CN108283943A - The method that alumina support and preparation method thereof, epoxidation of ethylene silver catalyst and ethylene epoxidizing prepare ethylene oxide - Google Patents
The method that alumina support and preparation method thereof, epoxidation of ethylene silver catalyst and ethylene epoxidizing prepare ethylene oxide Download PDFInfo
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- CN108283943A CN108283943A CN201710015107.7A CN201710015107A CN108283943A CN 108283943 A CN108283943 A CN 108283943A CN 201710015107 A CN201710015107 A CN 201710015107A CN 108283943 A CN108283943 A CN 108283943A
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- alumina support
- ethylene
- zirconium
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 48
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005977 Ethylene Substances 0.000 title claims abstract description 22
- WJNDLRMDNMIUGC-UHFFFAOYSA-N ethene;silver Chemical compound [Ag].C=C WJNDLRMDNMIUGC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052709 silver Inorganic materials 0.000 claims abstract description 48
- 239000004332 silver Substances 0.000 claims abstract description 48
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000008247 solid mixture Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 16
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 229910052702 rhenium Inorganic materials 0.000 claims description 11
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 10
- 239000002210 silicon-based material Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 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
- 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
- 230000001404 mediated effect Effects 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 claims 1
- 239000002006 petroleum coke Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 9
- 229940099259 vaseline Drugs 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 235000012241 calcium silicate Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 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 4
- 230000004913 activation Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052594 sapphire 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- -1 ethylene glycols Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- AOOCSKCGZYCEJX-OCNDCOMTSA-N argentamine Chemical compound C([C@H]1C[C@@H]2CN3CCC(C[C@H]31)O)N1C2=CC=CC1=O AOOCSKCGZYCEJX-OCNDCOMTSA-N 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
- 238000001354 calcination Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JOKVISWAQACXFU-UHFFFAOYSA-N acetic acid;strontium Chemical compound [Sr].CC(O)=O JOKVISWAQACXFU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 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
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent 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
- 239000013078 crystal Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- CDCIMUZJPLJFTE-UHFFFAOYSA-N ethene;oxirane Chemical compound C=C.C1CO1 CDCIMUZJPLJFTE-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-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
- 229920001296 polysiloxane Polymers 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical class [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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J21/16—Clays or other mineral silicates
-
- 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
-
- 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
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- 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
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Abstract
The present invention relates to epoxidation of ethylene field, a kind of alumina support and preparation method thereof is provided, the method that epoxidation of ethylene silver catalyst and ethylene epoxidizing prepare ethylene oxide；The alumina support includes alpha-aluminium oxide, zirconium, boron and contains silicon additive；On the basis of the total weight of the alumina support, the content of zirconium is 0.20~1.40 weight %, and the content of boron is 0.09~0.23 weight %, and the mass ratio of zirconium and boron is 1.7~15 ︰ 1, content containing silicon additive is 0.02~0.08 weight %, the weight % of the content of alpha-aluminium oxide >=95；In terms of total pore volume, 1.0~5.0 μm of hole accounts for 60~80 volume %.The alumina support has balanced intensity and pore structure parameter, and when being used in vinyl epoxide argentum catalyst, silver catalyst shows higher ethylene oxide selectivity, and catalyst is made to have higher catalytic activity and/or stability.
Description
Technical field
The present invention relates to epoxidation of ethylene fields, and specifically, the present invention provides a kind of alumina support, the oxidations
The preparation method of alumina supporter, the alumina support being prepared by this method, the present invention also provides a kind of ethylene epoxidizing is anti-
A kind of method for preparing ethylene oxide using silver catalyst and ethylene epoxidizing.
Background technology
Under the action of silver catalyst, epoxidation reaction mainly occurs for ethylene, generates ethylene oxide (EO), while pair occurs
Reaction generates carbon dioxide and water, wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to
Process for ethylene oxide production reaches reaction temperature required when certain reaction load, and reaction temperature is lower, and the activity of catalyst is got over
It is high；Selectivity refers to that ethylene is converted to the ratio between the molal quantity of ethylene oxide and the overall reaction molal quantity of ethylene in reaction；Stability
It is then expressed as the fall off rate of activity and selectivity, fall off rate is smaller, and the stability of catalyst is better.
At present there are three types of silver catalysts：First, high activity silver catalyst, this kind of catalyst activity is high, stability is good, initially
Selectivity 80~82%, service life were suitable for all ethylene oxide/ethylene glycols (EO/EG) process units in 2~5 years；Second is that
Highly selective silver catalyst, this kind of catalyst is just selective up to 88% or more, but requires CO in Reactor inlet reaction gas2Concentration
1.0% hereinafter, suitable for the EO/EG process units newly-built, space-time yield is relatively low；Third, intermediate selectivity silver is catalyzed
Agent (silver catalyst of the activity and selectivity between the former two), the selectivity of this kind of catalyst can reach 83~85%,
It is required that CO in the reaction gas of Reactor inlet2Concentration is below 3%.And the selectivity of different type silver catalyst can be according to reaction
CO in gas2Concentration and outlet EO concentration accordingly adjust.In recent years, the silver catalyst of highly selective silver catalyst and intermediate selectivity
It is widely used in industrial production and instead of original high activity silver catalyst.
The performance of silver catalyst is also used with catalyst other than the composition and preparation method with catalyst have important relationship
Carrier property and preparation method have important relationship.For with α-Al2O3For the carrier of key component, carrier of interest
Physical property generally includes compression strength, porosity, specific surface and pore size distribution etc..Wherein, higher porosity can reduce reactant with
Product gas diffusional resistance at reaction conditions；Carrier specific surface requires have minimum, to ensure that catalyst component can be impregnated into
On carrier；Compression strength be weigh carrier physical integrity a parameter, for catalyst be subjected to operating condition, ensure it is longer
Service life be necessary.However, there is carrier preferable specific surface and porosity, compression strength may reduce；On the contrary,
Compression strength is high, can reduce specific surface and porosity.Balance between different physical property is very important carrier, this is also referred to as
For one of the main direction of studying of silver catalyst carrier.
US5384302 uses two kinds of varigrained α-Al2O3And three water and a water aluminium oxide as raw material, be added simultaneously
Titaniferous auxiliary agent, pore creating material and vitrified bonding etc. prepare carrier, through 1500 DEG C calcining after, carrier have preferable compression strength and
Porosity, thus catalyst performance made from carrier is preferable.US7060651 discloses a kind of high silicon carrier, wherein silica
For content 70% or more, specific surface is 0.5~3.0m2/ g, catalyst is in the metal components such as platinum, palladium, silver, molybdenum, titanium, zirconium and copper
At least one or its oxide be active component, content in terms of metal be not more than 2%, active component is in the form of a solution in 40
~200 DEG C impregnate and are supported on carrier, then thermally treated obtained catalyst, the catalyst can be used for ethylene or epoxidation of propylene
Reaction.US7825062 is using varigrained Alpha-alumina as raw material, and addition is containing zirconium, titanium and contains silicon additive, through 1400~1550 DEG C
Carrier is made after high-temperature roasting, the specific surface of the carrier is in 1.3~5.0m20.25~0.8mL/g of/g, Kong Rongwei, wherein 0.1~
10 μm of holes account for 80% or more total pore volume, and average pore size is at 0.8~2 μm.CN1217233A elaborates to use varigrained three water
Alpha-alumina and a certain proportion of false water aluminium oxide, pore creating material, fluxing agent, mineralizer and auxiliary agent etc. are through high temperature 1300~1500
DEG C roasting prepares carrier, has higher selectivity by catalyst prepared by the carrier；CN1634652A discloses carrier preparation
Be not added with pore creating material in the process, using directly by 50~500 purpose, three water Alpha-alumina and a certain proportion of false water aluminium oxide, help
Flux, mineralizer and auxiliary agent etc. prepare carrier through 1250~1550 DEG C of roastings of high temperature.CN103372466A is used different proportion
Three water Alpha-aluminas, a false water aluminium oxide, mineralizer, alkaline earth metal compound auxiliary agent and can the mixing such as after-flame lubriation material it is equal
It is even, prepare carrier through kneading, extruded moulding and high-temperature calcination, wherein mineralizer, which can make aluminium oxide turn brilliant temperature, to be reduced, aluminium oxide
Cross-distribution, carrier have higher intensity to chip in the form of sheets.US8791280 discloses a kind of low surface alpha-phase aluminum oxide carrier
Preparation method, wherein alpha-phase aluminum oxide content be more than 90 weight %, silicone content be less than 6 weight %；The preparation method of the carrier is
By alpha-phase aluminum oxide and/or transition aluminas, binder and solid pore forming agent and the dry blended rear addition of water-soluble titanium compound
Water extrusion molding, drying are made then at 1150~1600 DEG C of roastings；Wherein, it is 0.2~0.8mL/g that carrier hole, which holds, and specific surface is
0.4~4.0m2/ g, crushing strength are more than 8 pounds, are preferably more than 10 pounds.
Above patent document is disclosed prepares silver catalyst carrier using different methods, and in order to obtain ideal hole knot
Structure can select different material matchings to use.However, the ethylene epoxidizing silver catalyst that carrier prepared by these methods is formed
Comprehensive not satisfactory, the especially selectivity of ethylene oxide, normally no higher than 86%.Therefore, in order to promote ethylene epoxy
Change the further development of reaction, there is still a need for study new silver catalyst carrier in the field.
Invention content
In view of the situation of the above-mentioned prior art, the present inventor is extensively and profoundly studying silver catalyst carrier
After find, a certain amount of zirconium and boron are introduced in alpha-alumina supports, silver catalyst can be improved in epoxidation of ethylene
Ethylene oxide selectivity, and catalyst is made to have higher catalytic activity and/or stability, it is based on the discovery, completes the present invention.
According to the first aspect of the invention, the present invention provides a kind of alumina support, which includes α-oxygen
Change aluminium, zirconium, boron and contains silicon additive；On the basis of the total weight of the alumina support, the content of zirconium is 0.20~1.40 weight
% is measured, the content of boron is 0.09~0.23 weight %, and the mass ratio of zirconium and boron is 1.7~15 ︰ 1, preferably 2.0~12.5 ︰
1, the content containing silicon additive is 0.02~0.08 weight %, the weight % of the content of Alpha-alumina >=95；
In the alumina support, in terms of total pore volume, 1.0~5.0 μm of hole accounts for 60~80 volume %.
According to the second aspect of the invention, the present invention provides a kind of method preparing alumina support, this method includes：
1) by solid mixture, binder and can after-flame lubriation material mediated, extrusion molding；
2) product that step 1) obtains is dried, roasted, to which the alumina support be made；
Wherein, with the total weight of the solid mixture, the solid mixture includes following components：
A) the three water α-A1 that the granularity of 30~80 weight % is 25~300 μm2O3；
B) granularity of 10~45 weight % is less than 75 μm of one water A1 of vacation2O3；
C) α-A1 that the granularity of 3~40 weight % is 3~8 μm2O3；
D) zirconium-containing compound of 0.01~1.8 weight %；
E) silicon-containing compound of 0.01~0.5 weight %；
F) boric acid of 0.1~1 weight %；
Relative to the solid mixture of 100 parts by weight, the dosage of the binder is 10~50 parts by weight, it is described can
The dosage of after-flame lubriation material is 0.01~5 parts by weight.
According to the third aspect of the invention we, the present invention provides the alumina supports that the above method is prepared.
According to the fourth aspect of the invention, the present invention provides a kind of epoxidation of ethylene silver catalyst, which urges
Agent includes：
A) alumina support described in；
B) silver-colored；
C) alkali metal, the alkali metal are selected from least one of lithium, sodium, potassium, rubidium and caesium；
D) alkaline-earth metal, the alkaline-earth metal are selected from least one of calcium, magnesium, strontium and barium；
E) rhenium auxiliary agent and its optional coassist agent.
According to the fifth aspect of the invention, the present invention provides a kind of methods that ethylene epoxidizing prepares ethylene oxide, should
Method includes：Ethylene is set to carry out epoxidation reaction in the presence of epoxidation of ethylene silver catalyst.
The alumina support of the present invention has balanced intensity and pore structure parameter, is used in vinyl epoxide argentum catalyst
When, so that silver catalyst is shown higher ethylene oxide selectivity in epoxidation of ethylene, and it is higher so that catalyst is had
Catalytic activity and/or stability.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of alumina support, which includes α-oxygen
Change aluminium, zirconium, boron and contains silicon additive；On the basis of the total weight of the alumina support, the content of zirconium is 0.20~1.40 weight
% is measured, the content of boron is 0.09~0.25 weight %, and the mass ratio of zirconium and boron is 1.7~15 ︰ 1, and the content containing silicon additive is
0.02~0.08 weight %, the weight % of the content of Alpha-alumina >=95.
The alumina support (also referred to as alpha-alumina supports) is catalyzed be especially suitable for epoxidation of ethylene silver
The carrier of agent.
The zirconium, boron refer to element zirconium, element boron.Wherein, the content of zirconium is higher, the Kong Rongyue of the alumina support
Greatly.
Preferably, in the alumina support, the mass ratio of zirconium and boron is 2.0~12.5 ︰ 1, in this way, ethylene ring can be improved
The ethylene oxide selectivity of oxidation reaction silver catalyst.
It is highly preferred that in the alumina support, the mass ratio of zirconium and boron is 2.0~7.0, can further increase silver in this way
The catalytic activity of catalyst.
Preferably, in the alumina support, the weight % of the content of Alpha-alumina >=97.
According to the present invention, it is described containing silicon additive can be existing silver catalyst alumina support in conventional selection, by
The silicon-containing compound for preparing the silver catalyst determines.The silicon-containing compound is preferably selected from the silicon of alkali metal, alkaline-earth metal
At least one of the oxide of hydrochlorate and silicon, is more preferably selected from the silicate of alkaline-earth metal.
Usually, the crushing strength of the alumina support is 40~120N/, and specific surface is 0.7~1.5m2/ g, hole
It is 0.35~0.50mL/g to hold.
Preferably, the crushing strength of the alumina support is 50~100N/, and specific surface is 0.9~1.3m2/ g, hole
It is 0.36~0.45mL/g to hold.
According to the second aspect of the invention, the present invention provides a kind of method preparing alumina support, this method includes：
1) by solid mixture, binder and can after-flame lubriation material mediated, extrusion molding；
2) product that step 1) obtains is dried, roasted, to which the alumina support be made；
Wherein, with the total weight of the solid mixture, the solid mixture includes following components：
A) the three water α-A1 that the granularity of 30~80 weight % is 25~300 μm2O3；
B) granularity of 10~45 weight % is less than 75 μm of one water A1 of vacation2O3；
C) α-A1 that the granularity of 3~40 weight % is 3~8 μm2O3；
D) zirconium-containing compound of 0.01~1.8 weight %；
E) silicon-containing compound of 0.01~0.5 weight %；
F) boric acid of 0.1~1 weight %；
Relative to the solid mixture of 100 parts by weight, the dosage of the binder is 10~50 parts by weight, it is described can
The dosage of after-flame lubriation material is 0.01~5 parts by weight.
In the method for the present invention, 3~8 μm of α-Al2O3Hydrated alumina can be reduced and turn crystalline substance into α-Al2O3Calcination temperature
Reduce α-Al simultaneously2O3Crystal size.
Preferably, with the total weight of the solid mixture, the α-A1 that granularity is 3~8 μm2O3Dosage be 10~25
Weight %.
In the method for the present invention, the effect of the zirconium-containing compound is to improve the Kong Rong of carrier.The zirconium-containing compound
It is preferably selected from least one of sulfate, nitrate, carbonate and the oxide of zirconium, more preferably zirconium dioxide.
Preferably, with the total weight of the solid mixture, the dosage of the zirconium-containing compound is 0.2~1.5 weight
Measure %.
In the method for the present invention, the silicon-containing compound can be such that the aperture in carrier increases, to increase alumina support
Specific surface, be the source containing silicon additive in alumina support.The silicon-containing compound is preferably selected from alkali metal, alkaline-earth metal
At least one of the oxide of silicate and silicon, is more preferably selected from the silicate of alkaline-earth metal.
Preferably, with the total weight of the solid mixture, the dosage of the silicon-containing compound is 0.05~0.4 weight
Measure %.
In the present invention, the effect of boric acid is to increase the compression strength of carrier.Preferably, with the total of the solid mixture
The dosage of weight meter, boric acid is 0.15~0.85 weight %.
In the present invention, it is described can the material being added to make after kneading of after-flame lubriation material be easy to be molded and be granulated,
Oxidation reaction occurs in material roasting process simultaneously and generates gas effusion, is not introduced when carrier is made or as few as possible
Impurity is introduced, to not influence the performance of catalyst.It is described can after-flame lubriation material can be powdered or paste, can be selected from stone
At least one of oil coke, carbon dust, graphite and vaseline.
Under preferable case, relative to the solid mixture of 100 parts by weight, it is described can after-flame lubriation material dosage be
0.05~4 parts by weight.
During preparing carrier, the binder and the one water A1 of vacation in solid mixture2O3It is molten that reaction generates aluminium
Glue is bonded together each component, becomes extrudable molding paste.Therefore, the binder and one water A1 of vacation2O3Also may be used
Completely or partially to be replaced with Aluminum sol.
The binder is the conventional selection that extrusion molding prepares alumina support, usually can be selected from acid, such as nitric acid, first
Acid, acetic acid, propionic acid and hydrochloric acid etc..It is preferred that the binder is the aqueous solution of nitric acid, the wherein weight ratio of nitric acid and water can be
1 ︰ 1.25~10.
In step 1), the shape of the extrusion molding can be annular, spherical, cylindricality or porous column shape.
In step 2), the water content in product that step 1) obtains is normally controlled in 10% or less by the drying.It is described
Dry temperature can be 80~120 DEG C, and the dry time can be controlled in 1~24 hour according to moisture.
In addition, as described above, 3~8 μm of α-A12O3Introducing so that the temperature of roasting is reduced.Specifically, the roasting
Temperature can be 1200~1450 DEG C, preferably 1250~1400 DEG C；Time can be 1~20 hour, and preferably 2~15 is small
When.
During preparing carrier, three water α-A12O3Dehydration turns crystalline substance into α-A1 in high-temperature calcination process2O3；A false water
A12O3The Aluminum sol generated is reacted with binder, and stable α-A1 are also translated into high-temperature calcination process2O3, become α-A12O3
A part for carrier.In addition, the zirconium-containing compound, boric acid are converted to zirconium oxide, three oxidations respectively in high-temperature calcination process
Two boron.
According to the third aspect of the invention we, the present invention provides the alumina supports that the above method is prepared.For second
For alkene epoxidation reaction, there is ideal porosity, specific surface by the alumina support that above method is prepared
And pore structure.In the alumina support, in terms of total pore volume, 1.0~5.0 μm of hole accounts for 60~80 volume %.In addition, according to one
Kind embodiment, the alumina support that the method is prepared can be the alumina support described in first aspect present invention,
I.e. the alumina support of first aspect present invention can be prepared by the above method.
According to the fourth aspect of the invention, the present invention provides a kind of epoxidation of ethylene silver catalyst, which urges
Agent includes：
A) alumina support of the present invention；
B) silver-colored；
C) alkali metal, the alkali metal are selected from least one of lithium, sodium, potassium, rubidium and caesium；
D) alkaline-earth metal, the alkaline-earth metal are selected from least one of calcium, magnesium, strontium and barium；
E) rhenium auxiliary agent and its optional coassist agent.
Usually, on the basis of the total weight of the silver catalyst, silver-colored content is 5~37 weight %, the content of alkali metal
For 5~3000ppm, the content of alkaline-earth metal is 100~3000ppm, and the content of rhenium is 10~1000ppm, coassist agent content with
Metal in coassist agent is calculated as 0~200ppm.
Preferably, on the basis of the total weight of the silver catalyst, silver-colored content is 8~32 weight %, the content of alkali metal
For 10~2000ppm, the content of alkaline-earth metal is 150~2500ppm, and the content of rhenium is 100~800ppm, coassist agent content with
Metal in coassist agent is calculated as 0~150ppm.
In the present invention, above-mentioned alumina support, the constituent content involved by silver catalyst are calculated all in accordance with inventory
It measures.
In the present invention, the silver catalyst can be prepared in the usual way, such as by with Ag-containing compound, organic amine, alkali
The solution dipping of metal promoter, the base earth metal promoter and rhenium-containing auxiliary agent and its optional coassist agent composition alumina support
To prepare.
The organic amine can be any organic amine compound suitable for preparing ethylene oxide silver catalyst, as long as
The organic amine compound can form argent-amine complex with silver compound, such as selected from pyridine, butylamine, ethylenediamine, 1,3-
One or more of propane diamine, ethanol amine.It is preferred that the organic amine is ethylenediamine and/or ethanol amine.
The alkali metal promoter is selected from the compound of corresponding alkali metal (lithium, sodium, potassium, rubidium or caesium)；Such as selected from the alkali
One or more of nitrate, sulfate and hydroxide of metal.
Preferably, the alkali metal promoter is one or more of lithium sulfate, cesium sulfate and cesium nitrate.
The base earth metal promoter is selected from the compound of corresponding alkaline-earth metal (magnesium, calcium, strontium or barium)；Such as selected from the alkali
One or more of oxide, oxalates, sulfate, acetate and nitrate of earth metal.
The base earth metal promoter is preferably selected from the compound of barium and/or strontium, is more preferably selected from barium acetate and/or acetic acid
Strontium.
In addition, the base earth metal promoter can be applied on the alumina support prior to, concurrently with, or after immersion silver,
It can also be immersed on carrier after the silver compound is reduced.
In the present invention, the rhenium auxiliary agent and its optional coassist agent can improve the activity of silver catalyst, selectivity and
The stability of activity and selectivity.
The rhenium auxiliary agent can be selected from one or more of oxide, perrhenic acid, perrhenate of rhenium, be preferably selected from height
Rehenic acid and perrhenate are more preferably selected from least one of perrhenic acid, perrhenic acid caesium and ammonium perrhenate.
The coassist agent can be the compound of any transition metal or several transistion metal compounds in the periodic table of elements
Mixture, the metal in the coassist agent is preferably selected from group vib and VIIB races element, and the coassist agent may include group vib
With the oxyacid and its salt of VIIB races elements, further preferably in wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate and cerous sulfate
It is at least one.
In addition, the rhenium auxiliary agent and its optional coassist agent can be applied to prior to, concurrently with, or after immersion silver it is described
On alumina support, it can also be immersed on carrier after silver compound is reduced.
In one embodiment, the silver catalyst is made by the following method：
1) with silver compound, organic amine, alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent and optional containing sufficient amount
The solution of coassist agent impregnate above-mentioned alumina support；
2) maceration extract, and dry impregnated carrier are filtered off；With
3) in containing oxygen gas mixture, to being activated through impregnated carrier, to which the silver catalyst be made.
In step 1), specifically can first it use silver-colored described in the aqueous dissolution of organic amine (such as ethylenediamine and/or ethanol amine)
Compound (such as silver oxalate) generates argent-amine complex, then is made into the maceration extract with auxiliary agents such as above-mentioned alkali metal；
In step 3), the purpose of activation is that product, which is carried out thermal decomposition, is made finished product silver catalyst.Wherein, the activation
It (can be carried out in the nitrogen oxygen atmosphere of such as oxygen-containing 8.0%), the temperature of activation is usual no more than 21% in air stream or oxygen content
It is 180~700 DEG C, preferably 200~500 DEG C, the time of activation can be 0.5~120 minute, preferably 1~60 minute.
According to the fifth aspect of the invention, the present invention provides a kind of methods that ethylene epoxidizing prepares ethylene oxide, should
Method includes：Ethylene is set to carry out epoxidation reaction in the presence of epoxidation of ethylene silver catalyst.
This method can improve the yield of ethylene oxide due to the use of epoxidation of ethylene silver catalyst.In addition,
The reaction unit that the method uses can be any device that can carry out epoxidation reaction.
It is described further with reference to embodiment, but the scope of the invention is not limited to these embodiments.
The various silver catalysts of following embodiment test it with laboratory reactor (hereinafter referred to as " micro- anti-") evaluating apparatus
Initial performance and stability.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating mantle
In.The admission space of catalyst is 1mL, and there is inert filler in lower part, catalyst bed is made to be located at the flat-temperature zone of heating mantle.
The determination condition of the activity and selectivity of silver catalyst is as follows：
The gas composition (mol%) of Reactor inlet：Ethylene (C2H4), 28.0 ± 1.0；Oxygen (O2), 7.4 ± 0.2；Dioxy
Change carbon (CO2), ＜ 3.0；Cause steady gas (N2), surplus；Inhibitor dichloroethanes (appropriate), ethylene oxide (EO) concentration, 2.50%.
Reaction pressure, 2.1MPa；Air speed, 4500/h；Space-time yield, 221kgEO/m3Cat./h。
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity as follows after shrinking correction：
Wherein, Δ EO is to work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, and the average of 10 groups or more test datas is taken to make
For the test result on the same day.
Embodiment 1
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 2.5g, boric acid 6.0g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 2
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 2.5g, boric acid 5.0g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 3
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 2.5g, boric acid 2.5g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 4
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 1.25g, boric acid 1.0g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 5
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 7.5g, boric acid 2.5g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 6
The present embodiment is used to illustrate the alumina support and preparation method thereof of the present invention.
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 9.0g, boric acid 2.5g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Comparative example 1
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, boric acid 2.5g are put into blender and are uniformly mixed, be transferred in kneader, and 12g vaseline is added
With the ︰ 3 of 100mL dust technology (Xiao Suan ︰ water=1, weight ratio), it is kneaded into extrudable molding paste.Extrusion molding is outer diameter
The single hole column of 8.0mm, long 6.0mm, internal diameter 3.0mm are dried 2 hours or more at 80~120 DEG C, make free water content drop
As low as 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1350 DEG C from room temperature through 33 hours,
It is calcined 5 hours under the conditions of 1350 DEG C, obtains white α-A12O3Carrier.The carrier measured mainly form and pore structure parameter respectively such as
Shown in the following table 1 and table 2.
Comparative example 2
By 25~300 μm of three water α-A12O3350g is less than 75 μm of one water A1 of vacation2O3150g, 3~8 μm of α-
A12O3100g, calcium silicates 1.0g, zirconium dioxide 2.5g, boric acid 0.3g are put into blender and are uniformly mixed, be transferred in kneader,
The ︰ 3 of 12g vaseline and 100mL dust technology (Xiao Suan ︰ water=1, weight ratio is added), it is kneaded into extrudable molding paste.It squeezes out
It is shaped to the single hole column of outer diameter 8.0mm, long 6.0mm, internal diameter 3.0mm, is dried 2 hours or more at 80~120 DEG C, makes trip
It is reduced to 10% or less from water content.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature increase
To 1350 DEG C, is calcined 5 hours under the conditions of 1350 DEG C, obtain white α-A12O3Carrier.The carrier measured mainly forms and hole knot
Structure parameter is distinguished shown in following Tables 1 and 2.
Embodiment 7~12
Embodiment 7~12 is used to illustrate the silver catalyst and preparation method thereof of the present invention.
98g ethylenediamines are dissolved in 150g deionized waters, under stiring, silver oxalate is slowly added into the mixed liquor,
Temperature is maintained at 40 DEG C hereinafter, silver oxalate is made all to dissolve, and the addition of silver oxalate is the silver in silver catalyst in terms of silver element
Content is 21 weight %, adds 0.9g cesium nitrates, 0.78g strontium acetates, 0.44g perrhenic acid, 0.10g lithium sulfates and deionized water
So that solution gross mass is reached 500g, it is for use to be configured to maceration extract.
The alumina support sample 250g that respectively prepared by Example 1~6, is put into the container that can be vacuumized, vacuumizes
To 10mmHg or more, above-mentioned maceration extract is introduced, 30min, leaching is kept to remove extra solution.Carrier after dipping is at 300 DEG C
3min is heated in air stream, it is cooling, that is, the silver catalyst of embodiment 7~12 is made.
The activity and selectivity of catalyst sample is evaluated under the conditions of previous process using the micro anti-evaluation device, is evaluated
As a result it is listed in the table below in 3.
Comparative example 3~4
Silver catalyst is prepared using the method for embodiment 7~12, the difference is that using oxygen prepared by comparative example 1~2 respectively
Change the carrier that alumina supporter replaces Examples 1 to 6, to which silver catalyst be made.
The activity and selectivity of catalyst sample is evaluated under the conditions of previous process using the micro anti-evaluation device, is evaluated
As a result it is listed in the table below in 3.
Table 1
Table 2
Table 3
| Catalyst | Reaction temperature (DEG C) | Selectivity (%) |
| Embodiment 7 | 232.4 | 87.84 |
| Embodiment 8 | 233.8 | 88.75 |
| Embodiment 9 | 235.6 | 89.26 |
| Embodiment 10 | 231.9 | 88.12 |
| Embodiment 11 | 243.4 | 89.21 |
| Embodiment 12 | 248.1 | 89.17 |
| Comparative example 3 | 230.8 | 85.37 |
| Comparative example 4 | 241.3 | 88.03 |
Table 1 to table 3 is combined as can be seen that compared with comparative example 3, the silver catalyst of embodiment 7~12 is for ethylene
When epoxidation is prepared in reacting ethylene oxide, the selectivity of ethylene oxide is significantly higher, 87.5% or more；And embodiment 8
~11 catalyst is even more to have both higher catalytic activity and selectivity.Compared with comparative example 4, the selectivity of embodiment 7 is slightly lower,
But catalytic activity is high, and the stability of the catalyst is better than comparative example 4；The selectivity of embodiment 12 is substantially better than comparative example 4, anti-
Temperature is answered also to allow in the temperature used (usually less than 260 DEG C) in silver catalyst, it is seen then that the catalyst of embodiment 8 and 12
Comprehensive performance is also superior to comparative example 4.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (11)
1. a kind of alumina support, which is characterized in that the alumina support includes Alpha-alumina, zirconium, boron and contains silicon additive；With institute
On the basis of the total weight for stating alumina support, the content of zirconium is 0.20~1.40 weight %, and the content of boron is 0.09~0.23 weight
% is measured, and the mass ratio of zirconium and boron is 1.7~15 ︰ 1, preferably 2.0~12.5 ︰ 1, the content containing silicon additive is 0.02~0.08
Weight %, the weight % of the content of Alpha-alumina >=95；
In the alumina support, in terms of total pore volume, 1.0~5.0 μm of hole accounts for 60~80 volume %.
2. alumina support according to claim 1, wherein the crushing strength of the alumina support is 40~120N/
Grain, preferably 50~100N/；Specific surface is 0.7~1.5m2/ g, preferably 0.9~1.3m2/g；Kong Rongwei 0.35~
0.50mL/g, preferably 0.36~0.45mL/g.
3. a kind of method preparing alumina support, which is characterized in that this method includes：
1) by solid mixture, binder and can after-flame lubriation material mediated, extrusion molding；
2) product that step 1) obtains is dried, roasted, to which the alumina support be made；
Wherein, with the total weight of the solid mixture, the solid mixture includes following components：
A) the three water α-Al that the granularity of 30~80 weight % is 25~300 μm2O3；
B) granularity of 10~45 weight % is less than 75 μm of one water Al of vacation2O3；
C) α-Al that the granularity of 3~40 weight % is 3~8 μm2O3；
D) zirconium-containing compound of 0.01~1.8 weight %；
E) silicon-containing compound of 0.01~0.5 weight %；
F) boric acid of 0.1~1 weight %；
Relative to the solid mixture of 100 parts by weight, the dosage of the binder is 10~50 parts by weight, it is described can after-flame
The dosage of lubriation material is 0.01~5 parts by weight.
4. according to the method described in claim 3, wherein, on the basis of the total weight of the solid mixture, granularity is 3~8 μ
α-the Al of m2The dosage of O is 10~25 weight %.
5. according to the method described in claim 3, wherein, the zirconium-containing compound is selected from sulfate, nitrate, the carbonate of zirconium
At least one of with oxide；
Preferably, on the basis of the total weight of the solid mixture, the dosage of the zirconium-containing compound is 0.2~1.5 weight
Measure %.
6. according to the method described in claim 3, wherein, the silicon-containing compound is selected from the silicate of alkali metal, alkaline-earth metal
And at least one of the oxide of silicon；
Preferably, on the basis of the total weight of the solid mixture, the dosage of the silicon-containing compound is 0.05~0.4 weight
Measure %.
7. according to the method described in claim 3, wherein, it is described can after-flame lubriation material be selected from petroleum coke, carbon dust, graphite and all
At least one of intellectual circle；
Preferably, relative to the solid mixture of 100 parts by weight, it is described can the dosage of after-flame lubriation material be 0.5~4 weight
Measure part.
8. according to the method described in claim 3, wherein, in step 2), the temperature of the roasting is 1200~1450 DEG C, the time
It is 1~20 hour.
9. the alumina support that any one of claim 3~8 the method is prepared.
10. a kind of epoxidation of ethylene silver catalyst, which is characterized in that the silver catalyst includes：
A) alumina support described in any one of claim 1~2 and 9；
B) silver-colored；
C) alkali metal, the alkali metal are selected from least one of lithium, sodium, potassium, rubidium and caesium；
D) alkaline-earth metal, the alkaline-earth metal are selected from least one of calcium, magnesium, strontium and barium；
E) rhenium auxiliary agent and its optional coassist agent.
11. a kind of method that ethylene epoxidizing prepares ethylene oxide, this method include：Make ethylene ethylene described in claim 10
Epoxidation reaction is carried out in the presence of epoxidation reaction silver catalyst.
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| CN111437888A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | α -alumina carrier, silver catalyst for ethylene epoxidation and application |
| CN112206798A (en) * | 2020-10-29 | 2021-01-12 | 润和催化材料(浙江)有限公司 | Silver catalyst for preparing ethylene oxide by ethylene oxidation and preparation method and application thereof |
| CN114100595A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene epoxidation and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation |
| CN115364833A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN116726919A (en) * | 2023-05-22 | 2023-09-12 | 大连瑞克科技股份有限公司 | Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof |
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| CN111437888A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | α -alumina carrier, silver catalyst for ethylene epoxidation and application |
| CN114100595A (en) * | 2020-08-28 | 2022-03-01 | 中国石油化工股份有限公司 | Silver catalyst carrier for ethylene epoxidation and preparation method thereof, silver catalyst and method for producing ethylene oxide by ethylene epoxidation |
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| CN115364833A (en) * | 2021-05-19 | 2022-11-22 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN116726919A (en) * | 2023-05-22 | 2023-09-12 | 大连瑞克科技股份有限公司 | Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof |
| CN116726919B (en) * | 2023-05-22 | 2024-04-09 | 大连瑞克科技股份有限公司 | Modified carrier of catalyst for synthesizing ethylene oxide by oxidizing ethylene and preparation method thereof |
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