CN109201027B - Alpha-alumina carrier and preparation method and application thereof - Google Patents
Alpha-alumina carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN109201027B CN109201027B CN201710532070.5A CN201710532070A CN109201027B CN 109201027 B CN109201027 B CN 109201027B CN 201710532070 A CN201710532070 A CN 201710532070A CN 109201027 B CN109201027 B CN 109201027B
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- China
- Prior art keywords
- component
- alpha
- less
- alumina carrier
- carrier
- Prior art date
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- 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 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 102
- 229910052709 silver Inorganic materials 0.000 claims abstract description 70
- 239000004332 silver Substances 0.000 claims abstract description 70
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 83
- 239000000203 mixture Substances 0.000 claims description 72
- 229910001679 gibbsite Inorganic materials 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 33
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- 229910052702 rhenium Inorganic materials 0.000 claims description 31
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910001648 diaspore Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 18
- -1 silicic acid compound Chemical class 0.000 claims description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002006 petroleum coke Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 229940099259 vaseline Drugs 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002210 silicon-based material Substances 0.000 claims description 9
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229940100890 silver compound Drugs 0.000 claims description 8
- 150000003379 silver compounds Chemical class 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002222 fluorine compounds Chemical group 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 16
- 150000004682 monohydrates Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical group [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000003345 natural gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000969 carrier Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002671 adjuvant Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000011160 research Methods 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
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical group [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation 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
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008247 solid mixture Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
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- 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
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- 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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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/635—0.5-1.0 ml/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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Abstract
The invention relates to an alpha-alumina carrier, a preparation method and application thereof, in particular to an alpha-alumina carrier applied to preparation of a silver catalyst, a preparation method thereof, a silver catalyst containing the carrier, a preparation method of the silver catalyst, and application of the silver catalyst in production of an epoxy compound by oxidation of olefin. The carrier improves the specific surface area, the strength, the water absorption and the pore distribution of the alpha-alumina carrier by adjusting the granularity of the carrier raw material, the type of the raw material and adding a substance with pore-forming effect. The silver catalyst prepared by the alpha-alumina carrier is used for preparing ethylene oxide by ethylene epoxidation, the activity and the selectivity of the catalyst are obviously improved, and the silver catalyst has wide application prospect in producing epoxy compounds by olefin oxidation.
Description
Technical Field
The invention belongs to the technical field of catalyst carriers and catalyst preparation, and particularly relates to an alpha-alumina carrier and a preparation method and application thereof.
Background
At present, the method for industrially producing the ethylene oxide in the world is directly obtained by oxidizing ethylene, and a silver catalyst is adopted. The catalyst carrier is an inert material, usually alpha-alumina, and the active component is silver, and other auxiliary agents are added. The direct oxidation of ethylene and oxygen to ethylene oxide over metallic silver is an important catalytic process. In the process of producing ethylene oxide by oxidizing ethylene, the use of the silver catalyst with high activity, high selectivity and good stability can greatly improve the economic benefit, so that the preparation of the silver catalyst with high activity, high selectivity and good stability is the main direction of the research of the silver catalyst. The performance of the silver catalyst has an important relationship with the composition of the catalyst and the preparation method, and also with the performance of the carrier and the preparation method.
The composition and preparation method of the catalyst mainly focuses on the research of auxiliary agent, wherein rhenium (Re) and cesium (Cs) are introduced, and the Shell company firstly discloses a rhenium-containing silver catalyst patent in 1986. Patents US4761394 and US4766105 continuously report on a porous refractory carrier supported silver catalyst containing an alkali metal, a rhenium promoter and a rhenium co-promoter with further improvement of the catalyst selectivity. In the patent CN102527384A of the beijing chemical research institute of china petrochemical company limited, the dipping sequence and dipping time in the preparation process of the catalyst are reported to have an influence on the performance of the catalyst, the addition sequence of the auxiliary is considered to have an influence on the performance of the catalyst, and the alkali metal auxiliary and the alkaline earth metal auxiliary cannot be added before the rhenium auxiliary. Patents on the amount of silver supported and the number of impregnation times are also reportedMXPA04008167(A) indicates a silver loading of at least 10 g/kg on the support and a surface area of greater than 1m2(ii) a pore diameter of from 0.2 to 10 microns in a total pore volume of greater than 70%, providing a pore volume of at least 0.27 ml/g. The patent US5691269(a) reports a silver catalyst for olefin epoxidation, the catalyst carrier being a porous carrier having a surface area of 0.1-2m2The pore volume is 0.1-1ml/g, the supported silver amount is 3-20 wt%, and the number of the supported silver particles per square micron on the fresh catalyst is 10-70.
The patents on the carrier focus on the preparation method, composition, pore distribution and the like of the carrier. Patents US 5063195 and US 5703001 report methods for the preparation of vectors. Patents US6787656 and US 5145824 indicate that the performance of the carrier can be improved by adding zirconium (Zr) to the alumina carrier. Chinese petrochemical patent CN101850243A reports that acid and water treatment carriers can change the pore structure of the carrier, thereby improving the performance of the catalyst.
Although the above patent documents bring about improvements in the activity or selectivity of the catalyst to various degrees by making improvements in the support preparation and catalyst preparation systems, respectively, the studies on these property improvements have been continued, and the ways of improving the properties will be more diversified, and it is expected that the activity and selectivity of the catalyst can be improved at the same time.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an alpha-alumina carrier aiming at the defects of the prior art, wherein the alpha-alumina carrier improves the specific surface area, the strength, the water absorption and the pore distribution of the alpha-alumina carrier by adjusting the granularity and the raw material ratio of carrier raw materials and adding substances with pore-forming effect. The invention also provides a preparation method of the alpha-alumina carrier, which is characterized in that proper pore distribution is produced by matching raw materials with different particle sizes, different raw material ratios can influence the crystal phase transformation, and substances with pore-forming effect can generate richer diffusion channels and larger specific surface area. The silver catalyst prepared by the alpha-alumina carrier is used for preparing ethylene oxide by ethylene epoxidation, and the activity and the selectivity of the catalyst can be obviously improved.
To this end, the present invention provides in a first aspect an α -alumina support obtained by forming, drying and calcining an α -alumina support precursor mixture, wherein the α -alumina support precursor mixture comprises:
component a, aluminum hydroxide with the grain size of less than 100 mu m and less than or equal to 10 mu m;
component b, 100 mu m or less aluminum hydroxide with granularity less than 300 mu m;
component c, carbon-containing combustible material with the granularity of more than or equal to 250 mu m and less than 800 mu m and/or carbon-containing combustible material with the granularity of more than or equal to 50 mu m and less than 300 mu m;
component d, C15-C40Mixtures of higher alkanes and higher alkenes;
component e, a mineralizer;
component f, an alkaline earth metal compound;
component g, a silicon-containing compound;
component h, a binder; and
component i, water.
According to some embodiments of the invention, the composition of the alpha-alumina support precursor mixture, by weight of its total batch, is as follows:
component a, aluminum hydroxide with the particle size of less than 100 mu m and less than or equal to 10 mu m, 1 to 90 weight percent;
component b, 100 mu m or less aluminum hydroxide with the granularity less than 300 mu m, 1 to 90 weight percent;
component c, 0-10 wt% of carbon-containing combustible material with the particle size less than 800 μm and less than or equal to 250 μm; and/or
0-30 wt% of carbon-containing combustible material with the particle size of less than 300 mu m and less than or equal to 50 mu m;
component d, C15-C401 to 10 weight percent of mixture of high-carbon alkane and high-carbon alkene;
component e, mineralizer, 0.1 wt% -5.0 wt%;
0.1-10 wt% of component f, alkaline earth metal compound;
component g, silicon-containing compound, 0.1 wt% -5.0 wt%;
component h, binder, 1 wt% to 10 wt%, and;
component i, water, and the balance;
wherein, the amount of the carbon-containing combustible material with the grain size of more than or equal to 250 mu m and less than 800 mu m and the carbon-containing combustible material with the grain size of more than or equal to 50 mu m and less than 300 mu m in the component c are not 0 percent at the same time.
In some preferred embodiments of the invention, the amount of aluminium hydroxide with a particle size of 100 μm or less and a particle size of < 300 μm of component b is 1 to 90 wt%, based on the total weight of the formulation, of the alpha-alumina carrier precursor mixture.
In some preferred embodiments of the invention, component c is a carbonaceous combustible of 250 μm particle size < 800 μm and a carbonaceous combustible of 50 μm particle size < 300 μm, the weight ratio of carbonaceous combustible of 250 μm particle size < 800 μm and carbonaceous combustible of 50 μm particle size < 300 μm being (10-1): 1.
According to some embodiments of the invention, the aluminum hydroxide in component a is gibbsite and/or diaspore.
In some preferred embodiments of the present invention, the aluminum hydroxide in component a is gibbsite and diaspore in a weight ratio of (1-10):1, preferably (1-5): 1.
According to some embodiments of the invention, the aluminum hydroxide in component b is gibbsite and/or diaspore. The aluminum hydroxide in the component b is gibbsite and diaspore, and the weight ratio of the gibbsite to the diaspore is (1-10):1, preferably (1-5): 1.
In some preferred embodiments of the invention, the weight ratio of component a to component b is from 0.1 to 15, preferably from 0.1 to 10.
In the present invention, said C15-C40The mixture of higher alkane and higher alkene is preferably a lubricating lipid material, and more preferably one or more of white oil and vaseline.
According to some embodiments of the invention, the alkaline earth metal compound comprises one or more of an oxide, nitrate, sulfate, carbonate, oxalate and chloride of an alkaline earth metal; preferably, the heavy alkaline earth metal is magnesium and/or barium.
In the present invention, the mineralizer is preferably a fluoride, including one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride, and lithium fluoride.
According to some embodiments of the invention, the silicon-containing compound comprises one or more of a silicon-containing oxide and a silicic acid compound, preferably one or more of sodium silicate, calcium silicate, zirconium silicate, silicic acid and silicon oxide.
In the present invention, the carbonaceous combustibles include petroleum coke and/or graphite.
According to some embodiments of the invention, the weight ratio of the binder to water is 1 (1.25-10).
In the present invention, the binder includes one or more of citric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and propionic acid.
In some embodiments of the invention, the specific surface of the alpha-alumina support is between 0.8 and 3.0m2The pore volume is 0.4-0.7ml/g, the water absorption is more than or equal to 50 percent, the crushing strength is 50-200N/grain, and according to the total pore volume, the pores with the pore diameter of 0.1 mu m or less and less than 5 mu m account for 40-80 percent, the pores with the pore diameter of 5 mu m or less and less than 10 mu m account for 1-40 percent, and the pores with the pore diameter of more than or equal to 10 mu m account for 0.1-10 percent.
In a second aspect, the present invention provides a method for preparing an α -alumina support according to the first aspect of the present invention, which comprises:
step S1, mixing the components a-i to form an alpha-alumina carrier precursor mixture;
and step S2, forming the alpha-alumina carrier precursor mixture, drying and roasting to obtain the alpha-alumina carrier.
According to some embodiments of the present invention, in step S2, the temperature of the roasting is 1200-1500 ℃; and/or the indicated calcination time is 10-50 h.
In a third aspect, the present invention provides a silver catalyst for the epoxidation of an olefin to produce an epoxide, comprising the following components, based on the total weight of the catalyst:
component i, an alpha-alumina carrier according to the first aspect of the present invention or prepared according to the method of the second aspect of the present invention;
component m, silver element 10% -22% (weight);
component n, 10-5000ppm (weight) of alkali metal element;
component o, alkaline earth metal element 10-2000ppm (weight);
component p, rhenium element less than or equal to 2000ppm (weight);
the metal elements in the component q and the co-promoter of the rhenium promoter are less than or equal to 2000ppm (weight).
In a fourth aspect, the present invention provides a method for preparing a silver catalyst for producing an epoxy compound by olefin epoxidation according to the third aspect, which comprises immersing the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared by the method according to the second aspect of the present invention in a solution of a silver compound, an organic amine compound and an auxiliary agent, and then carrying out filtration and activation heat treatment to obtain a silver catalyst; the promoter comprises an alkali metal promoter, an alkaline earth metal promoter, an optional rhenium promoter and an optional rhenium co-promoter.
In a fifth aspect, the present invention provides a process for the epoxidation of an olefin to produce an epoxide, the olefin being subjected to epoxidation in the presence of a silver catalyst prepared by the process of the third aspect of the present invention.
In some embodiments of the invention, the olefin comprises one or more of styrene, propylene, ethylene, and 1, 3-butadiene.
The alpha-alumina carrier provided by the invention improves the specific surface area, strength, water absorption and pore distribution of the alpha-alumina carrier by adjusting the granularity and the type of raw materials of the carrier and adding substances with pore-forming effect. The silver catalyst prepared by the alpha-alumina carrier is used for preparing ethylene oxide by ethylene epoxidation, the activity and the selectivity of the catalyst are obviously improved, and the silver catalyst has wide application prospect in producing epoxy compounds by olefin oxidation.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below.
As previously mentioned, although the prior art brings about improvements to the activity or selectivity of the catalyst to varying degrees by making improvements in the support preparation and catalyst preparation systems, respectively, the research on these improvements in properties has been continued again, and the ways of improving the properties will be more diversified, and it is expected that the activity and selectivity of the catalyst can be improved at the same time. In view of the above, the present inventors have conducted extensive studies on silver catalysts and α -alumina carriers, and have unexpectedly found that the physical properties of the carriers, including specific surface area, strength, water absorption rate and pore distribution, can be effectively improved by adjusting the particle size and the ratio of the carrier raw materials, and that the selectivity and activity of the catalyst can be improved when the amount of the catalyst supporting silver and the kind and amount of the auxiliary are within a certain range. The present invention has been made based on the above findings.
Thus, the alpha-alumina carrier according to the first aspect of the present invention is prepared by forming, drying and calcining a precursor mixture of the alpha-alumina carrier. The specific surface of the alpha-alumina carrier is 0.8-3.0m2(ii)/g; the pore volume is 0.4-0.7 ml/g; the water absorption rate is more than or equal to 50 percent; the crushing strength is 50-200N/grain; based on the total pore volume, the pores with the pore diameter of less than 5 μm and less than 0.1 μm account for 40-80%, the pores with the pore diameter of less than 10 μm and less than 5 μm account for 1-40%, and the pores with the pore diameter of more than 10 μm account for 0.1-10%.
In some embodiments of the invention, the alpha-alumina support precursor mixture comprises:
component a, aluminum hydroxide with the grain size of less than 100 mu m and less than or equal to 10 mu m;
component b, 100 mu m or less aluminum hydroxide with granularity less than 300 mu m;
component c, carbon-containing combustible material with the grain size of 250 mu m or less and less than 800 mu m and/or carbon-containing combustible material with the grain size of 50 mu m or less and less than 300 mu m
A carbon combustible;
component d, C15-C40Mixtures of higher alkanes and higher alkenes;
component e, a mineralizer;
component f, an alkaline earth metal compound;
component g, a silicon-containing compound;
component h, a binder; and
component i, water and the balance.
According to some embodiments of the present invention, the method for preparing an α -alumina support according to the second aspect of the present invention, as defined in the first aspect of the present invention, comprises the steps of:
(1) an alpha-alumina carrier precursor mixture was prepared having the following composition:
component a, aluminum hydroxide with the particle size of less than 100 mu m and less than or equal to 10 mu m, 1 to 90 weight percent;
component b, 100 mu m or less aluminum hydroxide with the granularity less than 300 mu m, 1 to 90 weight percent;
component c, 0-10 wt% of carbon-containing combustible material with the particle size less than 800 μm and less than or equal to 250 μm; and/or
0-10 wt% of carbon-containing combustible material with the particle size of less than 300 mu m and less than or equal to 50 mu m;
component d, C15-C401 to 10 weight percent of mixture of high-carbon alkane and high-carbon alkene;
component e, mineralizer, 0.1 wt% -5.0 wt%;
0.1-10 wt% of component f, alkaline earth metal compound;
component g, silicon-containing compound, 0.1 wt% -5.0 wt%;
component h, binder, 1 wt% to 10 wt%, and;
component i, water, and the balance;
wherein, the amount of the carbon-containing combustible material with the grain size of more than or equal to 250 mu m and less than 800 mu m and the carbon-containing combustible material with the grain size of more than or equal to 50 mu m and less than 300 mu m in the component c are not 0 percent at the same time.
(2) Kneading and extruding the alpha-alumina carrier precursor mixture in the step (1) to obtain a carrier blank, drying the carrier blank, and roasting at 1200-1500 ℃ to prepare alpha-A12O3And (3) a carrier.
In the preparation method of the carrier, the aluminum hydroxide of the component a is gibbsite or diaspore or a mixture of gibbsite and diaspore. When the aluminum hydroxide of component a is a mixture of gibbsite and diaspore, the weight ratio of gibbsite to diaspore is (1-10):1, preferably (1-5):1, more preferably (1-4):1, and still more preferably 4: 1.
In the above method for preparing the carrier, the component b is selected from the group consisting of aluminum hydroxide having a particle size of 100 μm to 300. mu.m in order to produce pores having various sizes, the aluminum hydroxide may be gibbsite or diaspore, and when the aluminum hydroxide having a particle size of 100 μm to 300. mu.m is not selected from the group consisting of gibbsite and diaspore, the amount added is more preferably 1 to 90%. When the aluminum hydroxide of component b is a mixture of gibbsite and diaspore, the weight ratio of gibbsite to diaspore is (1-10):1, preferably (1-5):1, more preferably (1-4):1, and still more preferably 4: 1.
In the above-mentioned method for producing a carrier, the weight ratio of the component a to the component b is 0.1 to 15, preferably 0.1 to 10, more preferably 5 to 10, still more preferably 10.
In the above-mentioned process for producing a carrier, said C15-C40The mixture of higher alkane and higher alkene is preferably grease-like material, which can lubricate and pore-forming, and is more preferably one or more of white oil and vaseline.
In the preparation step of the carrier, the carbon-containing combustible material is preferably petroleum coke and/or graphite, and is further preferably petroleum coke, so that the carbon-containing combustible material mainly plays a role of enlarging pores, and the carbon-containing combustible material with the particle size of 250-800 mu m and the particle size of 50-300 mu m can be added into one of the carbon-containing combustible materials or a mixture of the carbon-containing combustible materials with the particle sizes of the two carbon-containing combustible materials; when mixtures of carbonaceous combustibles with particle sizes of 250 μm to 800 μm and 50 μm to 300 μm are used, the ratio of the mixture of carbonaceous combustibles with particle sizes of 250 μm to 800 μm and 50 μm to 300 μm is preferably (10-1):1, preferably (5-1):1, more preferably (3.5-2): 1.
In the above method for preparing the carrier, the alkaline earth metal compound includes one or more of an oxide, a nitrate, a sulfate, a carbonate, an oxalate and a chloride of an alkaline earth metal; preferably, the alkaline earth metal is magnesium and/or barium, the purpose of which is to increase the strength of the support.
In the preparation method of the carrier, a binder solution is added, wherein the weight ratio of the binder to water in the binder solution is 1 (1.25-10); preferably the binder comprises one or more of citric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and propionic acid. The binder in the components of the silver catalyst carrier of the present invention and aluminum hydroxide form an aluminum sol, and the components are bound together to form an extrudable paste. The binder and aluminum hydroxide described in the present invention may be replaced in whole or in part with an aluminum sol.
In the preparation method of the carrier, the silicon-containing compound comprises one or more of silicon-containing oxide and silicic acid compound, and preferably one or more of sodium silicate, calcium silicate, zirconium silicate, silicic acid and silicon oxide.
The mineralizer used in the preparation step of the carrier according to the present invention is used to accelerate the crystal phase transition of aluminum hydroxide, and is usually selected from fluorides, which include one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride, and their mass accounts for 0.1% -5.0% of the mass of the solid mixture.
In the preparation method of the carrier, the precursor mixture is kneaded to obtain a paste, and then the paste is extruded and molded to obtain a carrier blank, wherein the carrier blank can be dried to the water content of less than 10%, the shape of the carrier blank can be spherical, block-shaped, cylindrical, single-hole cylindrical, porous cylindrical, Raschig ring-shaped, clover-shaped, honeycomb-shaped and the like, and is preferably a single-hole cylinder or a porous cylinder. The drying temperature of the carrier blank is preferably 60-120 ℃, and the drying time is preferably controlled within 10-30h according to the moisture content.
In some embodiments of the present invention, the calcination time in the step (2) is 10-40h, and the calcination converts all the alumina into alpha-A12O3。
According to some embodiments of the present invention, the silver catalyst for producing an epoxy compound by epoxidation of an olefin according to the third aspect of the present invention is obtained based on the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared by the method according to the second aspect of the present invention, and the silver catalyst contains, in addition to the α -alumina carrier, a metal element in a co-promoter of silver element, an alkali metal element, an alkaline earth metal element, rhenium element and a rhenium promoter.
In some embodiments of the invention, the alkali metal is selected from one or more of lithium, sodium, potassium, rubidium, and cesium.
In other embodiments of the present invention, the alkaline earth metal is selected from one or more of calcium, magnesium, strontium, and barium.
According to some embodiments of the invention, the silver element is present in the catalyst in an amount of 10% to 20% by weight, based on the total weight of the catalyst; the content of alkali metal element is 10-5000ppm (weight); the content of alkaline earth metal elements is 10-2000ppm (weight); the content of rhenium metal element is less than or equal to 2000ppm (weight); preferably 100-800ppm by weight; the content of the co-promoter of the rhenium promoter is less than or equal to 2000ppm (weight) calculated by metal elements in the co-promoter of the rhenium promoter; preferably 5 to 1000ppm by weight.
The term "optional" as used herein means either with or without, and with or without the addition of.
The term "≦" for a component defined as a range means that a component may be optionally or selectively added. For example, "the metallic element in the co-adjuvant of the rhenium adjuvant is 2000ppm by weight" means that the metallic element in the co-adjuvant of the rhenium adjuvant is an optional added component and is contained in an amount of 0ppm by weight or less of 2000ppm by weight or less of the metallic element in the co-adjuvant of the rhenium adjuvant.
In the present invention, X1. ltoreq.X < X2 indicates that the parameter X is in the range of X1 to X2.
The term "co-promoter for rhenium promoter" as used herein is also referred to as "co-promoter for rhenium".
According to some embodiments of the present invention, the method for preparing a silver catalyst for producing an epoxy compound by olefin epoxidation according to the fourth aspect of the present invention may be prepared in a conventional manner by immersing the α -alumina carrier according to the first aspect of the present invention or the α -alumina carrier prepared by the method according to the second aspect of the present invention in a solution of a silver compound, an organic amine compound and an auxiliary agent, filtering off the immersion liquid, and subjecting the resultant carrier to an activation treatment in an oxygen-containing mixed gas to prepare the silver catalyst; the promoter comprises an alkali metal promoter, an alkaline earth metal promoter, an optional rhenium promoter and an optional rhenium promoter co-promoter.
In the preparation method of the silver catalyst, the silver compound comprises one or more of silver oxide, silver nitrate and silver oxalate.
In the above method for producing a silver catalyst, the alkali metal promoter may be a compound of lithium, sodium, potassium, rubidium and cesium, such as a nitrate, sulfate or hydroxide thereof, or a combination of any two or more of the foregoing compounds; preferably, the alkali metal assistant is cesium sulfate and/or cesium nitrate.
In the above method for preparing silver catalyst, the alkaline earth metal promoter is selected from one or more of compounds of magnesium, calcium, strontium and barium, such as their oxides, oxalates, sulfates, acetates or nitrates, or a combination of any two or more of the foregoing compounds; preferably, the alkaline earth metal auxiliary agent is a barium and/or strontium compound; more preferably, the alkaline earth metal auxiliary agent is 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.
In the above silver catalyst preparation method, the rhenium promoter may be an oxide, perrhenic acid, perrhenate of rhenium, or a mixture of any two or more of the foregoing compounds; preferred rhenium promoters are perrhenic acid and perrhenates such as perrhenic acid, cesium perrhenate, ammonium perrhenate and the like.
According to some embodiments of the present invention, in the above method for preparing a silver catalyst, the rhenium co-promoter is selected from one or more of oxyanions in the form of salts or acids of cerium, sulfur, molybdenum, tungsten, and chromium.
In the present invention, the rhenium promoter and the co-promoter for the rhenium 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 and selectivity of the resulting silver catalyst can be further improved by adding a rhenium promoter and a co-promoter for the rhenium promoter.
In the above silver catalyst preparation method, 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-propanediamine, ethanolamine, or a mixture thereof; preferably, the organic amine compound is a mixture of ethylenediamine and ethanolamine.
According to some embodiments of the present invention, the method for preparing the silver catalyst comprises the steps of:
(1) impregnating the above porous alpha-alumina support with a solution of a sufficient amount of a silver compound, an organic amine compound, an alkali metal aid, an alkaline earth metal aid, a rhenium aid, and a co-aid of a rhenium aid;
(2) filtering to remove the impregnation solution, and drying the impregnated carrier;
(3) and (3) activating the impregnated carrier obtained in the step (2) in oxygen-containing mixed gas to prepare the silver catalyst.
In some specific embodiments of the present invention, firstly, the silver oxalate is dissolved by using the aqueous solution of ethylenediamine and ethanolamine to prepare a silver amine solution, and then the above-mentioned auxiliary agents are added to prepare a steeping liquor; 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 range of 180-700 ℃, preferably 200-500 ℃ for 0.5-120 minutes, preferably 1-60 minutes to prepare the finished product of the silver catalyst.
According to some embodiments of the present invention, the method for producing an epoxy compound by epoxidation of an olefin according to the fifth aspect of the present invention comprises placing the olefin in a reaction apparatus for epoxidation reaction in the presence of the silver catalyst described above or the silver catalyst prepared by the above method, and the reaction apparatus may be any apparatus capable of performing epoxidation reaction. The method for producing epoxy compounds by olefin epoxidation can also be understood as the application of the silver catalyst or the silver catalyst prepared by the method in the production of epoxy compounds by olefin epoxidation.
In some preferred embodiments of the invention, the olefin comprises one or more of styrene, propylene, ethylene, and 1, 3-butadiene.
The method for detecting the physical property of the alpha-alumina carrier and the performance of the silver catalyst comprises the following steps:
the specific surface area of the support is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.
The porosity, pore volume and pore structure distribution of the carrier are measured by mercury intrusion method. For example, the pore volume of the support can be determined using an AutoPore9510 model mercury porosimeter, a company mike, usa.
The term "crushing strength of an alpha-alumina carrier" refers to the lateral crushing strength of the alpha-alumina carrier, and can be obtained by randomly selecting 30 carrier samples and measuring the radial crushing strength and then averaging the samples by adopting a DL II type intelligent particle strength measuring instrument produced by the institute of chemical engineering and design of the great continuum, for example.
The term "water absorption" as used in the present invention refers to the volume of saturated adsorbed water per unit mass of the carrier, in mL/g. The measurement method is as follows: first, a certain amount of carrier (assuming its mass m) is weighed1) Boiling in boiling water for 1 hr, taking out the carrier, standing on wet gauze with moderate water content to remove excessive water on the surface of the carrier, and weighing the mass of the carrier after water adsorption (assuming that m is m)2) The water absorption of the carrier was calculated by the following formula.
Water absorption rate of (m)2-m1)/m1/ρWater (W)
Where ρ isWater (W)The density of water at temperature and atmospheric pressure was measured.
The selectivity of the silver catalyst is tested by a laboratory microreactor evaluation device. The reactor used in the microreactor evaluation apparatus was a stainless steel reaction tube having an inner diameter of 4mm, which was placed in a heating mantle. The filling volume of the catalyst is 1ml, and the lower part of the catalyst is provided with inert filler, so that a catalyst bed layer is positioned in a constant temperature area of the heating sleeve.
The conditions for measuring the activity and selectivity employed in the present invention are shown in Table 1.
TABLE 1 determination conditions for silver catalyst activity and selectivity
The reactor inlet and outlet gas compositions were continuously measured to stabilize to the above reaction conditions, the results were recorded and corrected for volume shrinkage, and the selectivity was calculated according to the following formula:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2The carbon dioxide concentration difference between the outlet gas and the inlet gas of the reactor is determined, and the average of more than 10 groups of test data is taken as the test result of the day.
Examples
In order that the invention may be readily understood, the invention will now be described in further detail with reference to the following examples; these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 100.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 50g of gibbsite with the particle size of 100 mu m to 300 mu m, 30g of petroleum coke with the particle size of 250 mu m to 800 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the components into a mixer, uniformly mixing, transferring the mixture into a kneader, adding dilute aqueous nitric acid solution 80g (nitric acid: water: 1:3, volume ratio) until kneading into paste capable of being extruded, putting the paste into a bar extruder, extruding into single-hole column, drying at 60-120 deg.C for 24 hr to reduce free water content to below 10%, and then placing the dried single-hole column into a natural gas kiln for roasting, wherein the roasting temperature is 1300 ℃, roasting at a constant temperature for 30 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) Preparation of the catalyst: adding 72g of ethylenediamine, 25.0g of ethanolamine and 110g of deionized water into a glass flask with a stirrer, slowly adding 159g of silver oxalate with 64% of silver content into an ammonium solution, continuously stirring to completely dissolve the silver oxalate, keeping the temperature of the mixed solution at 0-15 ℃, then sequentially adding 0.6g of cesium hydroxide, 0.4g of strontium sulfate, 0.5g of ammonium perrhenate, 0.5g of tungstic acid and 0.1g of lithium hydroxide into the mixed solution, adding deionized water to ensure that the total mass of the solution reaches 400g, and uniformly mixing to prepare an impregnation solution for later use.
A sample of 20g of the support was taken and placed in a glass vessel capable of being evacuated, the prepared impregnation solution was poured in, the support was completely immersed, evacuated to less than 10mmHg for about 15min, and then the excess solution was leached away. Finally, the impregnated carrier sample is placed in air at 320 ℃ for heating for 3min and cooled to prepare the silver catalyst.
The activity and selectivity of the catalyst samples were measured under the aforementioned process conditions using a microreactor (microreaction) evaluation apparatus, and the results of the microreaction evaluation are shown in Table 3.
Example 2:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 100.0g of diaspore with the particle size of 10 mu m to 100 mu m, 50g of diaspore with the particle size of 100 mu m to 300 mu m, 30g of petroleum coke with the particle size of 250 mu m to 800 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer, uniformly mixing the mixture, transferring the mixture into a kneader, adding dilute aqueous nitric acid solution 80g (nitric acid: water: 1:3, volume ratio) until kneading into paste capable of being extruded, putting the paste into a bar extruder, extruding into single-hole column, drying at 60-120 deg.C for 24 hr to reduce free water content to below 10%, and then placing the dried single-hole column into a natural gas kiln for roasting, wherein the roasting temperature is 1300 ℃, roasting at a constant temperature for 30 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 3:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10-100 mu m, 100.0g of monohydrate with the particle size of 10-100 mu m, 20g of gibbsite with the particle size of 100-300 mu m, 15g of monohydrate with the particle size of 100-300 mu m, 30g of petroleum coke with the particle size of 50-300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the gibbsite into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 80g of dilute aqueous solution of nitric acid (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a strip extruding machine, extruding the paste into a single-hole column, drying the paste at the temperature of 60-120 ℃ for 24 hours to reduce the free water content to below 10 percent, putting the dried single-hole column into natural gas, roasting the paste at the constant temperature of 1300 ℃ for 30 hours, and finally, cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 4:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 100.0g of monohydrate with the particle size of 10 mu m to 100 mu m, 140g of gibbsite with the particle size of 100 mu m to 300 mu m, 20g of petroleum coke with the particle size of 50 mu m to 300 mu m, 70g of petroleum coke with the particle size of 250 mu m to 800 mu m, 30.65g of ammonium fluoride, 15.12g of barium acetate, 5.0g of silicic acid and 90g of vaseline, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 90g of dilute nitric acid aqueous solution (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a strip extruder, extruding the paste into a single-hole column, drying the single-hole column for 24 hours at the temperature of 60 to 120 ℃ to reduce the free water content to below 10 percent, putting the dried single-hole column into a natural gas kiln for roasting at the constant temperature of 1300 ℃ for 30 hours, and finally cooling the mixture to the room temperature, to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 5:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 100.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 50g of gibbsite with the particle size of 100 mu m to 300 mu m, 30g of petroleum coke with the particle size of 250 mu m to 800 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of white oil, putting the components into a mixer, uniformly mixing, transferring the mixture into a kneader, adding dilute aqueous nitric acid solution 80g (nitric acid: water: 1:3, volume ratio) until kneading into paste capable of being extruded, putting the paste into a bar extruder, extruding into single-hole column, drying at 60-120 deg.C for 24 hr to reduce free water content to below 10%, and then placing the dried single-hole column into a natural gas kiln for roasting, wherein the roasting temperature is 1300 ℃, roasting at a constant temperature for 30 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 6:
(1) preparation of the carrier: weighing 40.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 10.0g of monohydrate with the particle size of 10 mu m to 100 mu m, 400g of gibbsite with the particle size of 100 mu m to 300 mu m, 100g of monohydrate with the particle size of 100 mu m to 300 mu m, 30g of petroleum coke with the particle size of 50 mu m to 300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 30g of white oil, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 80g of dilute aqueous solution of nitric acid (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into an extrudable paste, putting the paste into a strip extruder, extruding into a single-hole column, drying for 24 hours at the temperature of 60 to 120 ℃ to reduce the free water content to below 10 percent, putting the dried single-hole column into natural gas, roasting at the temperature of 1300 ℃ for 30 hours, finally cooling to the constant temperature in a kiln, to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 7:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10-100 mu m, 100.0g of monohydrate with the particle size of 10-100 mu m, 30g of gibbsite with the particle size of 100-300 mu m, 20g of monohydrate with the particle size of 100-300 mu m, 30g of petroleum coke with the particle size of 50-300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the gibbsite into a mixer, uniformly mixing, transferring the mixture into a kneader, adding dilute nitre and 80g (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a strip extruding machine, extruding the paste into a single-hole column, drying the paste at the temperature of 60-120 ℃ for 24 hours to reduce the free water content to below 10 percent, then putting the dried single-hole column into natural gas, roasting the paste at the temperature of 1300 ℃ for 30 hours, finally cooling the paste to the constant temperature in a kiln, to obtain the alpha-alumina carrier. The measured physical properties of the carrier are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 8:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10 mu m to 100 mu m, 100.0g of monohydrate with the particle size of 10 mu m to 100 mu m, 50g of gibbsite with the particle size of 100 mu m to 300 mu m, 20g of petroleum coke with the particle size of 250 mu m to 800 mu m, 10g of petroleum coke with the particle size of 50 mu m to 300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 80g of dilute nitric acid aqueous solution (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a strip extruder, extruding the paste into a single-hole column, drying the single-hole column for 24 hours at the temperature of 60 to 120 ℃ to reduce the free water content to below 10 percent, putting the dried single-hole column into a natural gas kiln for roasting at the constant temperature of 1300 ℃ for 30 hours, and finally cooling the mixture to the room temperature, to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Example 9:
(1) preparation of the carrier: weighing 150.0g of gibbsite with the particle size of 10-100 mu m, 150.0g of monohydrate with the particle size of 10-100 mu m, 150g of gibbsite with the particle size of 100-300 mu m, 150g of monohydrate with the particle size of 100-300 mu m, 10g of petroleum coke with the particle size of 50-300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 90g of dilute aqueous solution of nitric acid (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a strip extruding machine, extruding the paste into a single-hole column, drying the paste for 24 hours at the temperature of 60-120 ℃ to reduce the free water content to below 10 percent, then putting the dried single-hole column into natural gas, roasting the paste at the constant temperature of 1300 ℃ for 30 hours, and finally, cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 1:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10-100 microns, 100.0g of monohydrate with the particle size of 10-100 microns, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 90g of dilute nitric acid aqueous solution (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a bar extruder, extruding the paste into a single-hole column, drying for 24 hours at the temperature of 60-120 ℃ to reduce the free water content to below 10%, then putting the dried single-hole column into a natural gas kiln for roasting at the roasting temperature of 1300 ℃, roasting for 30 hours at constant temperature, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 2:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10-100 microns, 500.0g of monohydrate with the particle size of 10-100 microns, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer, uniformly mixing, transferring the mixture into a kneader, adding 90g of dilute nitric acid aqueous solution (nitric acid: water: 1:3, volume ratio) until the mixture is kneaded into paste which can be extruded, putting the paste into a bar extruder, extruding the paste into a single-hole column, drying for 24 hours at the temperature of 60-120 ℃ to reduce the free water content to below 10%, then putting the dried single-hole column into a natural gas kiln for roasting at the roasting temperature of 1300 ℃, roasting for 30 hours at constant temperature, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 3:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 10-100 mu m, 100.0g of monohydrate with the particle size of 10-100 mu m, 600g of monohydrate with the particle size of 100-300 mu m, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the mixture into a mixer to be uniformly mixed, transferring the mixture into a kneader, adding 90g of dilute nitric acid aqueous solution (nitric acid: water is 1:3 in volume ratio) until the mixture is kneaded into paste capable of being extruded and formed, putting the paste into a bar extruder to be extruded into a single-hole column, drying the single-hole column at the temperature of 60-120 ℃ for 24 hours to reduce the free water content to below 10%, then putting the dried single-hole column into a natural gas kiln to be calcined, the calcination temperature is 1300 ℃, the constant-temperature calcination is carried out for 30 hours, and finally cooling to the room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
Comparative example 4:
(1) preparation of the carrier: weighing 400.0g of gibbsite with the particle size of 100-300 microns, 100.0g of monohydrate with the particle size of 100-300 microns, 6.33g of ammonium fluoride, 4.15g of barium acetate, 1.0g of silicic acid and 10g of vaseline, putting the materials into a mixer, uniformly mixing, transferring the materials into a kneader, adding 90g of dilute nitric acid aqueous solution (nitric acid: water: 1:3, volume ratio) until the materials are kneaded into paste which can be extruded, putting the paste into a bar extruder, extruding the paste into a single-hole column, drying for 24 hours at the temperature of 60-120 ℃ to reduce the free water content to below 10%, then putting the dried single-hole column into a natural gas kiln for roasting at the roasting temperature of 1300 ℃, roasting for 30 hours at constant temperature, and finally cooling to room temperature to obtain the alpha-alumina carrier. The measured carrier physical property data are shown in Table 2.
(2) The catalyst was prepared as in example 1, and the results of the micro-reverse evaluation are shown in Table 3.
TABLE 2 physical Properties of the vectors
TABLE 3 Properties of the catalysts
| Sources of catalyst | Reaction temperature (. degree.C.) | Selectivity (%) |
| Example 1 | 225.0 | 83.6 |
| Example 2 | 224.6 | 83.3 |
| Example 3 | 224.4 | 83.2 |
| Example 4 | 228.5 | 84.2 |
| Example 5 | 226.0 | 83.5 |
| Example 6 | 227.1 | 84.3 |
| Example 7 | 225.2 | 83.4 |
| Example 8 | 225.8 | 83.5 |
| Example 9 | 224.2 | 83.9 |
| Comparative example 1 | 235.5 | 82.2 |
| Comparative example 2 | 240.1 | 82.1 |
| Comparative example 3 | 241.2 | 81.9 |
| Comparative example 4 | 239.2 | 82.2 |
The specific surface area of the carriers of the above examples 1 to 9 was 1.0 to 2.0m2The crushing strength is 100-200N/particle, the water absorption rate is more than or equal to 50 percent, the pore volume is 0.4-0.7ml/g, the pores with the pore diameter of less than 5 mu m and less than 0.1 mu m are distributed in the range of 40-60 percent, the pores with the pore diameter of less than 10 mu m and less than 5 mu m and less than 10-40 percent, and the pores with the pore diameter of more than or equal to 10 mu m and less than 1-10 percent. The specific surface area of the carriers of the above comparative examples 1 to 4 was 1.0 to 2.0m2The crushing strength is 100-200N/particle, the water absorption is less than or equal to 50 percent, the pore volume is less than 0.4ml/g, the pores with the pore diameter of less than 5 mu m and less than or equal to 0.1 mu m in pore distribution account for more than or equal to 60 percent, and the pores with the pore diameter of less than 10 mu m and less than or equal to 5 mu m account for 10-40 percent.
As can be seen from table 2, the silver catalysts prepared using the carriers described in examples 1 to 9 all had higher selectivity than the silver catalysts prepared using the carriers described in comparative examples 1 to 4, and the reaction temperature was lower, indicating that the silver catalysts prepared using the carriers described in examples 1 to 9 had better selectivity and activity than the silver catalysts prepared using comparative examples 1 to 4. Wherein, the addition of the component b, namely 100-300 μm gibbsite and 100-300 μm diaspore, is beneficial to increasing macropores, the occurrence of macropores is beneficial to diffusion, so that the selectivity of the catalyst is improved, the selectivity is improved but the temperature is increased if the dosage is too much, the selectivity is not obviously improved if the dosage is too low, the selectivity and the activity are balanced, and the dosage of the granularity has an optimal range.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (16)
1. An alpha-alumina carrier prepared by forming, drying and calcining an alpha-alumina carrier precursor mixture, wherein the alpha-alumina carrier precursor mixture comprises, based on the total weight of the total ingredients:
component a, aluminum hydroxide with the particle size of less than 100 mu m and less than or equal to 10 mu m, 1 to 90 weight percent;
component b, 100 mu m or less aluminum hydroxide with the granularity less than 300 mu m, 1 to 90 weight percent;
component c, 0-10 wt% of carbon-containing combustible material with the particle size less than 800 μm and less than or equal to 250 μm; and/or carbonaceous combustible material with particle size less than 300 μm and less than or equal to 50 μm, 0-10 wt%;
component d, C15-C401 to 10 weight percent of mixture of high-carbon alkane and high-carbon alkene;
component e, mineralizer, 0.1 wt% -5.0 wt%;
0.1-10 wt% of component f, alkaline earth metal compound;
component g, silicon-containing compound, 0.1 wt% -5.0 wt%;
component h, adhesive, 1-10 wt%; and
component i, water, and the balance;
wherein, the amount of the carbon-containing combustible material with the grain size of more than or equal to 250 mu m and less than 800 mu m and the amount of the carbon-containing combustible material with the grain size of more than or equal to 50 mu m and less than 300 mu m in the component c are not 0 percent at the same time;
the aluminum hydroxide in the component a is gibbsite and diaspore, and the weight ratio of the gibbsite to the diaspore is (1-10): 1.
2. The alpha-alumina carrier as claimed in claim 1, wherein component c is a carbonaceous combustible of 250 μm or less and a particle size < 800 μm and a carbonaceous combustible of 50 μm or less and a particle size < 300 μm, the weight ratio of the carbonaceous combustible of 250 μm or less and the particle size < 800 μm and the carbonaceous combustible of 50 μm or less and a particle size < 300 μm being (10-1): 1; and/or the aluminium hydroxide of component b is gibbsite and/or diaspore.
3. The alpha-alumina carrier as claimed in claim 1, wherein the aluminum hydroxide in component a is gibbsite and diaspore in a weight ratio of (1-5) to 1.
4. The α -alumina support according to any one of claims 1 to 3, wherein the aluminum hydroxide in component b is gibbsite and diaspore in a weight ratio of gibbsite to diaspore of (1-10): 1.
5. The alpha-alumina carrier as set forth in claim 4, wherein the aluminum hydroxide in component b is gibbsite and diaspore in a weight ratio of (1-5): 1.
6. An α -alumina support according to any one of claims 1 to 3, wherein the weight ratio of component a to component b is from 0.1 to 15.
7. The α -alumina support according to claim 6, wherein the weight ratio of component a to component b is 0.1 to 10.
8. The alpha-alumina carrier according to any one of claims 1 to 3,
the mixture of C15-C40 high-carbon alkane and high-carbon alkene is a lubricating lipid substance; and/or
The alkaline earth metal compound comprises one or more of oxide, nitrate, sulfate, carbonate, oxalate and chloride of alkaline earth metal; and/or
The mineralizer is fluoride;
the silicon-containing compound comprises one or more of silicon-containing oxide and silicic acid compound;
the carbonaceous combustible comprises petroleum coke and/or graphite;
the weight ratio of the binder to the water is 1 (1.25-10); the binder comprises one or more of citric acid, nitric acid, hydrochloric acid, formic acid, acetic acid and propionic acid.
9. The alpha-alumina carrier according to claim 8,
the mixture of C15-C40 high-carbon alkane and high-carbon alkene is one or more of white oil and vaseline; and/or
The alkaline earth metal is magnesium and/or barium; and/or
The mineralizer comprises one or more of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride;
the silicon-containing compound is one or more of sodium silicate, calcium silicate, zirconium silicate, silicic acid and silicon oxide.
10. An alpha-alumina carrier as claimed in any one of claims 1 to 3, wherein the specific surface area of the alpha-alumina carrier is in the range of 0.8 to 3.0m2(ii)/g; the pore volume is 0.4-0.7 ml/g; water absorptionThe rate is more than or equal to 50 percent; the crushing strength is 50-200N/grain; based on the total pore volume, the pores with the pore diameter of less than 5 μm and less than 0.1 μm account for 40-80%, the pores with the pore diameter of less than 10 μm and less than 5 μm account for 1-40%, and the pores with the pore diameter of more than 10 μm account for 0.1-10%.
11. A method of preparing an alpha-alumina support as claimed in any one of claims 1 to 10, which comprises:
step S1, mixing the components a-i to form an alpha-alumina carrier precursor mixture;
and step S2, forming the alpha-alumina carrier precursor mixture, drying and roasting to obtain the alpha-alumina carrier.
12. The preparation method as claimed in claim 11, wherein in step S2, the roasting temperature is 1200-1500 ℃; and/or the roasting time is 10-50 h.
13. A silver catalyst for the epoxidation of olefins to produce epoxides, comprising the following components, based on the total weight of the catalyst:
component i, an α -alumina support as defined in any one of claims 1 to 10 or an α -alumina support prepared by a process as defined in claim 11 or 12;
14. a method for preparing a silver catalyst for producing an epoxy compound by olefin epoxidation, which comprises the steps of immersing the alpha-alumina carrier according to any one of claims 1-10 or the alpha-alumina carrier prepared by the method according to claim 11 or 12 in a solution of a silver compound, an organic amine compound and an auxiliary agent, and then carrying out filtration and activation heat treatment to obtain the silver catalyst; the promoter comprises an alkali metal promoter, an alkaline earth metal promoter, an optional rhenium promoter and an optional rhenium co-promoter.
15. A process for the epoxidation of an olefin to produce an epoxide, the epoxidation being carried out in the presence of a silver catalyst as claimed in claim 13 or a silver catalyst prepared by a process as claimed in claim 14.
16. The method of claim 15, wherein the olefin comprises one or more of styrene, propylene, ethylene, and 1, 3-butadiene.
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| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN106622195A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alpha- alumina supporter and preparation method thereof and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN103372466A (en) * | 2012-04-25 | 2013-10-30 | 中国石油化工股份有限公司 | Preparation method of silver catalyst carrier for production of ethylene oxide and application thereof |
| CN106622195A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alpha- alumina supporter and preparation method thereof and application |
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