystal transition temperature of alumina, the alumina wafers are distributed in a flaky cross manner, and the carrier has higher strength. US8791280 describes a preparation method of a low-surface-area alpha-phase alumina carrier, wherein the content of alpha-phase alumina is more than 90% (wt%), the content of silicon is less than 6% (wt%), the alpha-phase alumina and/or transition-phase alumina, a binder, a solid pore-forming agent and a water-soluble titanium compound are subjected to dry mixing, then water is added to the mixture to be extruded and molded, the mixture is dried and roasted at 1150-1600 ℃ to prepare a carrier, and the pore volume of the carrier is 0.2-0.8 ml/g, preferably 0.25-0.6 ml/g; the specific surface area is 0.4 to 4.0m2A concentration of 0.6 to 1.5 ml/g; the crush strength is greater than 8 pounds, more preferably greater than 10 pounds.
The method improves the performances of the silver catalyst carrier to different degrees, but along with the large-scale industrial application of the silver catalyst, the requirement of the field on the performance of the alumina carrier is continuously increased. Therefore, the development of alumina supports with superior performance is still a need in the field of silver catalysts.
Disclosure of Invention
The inventor of the invention has conducted extensive and intensive research in the field of preparation of silver catalyst carriers, and found that when trihydrate alpha-alumina with different particle sizes is used as a raw material, in the preparation process of the carriers, the carriers can be kneaded and molded by adjusting the molecular weight and proportion of polyvinylpyrrolidone added, and the pore volume of the carriers is increased; the alpha-alumina carrier after high-temperature calcination has higher pore volume and specific surface. When the catalyst prepared by the carrier is used for preparing ethylene oxide by ethylene epoxidation, the activity and selectivity of the catalyst are obviously improved.
The invention provides a preparation method of an alpha-alumina carrier, which comprises the following steps:
I) obtaining a solid mixture comprising:
a) 45-80 wt% of alpha-A1 with particle size of 10-30 μm based on the total weight of the solid mixture2O3；
b) The content of the solid mixture is 10 to 30 weight portions based on the total weight of the solid mixturealpha-A1 having a particle size of 1 to 3 μm in% by weight2O3；
c) 7-15 wt% of low molecular weight polyvinylpyrrolidone (PVP) based on the total weight of the solid mixture, wherein the molecular weight of the low molecular weight polyvinylpyrrolidone is 5000-30000 g/mol;
d) a burnable lubricating material in an amount of 5 to 20 wt% based on the total weight of the solid mixture;
e) a silicon-containing compound in an amount of 0.05 to 1 wt% based on the total weight of the solid mixture;
f) a zirconium-containing compound in an amount of 0.15 to 1.5 wt% based on the total weight of the solid mixture;
II) adding water into the solid mixture obtained in the step I) for kneading and forming, wherein the using amount of the water is 25-60 wt% of the total weight of the solid mixture;
III) drying the sample green body obtained in the step II), and roasting at 1250-1450 ℃ to obtain alpha-A12O3And (3) a carrier.
In a second aspect, the present invention provides an α -alumina support prepared by the above preparation method.
In a third aspect, the present invention provides a silver catalyst for ethylene epoxidation comprising:
a) the above-mentioned α -alumina carrier;
b) silver;
c) an alkali metal selected from at least one of lithium, sodium, potassium, rubidium, and cesium;
d) an alkaline earth metal selected from at least one of calcium, magnesium, strontium, and barium;
e) a rhenium promoter derived from at least one of perrhenic acid, cesium perrhenate, and ammonium perrhenate, and a co-promoter derived from at least one of tungstic acid, cesium tungstate, molybdic acid, and ammonium molybdate.
In a fourth aspect, the present invention provides a process for the epoxidation of ethylene to ethylene oxide, said ethylene being subjected to an epoxidation reaction in a reaction apparatus in the presence of the silver catalyst as described above.
According to the invention, micron-sized alpha-alumina crystal grains, zirconium-containing and silicon-containing auxiliary agents and low molecular weight polyvinylpyrrolidone are added into the carrier in a certain proportion in the preparation process, and the carrier prepared by high-temperature roasting has more ideal porosity, specific surface and pore structure. Compared with the prior art, the silver catalyst prepared by the carrier provided by the invention is applied to the reaction of producing ethylene oxide by oxidizing ethylene, and has the advantages of high activity and selectivity.
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.
The invention provides a preparation method of an alpha-alumina carrier, which comprises the following steps:
I) obtaining a solid mixture comprising:
a) 45-80 wt% of alpha-A1 with particle size of 10-30 μm based on the total weight of the solid mixture2O3(ii) a Preferably, the alpha-A1 with the particle size of 10-30 mu m is calculated by the total weight of the solid mixture2O3The content of (b) is 50 to 70 wt%, more preferably 50 to 60 wt%;
b) 10-30 wt% of alpha-A1 with particle size of 1-3 μm based on the total weight of the solid mixture2O3(ii) a Preferably, the alpha-A1 with the particle size of 1-3 mu m is calculated by the total weight of the solid mixture2O3The content of (b) is 12 to 25 wt%, more preferably 15 to 24 wt%;
c) 7-15 wt% of low molecular weight polyvinylpyrrolidone (PVP) based on the total weight of the solid mixture, wherein the molecular weight of the low molecular weight polyvinylpyrrolidone is 5000-30000 g/mol, preferably 8000-20000 g/mol;
d) a burnable lubricating material in an amount of 5 to 20 wt% based on the total weight of the solid mixture;
e) a silicon-containing compound in an amount of 0.05 to 1 wt% based on the total weight of the solid mixture;
f) a zirconium-containing compound in an amount of 0.15 to 1.5 wt% based on the total weight of the solid mixture;
II) adding water into the solid mixture obtained in the step I) for kneading and forming, wherein the using amount of the water is 25-60 wt% of the total weight of the solid mixture;
III) drying the sample green body obtained in the step II), and roasting at 1250-1450 ℃ to obtain alpha-A12O3And (3) a carrier.
In the preparation method of the carrier, the alpha-A1 with the granularity of 10-30 mu m and 1-3 mu m2O3The powder materials are mutually overlapped in the high-temperature roasting process to generate alpha-A1 with larger porosity and certain strength2O3A carrier; the low molecular weight polyvinylpyrrolidone as an organic binder can be burnt out to generate pores with different apertures in the high-temperature roasting process; two different particle sizes of alpha-A12O3The organic binder is used in a matching way, so that the pore volume of the carrier is increased and the specific surface of the carrier can be increased at the same time.
In the preparation method of the carrier, the low molecular weight polyvinylpyrrolidone plays the role of a binder, reacts with deionized water to bind the solid powder together, and becomes paste which can be extruded and formed. Therefore, the molecular weight of the polyvinylpyrrolidone used needs to be controlled to achieve a proper binding effect. The low molecular weight polyvinylpyrrolidone used in the present invention is preferably polyvinylpyrrolidone k15-19, provided that the above molecular weight is satisfied. The K value is a parameter well known in the art reflecting the molecular weight of polyvinylpyrrolidone, which is commercially available as K15-19. The content of the low molecular weight polyvinylpyrrolidone is preferably 7.5 to 14.5 wt%, and more preferably 9.5 to 12 wt%, based on the total weight of the solid mixture.
In the preparation method of the carrier, the combustible lubricating material is added to ensure that the kneaded material is easy to form and granulate, meanwhile, oxidation reaction is generated in the roasting process of the material, generated gas escapes, larger holes are left in the carrier, and the heat transfer effect is realized in the application process of the catalyst. The burnout lubricating material is preferably at least one of petroleum coke, carbon powder, graphite, rosin, polyethylene and polypropylene, and the content of the burnout lubricating material is preferably 6-15 wt% based on the total weight of the solid mixture.
In the above method for producing a carrier, the silicon-containing compound is preferably at least one of an alkali metal, an alkaline earth metal silicate and a silicon oxide, and has a function of increasing pores in the carrier and maintaining a high specific surface area of the carrier; the content of the silicon-containing compound is preferably 0.1-0.5 wt% based on the total weight of the solid mixture.
In the above method for producing a carrier, the zirconium-containing compound is preferably at least one of a sulfate, a nitrate, a carbonate and an oxide of zirconium, and functions to increase the pore volume of the carrier; the content of the zirconium-containing compound is preferably 0.5 to 1.2 wt% based on the total weight of the solid mixture.
In the preparation method of the carrier, the solid mixture is kneaded under the action of low molecular weight polyvinylpyrrolidone as an organic binder to obtain a paste, and then the paste is extruded and molded and then dried to the water content of less than 10 percent, and the carrier can be in a ring shape, a spherical shape, a cylindrical shape or a porous cylindrical shape. The drying temperature is 80-120 ℃, and the drying time is controlled to be 1-24 hours according to the moisture content.
In the preparation method of the carrier, the roasting time in the step IV) is 1-20 hours, preferably 2-15 hours, and the roasting is carried out to convert all alumina into alpha-A12O3。
In a second aspect, the present invention provides an α -alumina support prepared by the above preparation method. Preferably, said alpha-A12O3The carrier has the following characteristics: alpha-A12O3The content is more than 90 percent; the crushing strength of the carrier is 45-150N, preferably 50-140N; the specific surface area is 1.0-2.0 m2A preferred concentration is 1.1 to 1.9m2(ii)/g; the pore volume is 0.30 to 0.65ml/g, preferably 0.35 to 0.60 ml/g.
In the invention, the lateral crushing strength of the carrier is obtained by selecting a carrier sample and measuring the radial crushing strength and then averaging by adopting a DL II type intelligent particle strength measuring instrument; the specific surface area is measured by adopting a nitrogen physical adsorption BET method; the porosity, pore volume and pore structure distribution are measured by mercury intrusion method.
In a third aspect, the present invention provides a silver catalyst for ethylene epoxidation comprising:
a) the above-mentioned α -alumina carrier;
b) silver;
c) an alkali metal selected from at least one of lithium, sodium, potassium, rubidium, and cesium;
d) an alkaline earth metal selected from at least one of calcium, magnesium, strontium, and barium;
e) a rhenium promoter derived from at least one of perrhenic acid, cesium perrhenate, and ammonium perrhenate, and a co-promoter derived from at least one of tungstic acid, cesium tungstate, molybdic acid, and ammonium molybdate.
According to the invention, the amount of each component in the silver catalyst can be the conventional amount in the field, preferably, the mass content of the silver is 5-37 wt%, preferably 8-32 wt% based on the total weight of the catalyst for ethylene epoxidation; the mass content of the alkali metal is 5-3000 ppm, preferably 10-2000 ppm; the mass content of the alkaline earth metal is 100-3000 ppm, preferably 150-2500 ppm; the mass content of rhenium metal is 10-1000 ppm, preferably 100-800 ppm; the mass content of the co-promoter is 5-200 ppm, preferably 20-150 ppm, calculated by the metal in the co-promoter.
The silver catalyst of the present invention can be prepared in a conventional manner by impregnating the alumina support with a solution of 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. The organic amine compound 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, such as pyridine, butylamine, ethylenediamine, 1, 3-propylenediamine, ethanolamine, or a mixture thereof, preferably a mixture of ethylenediamine and ethanolamine.
The alkali metal promoter may be a compound of lithium, sodium, potassium, rubidium or cesium, such as a nitrate, sulfate or hydroxide thereof, or a combination of any two or more of the foregoing compounds, preferably cesium sulfate and/or cesium nitrate.
The alkaline earth metal promoter may be a compound of magnesium, calcium, strontium or barium, such as an oxide, oxalate, sulphate, acetate or nitrate thereof, or a combination of any two or more of the foregoing compounds, preferably a barium or strontium compound, more preferably barium acetate and/or strontium acetate. The alkaline earth metal promoter may be applied to the support before, simultaneously with, or after impregnation of the silver, or may be impregnated on the support after the silver compound has been reduced.
The rhenium promoter may be an oxide, perrhenic acid, perrhenate, or mixtures thereof, preferably perrhenic acid and perrhenate, such as, for example, perrhenic acid, cesium perrhenate, ammonium perrhenate, and the like; the co-promoter may be a compound of any transition metal in the periodic table of the elements, or a mixture of several transition metal compounds, the metal in the co-promoter is preferably selected from the group consisting of group VIB and group VIIB elements, and the co-promoter may include oxyacids of group VIB and group VIIB elements and salts thereof, such as at least one of tungstic acid, cesium tungstate, molybdic acid, ammonium molybdate and cerium sulphate. The rhenium promoter and its co-promoter may be applied to the carrier before, simultaneously with, or after impregnation of the silver, or may be impregnated on the carrier after the silver compound has been reduced. The activity, selectivity, and stability of activity and selectivity of the resulting silver catalyst can be further improved by the addition of a rhenium promoter and its co-promoter.
The preparation method of the silver catalyst in the specific embodiment comprises the following steps:
1) impregnating the porous alpha-alumina carrier with a solution containing sufficient amounts of a silver compound, an organic amine, an alkali metal auxiliary agent, an alkaline earth metal auxiliary agent, a rhenium-containing auxiliary agent and a co-auxiliary agent thereof;
2) filtering to remove the impregnation solution, and drying the impregnated carrier; and
3) activating the carrier obtained in the step 2) in oxygen-containing mixed gas to prepare the silver catalyst.
In the preparation of the silver catalyst, firstly, the silver oxalate is dissolved by using the aqueous solution of ethylenediamine and ethanolamine to prepare silver amine solution, and then the auxiliary agent is added to prepare impregnation liquid; then soaking the alpha-alumina carrier by using the prepared impregnation liquid, draining, and carrying out thermal decomposition in air flow or nitrogen-oxygen mixed gas with oxygen content not more than 21 percent (such as oxygen content of 8.0 percent) at the temperature of 180-700 ℃, preferably 200-500 ℃ for 0.5-120 minutes, preferably 1-60 minutes to prepare the finished product of the silver catalyst.
The present invention also provides a process for producing ethylene oxide by epoxidation of ethylene in the presence of the above silver catalyst in a reaction apparatus, which may be any apparatus capable of carrying out epoxidation.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Various silver catalysts of the present invention were tested for their initial performance and stability using a laboratory reactor (hereinafter referred to as "micro-reactor") evaluation apparatus. The reactor used in the microreaction evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reactor 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 assay conditions for activity and selectivity used in the present invention are as follows:
gas composition at the reactor inlet (mol%): ethylene (C)2H4) 28.0 +/-1.0; oxygen (O)2) 7.4 plus or minus 0.2; carbon dioxide (CO)2) < 1.0; cause steady qi (N)2) And the rest; the inhibitor dichloroethane (approx.), Ethylene Oxide (EO) concentration, 2.50%. The reaction pressure is 2.1 MPa; the space velocity is 6000/h; space-time yield, 295KgEO/m3Cat./h。
When the reaction conditions are stably achieved, the gas compositions at the inlet and outlet of the reactor are continuously measured. The selectivity was calculated after volume shrinkage correction of the measurement results according to the following formula:
where S is the selectivity, Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2Is the concentration difference of carbon dioxide in the outlet gas and the inlet gas of the reactor, and the average of more than 10 groups of test data is taken as the test result of the current day.
The examples, in which the specific conditions are not specified, were conducted under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. Polyvinylpyrrolidone k15-19 was purchased from Beijing carbofuran technologies Inc. and has a molecular weight of 8000-. Polyvinylpyrrolidone K29-32 was also available from Bailingwei technologies, Beijing at a molecular weight of 50000-.
Comparative example 1
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, less than 75 μm pseudo-monohydrate A12O3150g of petroleum coke, 50g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 120mL of dilute nitric acid (nitric acid: water: 1: 3 by weight ratio) and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Comparative example 2
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-5 mu m2O3150g, 45g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 125mL of deionized water and kneaded into paste which can be extruded and molded. Extruding to form a single-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm at the temperature of 80-120 DEG CDrying for more than 2 hours to reduce the free water content to below 10 percent. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Comparative example 3
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-5 mu m2O3150g, 100g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 90mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Comparative example 4
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 50g of polyvinylpyrrolidone k29-32, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 100mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 1
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 95g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 95mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 2
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 85g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 100mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 3
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 75g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 105mL of deionized water and kneaded into paste which can be extruded and molded. Extruding to form a single-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at 80-120 ℃ for more than 2 hours to enable the column to be freeThe water content is reduced to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 4
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 65g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 110mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 5
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 60g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 115mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Example 6
alpha-A1 with the particle size of 10-30 μm2O3350g of alpha-A1 with the particle size of 1-3 mu m2O3150g, 50g of polyvinylpyrrolidone k15-19, 75g of petroleum coke, 2.0g of calcium silicate and 5.0g of zirconium dioxide are put into a mixer to be uniformly mixed, transferred into a kneader, added with 120mL of deionized water and kneaded into paste which can be extruded and molded. Extruding and forming into a single-hole columnar object with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 2.0mm, and drying at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. Placing the kneaded and molded carrier into a bell jar kiln, increasing the temperature from room temperature to 1350 ℃ after 33 hours, and calcining the carrier at 1350 ℃ for 5 hours to obtain white alpha-A12O3And (3) a carrier. The measured physical properties of the support and the measured data of the pore structure distribution are shown in Table 1 below, respectively.
Examples of preparation of catalysts
Dissolving 98g of ethylenediamine in 150g of deionized water, slowly adding silver oxalate into the mixed solution under stirring, keeping the temperature below 40 ℃ to completely dissolve the silver oxalate, wherein the addition amount of the silver oxalate is 21 percent (weight) of silver content in the silver catalyst calculated by silver element, and then adding 0.9g of cesium nitrate, 0.78g of strontium acetate, 0.44g of perrhenic acid, 0.10g of lithium sulfate and deionized water to make the total mass of the solution reach 500g to prepare impregnation liquid for later use.
Taking 250g of carrier sample, placing into a vacuum-pumping container, vacuumizing to above 10mmHg, introducing the above immersion liquid, maintaining for 30min, and leaching to remove excessive solution. Heating the impregnated carrier in 300 deg.C air flow for 3min, and cooling to obtain comparative silver catalyst DC1-DC4 and silver catalyst C1-C6.
Test example
The activity and selectivity of the catalyst samples were evaluated using a microreactor apparatus under the aforementioned process conditions, and the results of the evaluation are shown in table 2 below.
TABLE 1 Carrier Properties
TABLE 2 Properties of the catalysts
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.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (12)
1. A preparation method of an alpha-alumina carrier comprises the following steps:
I) obtaining a solid mixture comprising:
a) 45-80 wt% of alpha-A1 with particle size of 10-30 μm based on the total weight of the solid mixture2O3；
b) 10-30 wt% of alpha-A1 with particle size of 1-3 μm based on the total weight of the solid mixture2O3；
c) 7-15 wt% of low molecular weight polyvinylpyrrolidone (PVP) based on the total weight of the solid mixture, wherein the molecular weight of the low molecular weight polyvinylpyrrolidone is 5000-30000 g/mol, preferably 8000-20000 g/mol;
d) a burnable lubricating material in an amount of 5 to 20 wt% based on the total weight of the solid mixture;
e) a silicon-containing compound in an amount of 0.05 to 1 wt% based on the total weight of the solid mixture;
f) a zirconium-containing compound in an amount of 0.15 to 1.5 wt% based on the total weight of the solid mixture;
II) adding water into the solid mixture obtained in the step I) for kneading and forming, wherein the using amount of the water is 25-60 wt% of the total weight of the solid mixture;
III) drying the sample green body obtained in the step II), and roasting at 1250-1450 ℃ to obtain alpha-A12O3And (3) a carrier.
2. The method according to claim 1, wherein the alpha-A1 has a particle size of 10-30 μm based on the total weight of the solid mixture2O3The content of (b) is 50 to 70 wt%, preferably 50 to 60 wt%.
3. The method according to claim 1, wherein the alpha-A1 has a particle size of 1-3 μm based on the total weight of the solid mixture2O3The content of (b) is 12 to 25% by weight, preferably 15 to 24% by weight.
4. The method of claim 1, wherein the low molecular weight polyvinylpyrrolidone is polyvinylpyrrolidone k 15-19; the content of the low molecular weight polyvinylpyrrolidone is 7.5-14.5 wt%, preferably 9.5-12 wt% based on the total weight of the solid mixture.
5. The production method according to claim 1, wherein the burnout lubricating material is selected from at least one of petroleum coke, carbon powder, graphite, rosin, polyethylene, and polypropylene; the content of the burnout lubricating material is 6-15 wt% based on the total weight of the solid mixture.
6. The production method according to claim 1, wherein the silicon-containing compound is selected from at least one of a silicate of an alkali metal, an alkaline earth metal, and an oxide of silicon; the content of the silicon-containing compound is 0.1-0.5 wt% based on the total weight of the solid mixture.
7. The production method according to claim 1, wherein the zirconium-containing compound is selected from at least one of a sulfate, a nitrate, a carbonate, and an oxide of zirconium; the content of the zirconium-containing compound is 0.5-1.2 wt% based on the total weight of the solid mixture.
8. An α -alumina support obtained by the production method according to any one of claims 1 to 7.
9. The alpha-alumina support according to claim 8, wherein the alpha-A12O3The carrier has the following characteristics: alpha-A12O3The content is more than 90 percent; the crushing strength of the carrier is 45-150N, preferably 50-140N; the specific surface area is 1.0-2.0 m2A preferred concentration is 1.1 to 1.9m2(ii)/g; the pore volume is 0.30 to 0.65ml/g, preferably 0.35 to 0.60 ml/g.
10. A silver catalyst for the epoxidation of ethylene comprising:
a) an alpha-alumina support as claimed in claim 8 or 9;
b) silver;
c) an alkali metal selected from at least one of lithium, sodium, potassium, rubidium, and cesium;
d) an alkaline earth metal selected from at least one of calcium, magnesium, strontium, and barium;
e) a rhenium promoter derived from at least one of perrhenic acid, cesium perrhenate, and ammonium perrhenate, and a co-promoter derived from at least one of tungstic acid, cesium tungstate, molybdic acid, and ammonium molybdate.
11. The silver catalyst for ethylene epoxidation according to claim 10, wherein the mass content of silver is 5 to 37 wt%, preferably 8 to 32 wt%, based on the total weight of the catalyst for ethylene epoxidation; the mass content of the alkali metal is 5-3000 ppm, preferably 10-2000 ppm; the mass content of the alkaline earth metal is 100-3000 ppm, preferably 150-2500 ppm; the mass content of rhenium metal is 10-1000 ppm, preferably 100-800 ppm; the mass content of the co-promoter is 5-200 ppm, preferably 20-150 ppm, calculated by the metal in the co-promoter.
12. A process for the epoxidation of ethylene to ethylene oxide, said ethylene being subjected to epoxidation in a reaction unit in the presence of a silver catalyst as claimed in claim 10 and/or 11.
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Application publication date: 20220301 |