CN109499558A - A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process - Google Patents
A kind of alpha-alumina supports, silver catalyst and olefin epoxidation process Download PDFInfo
- Publication number
- CN109499558A CN109499558A CN201710832849.9A CN201710832849A CN109499558A CN 109499558 A CN109499558 A CN 109499558A CN 201710832849 A CN201710832849 A CN 201710832849A CN 109499558 A CN109499558 A CN 109499558A
- Authority
- CN
- China
- Prior art keywords
- alpha
- alumina
- alumina supports
- silver
- silver catalyst
- 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 162
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 79
- 239000004332 silver Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 11
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 19
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- -1 oxygen anion Chemical class 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 229910001680 bayerite Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 229910000765 intermetallic Inorganic materials 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 23
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 7
- 241000446313 Lamella Species 0.000 abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 20
- 239000012752 auxiliary agent Substances 0.000 description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000036314 physical performance Effects 0.000 description 6
- 229940100890 silver compound Drugs 0.000 description 6
- 150000003379 silver compounds Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000004438 BET method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000001404 mediated effect Effects 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
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
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- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to catalyst fields, disclose a kind of alpha-alumina supports, silver catalyst and olefin epoxidation process, the alpha-alumina supports are prepared by a method comprising the following steps: step S1, prepare the solid, powdery object with following component: compound phase alumina, boehmite, alkaline earth metal compound and the gibbsite optionally contained, fluorochemical, the solid, powdery object is mixed with binder and water, obtains mixture；The resulting mixture of step S1 is formed, obtains formed body by step S2；The resulting formed body of step S2 is dried and is roasted by step S3.Alpha-alumina supports of the invention have suitable surface area and pore structure, small and thick spherical apparent form is presented in particle, different from the alpha-alumina supports of lamella pattern, thus the silver catalyst of carrier preparation shows good selectivity and stability in epoxidation reaction of olefines, and activity does not reduce.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of alpha-alumina supports, and the silver catalyst being made from it
And its application.More particularly, it relates to a kind of α-for alkene epoxidation production epoxide silver catalyst
Alumina support and the silver catalyst as made from the carrier, further relate to the olefin epoxidation process using this catalyst.
Background technique
Ethylene oxide is the derivative of ethylene, and as one of epoxide, it is not only important organic chemical industry
Raw material, the status in ethene derivatives are only second to polyethylene, polyvinyl chloride, mainly for the production of ethylene glycol, and epoxy second
Alkane is a kind of very important fine chemical material, and it is more can to derive nonionic surfactant, ethanol amine, glycol ether etc.
Kind fine chemical product, and then produce detergent, emulsifier, antifreeze, plasticizer, lubricant, four or five thousand kinds of agrochemical productions
Product.
So far, silver catalyst is still unique effective catalyst of industrial ethylene epoxidizing production ethylene oxide.
In the prior art, silver catalyst is also usually co-deposited on carrier with one or more with it other than including silver-colored ingredient
For improve silver catalyst catalytic performance other elements, carrier usually by it is resistant to high temperature, there is suitable specific surface and hole to tie
The Alpha-alumina of structure forms.Ethylene mainly generates ethylene oxide under silver catalyst effect, while side reaction generation occurs
Carbon dioxide and water, wherein activity, selectivity and stability are the main performance index of silver catalyst.So-called activity refers to epoxy
Ethane production process reaches reaction temperature required when certain reaction load.Reaction temperature is lower, and the activity of catalyst is higher.Institute
Meaning 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.So-called stabilization
Property is then expressed as the fall off rate of activity and selectivity, and the stability of fall off rate more small catalyst is better.In ethylene oxy metaplasia
Economic effect can be greatly improved using high activity, silver catalyst that is highly selective and having good stability during production ethylene oxide
Benefit, therefore manufacture high activity, highly selective and good stability " three high " silver catalyst are the main sides of silver catalyst research
To.However, it is generally the case that the activity and selectivity of silver catalyst mutually restricts.The performance of silver catalyst is removed and is catalyzed
The composition and preparation method of agent have outside important relationship, and the performance and preparation method of the carrier also used with catalyst have important pass
System.
A kind of preparation method of alpha-alumina supports, including mixing industry α-three water oxygen are disclosed in CN102133544A
Aluminium, a false water aluminium oxide, 0-30% burn out pore forming material, the alkali salt of 0-2.5%, the fluoride of 0-3%, bonding
Agent and water, the percentage are based on the gross mass of raw alumina, wherein the weight of α-gibbsite and a false water aluminium oxide
Ratio is measured as 1-4:1, the total amount of binder and water is the 15-30% of alumina raw material total weight；Then pass through extrusion forming, drying
The alpha-alumina supports are obtained with roasting.In the method, using the oxidation for burning out carbonaceous material release of 0-30%
Carbon and/or carbon dioxide gas carry out reaming.
US4410453 discloses a kind of alpha-alumina supports containing zinc, lanthanum, magnesium elements, these elements are prepared in carrier
It is added in a manner of aluminium oxide or oxide precursor in the process, which is used for used in ethylene production ethylene oxide
Silver catalyst, the silver catalyst for introducing zinc oxide, lanthana or magnesia preparation in the carrier has preferable activity and choosing
Selecting property.Alkaline-earth metal, silicon, zirconium are added by US5100859, US5145824, EP0900126, US5801259, US5733842 etc.
Alpha-alumina manufactures carrier, the preferred calcium of alkaline-earth metal, and strontium and barium salt are used together with the compound of zirconium, and the silver of carrier preparation is urged
Agent has preferable selectivity.
Although above patent document is improved in terms of improving alpha-alumina supports and addition carrier auxiliary agent respectively, and
And the catalytic performance of the silver catalyst of preparation is improved, still, there is still a need for catalyzing expoxidation of olefines performance is more preferable for this field
Alumina support silver catalyst corresponding with its, especially preparation process environmental protection and not reducing silver catalyst it is active
In the case of, still there is the silver catalyst of selectivity and stability very well.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of existing technologies, a kind of alpha-alumina supports are provided, with the α-oxygen
Change a kind of silver catalyst that alumina supporter is carrier, and the olefin epoxidation process using this catalyst.α-oxygen of the invention
Change alumina supporter in load silver and preferably load after silver catalyst is made in various active components, the silver catalyst is anti-in alkene epoxidation
Good selectivity and stability are shown in answering, and activity does not reduce.
In view of the situation of the above-mentioned prior art, the present inventor has carried out extensively in improvement silver catalyst performances areas
General, in-depth study, the study found that in carrier preparation process with compound phase alumina replace pore creating material (such as can after-flame moisten
Slide material) and a variety of expensive auxiliary agent preparation alpha-alumina supports, which has suitable surface area and pore structure, different from piece
Small and thick spherical apparent form is presented in the alpha-alumina supports of layer pattern, alpha aluminium oxide particle of the invention, thus carrier
The silver catalyst of preparation shows good selectivity and stability in epoxidation reaction of olefines, and activity does not reduce.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of alpha-alumina supports, the alpha-oxidation
Alumina supporter is prepared by a method comprising the following steps:
Step S1 prepares the solid, powdery object with following component: compound phase alumina, boehmite, alkaline-earth metal
The solid, powdery object is mixed with binder and water, is obtained by compound and the gibbsite optionally contained, fluorochemical
To mixture；
The resulting mixture of step S1 is formed, obtains formed body by step S2；
The resulting formed body of step S2 is dried and is roasted, the alpha-alumina supports are made by step S3；
The alpha-alumina supports have spherical apparent form.
The second aspect of the present invention provides a kind of alkene epoxidation silver catalyst, and the silver catalyst includes carrier and bears
Carry active component silver on this carrier, wherein the carrier is alpha-alumina supports provided by the invention.
The third aspect of the present invention provides a kind of olefin epoxidation process, wherein this method includes by alkene in the present invention
Epoxidation reaction of olefines is carried out under the action of alkene epoxidation silver catalyst, obtains epoxide.
There is alpha-alumina supports of the invention suitable surface area and pore structure, particle small and thick spherical table is presented
Pattern is seen, different from the alpha-alumina supports of lamella pattern, thus the silver catalyst of carrier preparation is in epoxidation reaction of olefines
Good selectivity and stability are shown, and activity does not reduce.In addition, preparation process environmental protection of the invention, material at
This is low.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Exemplary embodiment of the invention is described in more detail in conjunction with the accompanying drawings.
Fig. 1 is according to a kind of electron microscope of the alpha-alumina supports of preferred embodiment of the present invention.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the present invention, the alpha-alumina supports are prepared by a method comprising the following steps:
Step S1 prepares the solid, powdery object with following component: compound phase alumina, boehmite, alkaline-earth metal
The solid, powdery object is mixed with binder and water, is obtained by compound and the gibbsite optionally contained, fluorochemical
To mixture；
The resulting mixture of step S1 is formed, obtains formed body by step S2；
The resulting formed body of step S2 is dried and is roasted, the alpha-alumina supports are made by step S3；
The alpha-alumina supports have spherical apparent form.
In the present invention, " optionally containing " refers to and can contain in the mixture, can also not contain.
According to the present invention, the compound phase alumina include gama-alumina, θ-aluminium oxide, κ-aluminium oxide, η-aluminium oxide and
At least two in Alpha-alumina.Under preferable case, the compound phase alumina is the compound phase as made of Aluminium hydroxide roasting
Aluminium oxide, it is further preferred that the compound phase alumina is to roast aluminium hydroxide at 750-1100 DEG C to obtain, the aluminium hydroxide
Preferably zirlite and/or bayerite.
According to the present invention, it is suitable for although can prepare to have using compound phase alumina when preparing alpha-alumina supports
Surface area and pore structure the alpha aluminium oxide particle of small and thick spherical apparent form is presented, however, it is preferred in the case of, from into
From the point of view of one step improves the performance of the alpha-alumina supports, a preferred embodiment according to the present invention, with described
In mixture on the basis of the total weight of solid component, the content of the compound phase alumina is 1-70 weight %, preferably 5-40
Weight %, further preferably 8-30 weight %.
According to the present invention, in order to further improve the performances of alpha-alumina supports, during preparing alpha-alumina supports
It is additionally added alkaline earth metal compound.The alkaline earth metal compound is preferably selected from the oxide, sulfate, nitric acid of strontium and/or barium
One of salt, acetate and oxalates are a variety of.On the basis of the total weight of the solid, powdery object, the alkaline-earth metal
The content for closing object is preferably 0.1-5 weight %.
In the present invention, the gibbsite is the component optionally contained, is preferably selected from promise diaspore, zirlite and three
One of zirlite is a variety of.A preferred embodiment according to the present invention, the gibbsite and intends thin water aluminium
The weight ratio of stone is 0-4:1.Catalyst made from carrier containing the gibbsite in above range has better choice
Property and stability.
According to the present invention, it for the crystal transfer of accelerated oxidation aluminium, is additionally added and contains during preparing alpha-alumina supports
Fluorine compounds.Fluorochemical of the present invention is preferably selected from one of hydrogen fluoride, ammonium fluoride, magnesium fluoride and lithium fluoride or more
Kind.On the basis of the total weight of the solid, powdery object, the content of the fluorochemical is preferably 0-3 weight %.
It is usually added into binder during preparing alpha-alumina supports, it is raw with the boehmite in solid, powdery object
At Aluminum sol, each component is bonded together, becomes extrudable molding paste.The binder include citric acid, nitric acid,
One of hydrochloric acid, formic acid and acetic acid are a variety of, more preferably nitric acid, can also be all or part of by binder and boehmite
It is replaced with Aluminum sol.Preferably, the weight ratio of the binder and water is 1:1-10；The total weight of the binder and water and solid
The weight ratio of body powder is 1:2-10.
According to the present invention, in step S1, the preparation method of mixture is known to those skilled in the art, for example, will answer
Conjunction phase alumina, gibbsite, alkaline earth metal compound, fluorochemical, which are uniformly mixed, obtains solid, powdery object, adds
Binder and water obtain mixture.
According to the present invention, the method that formed body is obtained in step S2 can be carried out according to the ordinary skill in the art.Wherein,
The shape of formed body can be annular, spherical, cylindricality or porous column shape.Wherein, solid, powdery object obtains after binder and water is added
It is mediated, is mediated can be to carry out in kneader, kneading time can be 20-60min, pinch into extrudable to mixture
Molding paste, paste form in molding machine, become single hole or porous cylindrical object.
According to the present invention, in the step S3, dry and roasting method can be carried out with reference to the usual manner of this field.
Under preferable case, the formed body can dry to containing 10 weight % of free water hereinafter, drying temperature can be done for 20-100 DEG C
The dry time controls according to moisture content at 20-48 hours.The time of roasting can be 2-48 hours, and maturing temperature can be
1200-1500℃。
The alumina support of the invention have the feature that Alpha-alumina component account for the percentage of total weight of carrier >=
98%, specific surface 0.5-3.5m2/ g, Kong Rongwei 0.3-1.0mL/g, most probable pore size are 0.1-30.0 μm, water absorption rate >=
40%, crushing strength be 30-400N/, preferably 40-300N/, further preferably 120-250N/, most preferably
150-230N/.
In the present invention, the side crush intensity of alumina support uses II type intelligence detector for strength of particles of DL, chooses
Support samples are averaged to obtain after measuring radial crushing strength；Water absorption rate is measured by densimetry；Specific surface area uses nitrogen
The measurement of physical absorption BET method；Pore size distribution is using pressure mercury method measurement.
According to another aspect of the present invention, described the present invention also provides a kind of alkene epoxidation silver catalyst
Silver catalyst includes the active component silver of carrier and load on this carrier, wherein the carrier is α-oxygen provided by the invention
Change alumina supporter.
A kind of preferred embodiment according to the present invention, the silver catalyst also contain:
Alkali metal and/or alkaline-earth metal or compound based on alkali metal and/or alkaline-earth metal；
Rhenium metal and/or compound based on rhenium；And
Optionally, the coassist agent element of rhenium, selected from cerium, sulphur, molybdenum, chromium, salt or sour form one of oxygen anion or
It is a variety of.
After preparing alpha-alumina supports of the invention, those skilled in the art can be by known methods or any normal
Rule mode prepares silver catalyst of the invention.As usually with the organic amine containing sufficient amount, silver compound, alkali metal promoter, alkali
The solution of the coassist agent of earth metal auxiliary agent, optional rhenium auxiliary agent and rhenium auxiliary agent impregnates above-mentioned alpha-alumina supports.
A preferred embodiment according to the invention, the silver catalyst are prepared by method comprising the following steps
It obtains: I) with the organic amine containing sufficient amount, silver compound, alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium
The solution of the coassist agent of auxiliary agent impregnates the alpha-alumina supports of method preparation according to the present invention；II) leaching maceration extract；
III) to step II in oxygen-containing gas) resulting carrier activates, the silver catalyst is made.
In the present invention, during preparing silver catalyst, organic amine is added to be formed with silver compound
Argent-amine complex.The organic amine can be selected from 1,2- propane diamine, 1,3- propane diamine, ethylenediamine, 1,2- butanediamine, 1,3- fourth
Diamines, pyridine, ethamine, n-propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, ethanol amine, Propanolamine and butanol
One of amine is a variety of.
In silver catalyst preparation process, the silver compound can be selected from one in silver oxide, silver nitrate and silver oxalate
Kind is a variety of, and the quality of the silver element accounts for the 10-40% of the silver catalyst quality.
In the present invention, the alkali metal promoter can be selected from one of lithium, sodium, potassium, rubidium, caesium or a variety of, and described
The quality of alkali metal promoter accounts for the 5-2000ppm of the silver catalyst quality.
In the present invention, the base earth metal promoter can be selected from one of magnesium, calcium, strontium, barium or a variety of, and the alkali
The quality of earth metal auxiliary agent accounts for the 5-20000ppm of the silver catalyst quality.
In the present invention, the rhenium auxiliary agent can be selected from one of rheium oxide, ammonium perrhenate, perrhenic acid and perrhenic acid caesium
Or it is a variety of, and the quality of the rhenium auxiliary agent accounts for the 50-10000ppm of the silver catalyst quality.
In the present invention, the coassist agent of the rhenium auxiliary agent can be by the oxygen anion in the form of selected from cerium, sulphur, molybdenum, chromium, salt or acid
One of or it is a variety of.
In silver catalyst preparation process of the invention, in order to use the organic amine containing sufficient amount, silver compound, alkali metal
Auxiliary agent, base earth metal promoter, optional rhenium auxiliary agent and rhenium auxiliary agent the solution of coassist agent be sufficiently impregnated method of the present invention
The alpha-alumina supports of preparation usually impregnate alpha-alumina supports under conditions of vacuum degree is less than 10mmHg, and dip time is
5-60min.Leaching maceration extract after dipping, then live in the nitrogen oxygen atmosphere of air or oxygen content no more than 21% volume
Change, activation temperature is 150-400 DEG C, activation time 1-120min.
In the present invention, in order to prepare silver catalyst of the invention, can make first silver nitrate aqueous solution and ammonium oxalate or
Silver oxalate precipitate is precipitated in oxalic acid aqueous solution reaction, and filtering is washed with deionized, and up to the presence of no nitrate ion, then will
Silver oxalate is added in the aqueous solution of organic amine, is added alkali metal promoter, base earth metal promoter, optional rhenium auxiliary agent and rhenium and is helped
The coassist agent of agent, is made into maceration extract, and the alpha-alumina supports of the method for the invention preparation, leaching leaching are impregnated with gained maceration extract
Stain liquid, activation, is finally made the silver catalyst.
In order to obtain the silver catalyst compared with high silver content and/or auxiliary agent content, the present invention can pass through one or many leachings
The method of stain prepares silver-containing catalyst.
Alkali metal, alkaline-earth metal, rhenium auxiliary agent and coassist agent of rhenium for adding in silver catalyst preparation process of the present invention etc. help
Agent can deposit on carrier prior to, concurrently with, or after immersion silver, can also deposit after silver compound is activated reduction
On carrier.
According to another aspect of the present invention, the present invention also provides a kind of olefin epoxidation process, wherein this method
Including alkene is carried out epoxidation reaction of olefines under the action of silver catalyst of the present invention, epoxide is obtained.Its
In, the alkene may include one of styrene, propylene, ethylene and 1,3-butadiene or a variety of.Wherein, alkene epoxidation
Reaction unit can be any device that can carry out epoxidation reaction.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Below with reference to embodiment, the invention will be further described, but the scope of the invention is not limited to these implementations
Example.
The measurement of silver catalyst catalytic performance:
Various silver catalysts of the invention test its activity and selectivity using laboratory microreactor evaluating apparatus.It is micro-
Reactor used in type reactor evaluations device is the stainless steel reaction pipe of internal diameter 4mm, and reaction tube is placed in heating mantle.Catalysis
The admission space of agent 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 for the activity and selectivity that the present invention uses such as table 1.
Table 1
After stably reaching above-mentioned reaction condition, METHOD FOR CONTINUOUS DETERMINATION reactor inlet and exit gas composition.Measurement result into
Selectivity is calculated as follows after the correction of row volume contraction:
Selectivity
Wherein Δ EO is reactor outlet gas and inlet gas ethylene oxide concentration difference, Δ CO2Reactor outlet gas with
Gas concentration lwevel is poor in inlet gas, takes test result of the average of 10 groups or more test datas as the same day.
In the following embodiments, the side crush intensity of alumina support uses II type intelligence detector for strength of particles of DL,
Alumina support sample is chosen, is averaged to obtain after measuring radial crushing strength；Water absorption rate is measured by densimetry；Specific surface
Product is measured using nitrogen physisorption BET method；Pore size distribution is using pressure mercury method measurement.
Embodiment 1
(1) preparation of carrier:
Zirlite is roasted under the conditions of 950 DEG C, 10h, obtains gama-alumina, the compound phase alumina of κ-aluminium oxide, is claimed
The compound phase alumina of 100g is taken, 360.0g zirlite, 240.0g boehmite, 8.0g ammonium fluoride, 5.0g barium sulfate are put into
It is uniformly mixed, is transferred in kneader in blender, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into and can squeeze
Molding paste out, pastes placed into banded extruder, is extruded into seven apertures in the human head column, dries more than for 24 hours, makes at 60-120 DEG C
Free water content is reduced to 10 weight % hereinafter, then roasting dried seven apertures in the human head column, and maturing temperature is 1350 DEG C, permanent
Temperature roasting 10h, is finally cooled to room temperature, obtains alpha-alumina supports.The alpha-alumina supports of the embodiment 1 preparation, which are numbered, is
Scar-1, related physical performance data are shown in Table 2, and electromicroscopic photograph is shown in Fig. 1, as seen from Figure 1, alpha aluminium oxide particle of the invention
Small and thick spherical apparent form is presented, different from the lamella pattern of alpha-alumina supports in the prior art.
(2) preparation of catalyst:
It weighs 140g silver nitrate to be dissolved in 150ml deionized water, weighs 64g ammonium oxalate and be dissolved in 520ml deionized water, obtain
To silver nitrate solution and ammonium oxalate solution, two kinds of solution are mixed with vigorous stirring, generate white silver oxalate precipitate, and aging 30 divides
More than clock, filtering is washed with deionized and is precipitated to no nitrate ion.Filter cake argentiferous about 60%, aqueous about 15%.It is stirred in band
Add 60g ethylenediamine in the glass flask mixed, 22g ethanol amine, mixed liquor is made in 75g deionized water, silver oxalate paste obtained
Object is slowly added into mixed liquor, and lasting stirring dissolves silver oxalate all, and the additional amount of silver oxalate makes maceration extract argentiferous obtained
22% (quality), then sequentially adds 0.35g cesium acetate, 0.50g barium acetate, 0.70g ammonium perrhenate, then plus deionized water make it is molten
Liquid gross mass reaches 400g, is uniformly mixed that dipping solution is made is stand-by.20g Scar-1 carrier is taken to be put into the container that can be vacuumized
In, the dipping solution prepared is poured into, carrier is submerged, is evacuated to lower than 10mmHg, keeps about 30min, leaching is removed extra
Solution.Finally the carrier after dipping is placed in 300 DEG C of air and heats 3min, it is cooling, that is, silver catalyst is made.
(3) catalyst performance evaluation:
The different times of catalyst sample made of being measured under the conditions of previous process using microreactor evaluating apparatus
Activity and selectivity, test result are listed in table 3.
Embodiment 2
(1) preparation of carrier:
Zirlite is roasted under the conditions of 1080 DEG C, 10h, obtains θ-aluminium oxide, the compound phase alumina of κ-aluminium oxide, is claimed
This compound phase alumina of 60g is taken to replace the compound phase alumina in embodiment 1, the other the same as in Example 1.The embodiment 2 preparation
Alpha-alumina supports number is Scar-2, and related physical performance data is shown in Table 2.
(2) preparation of catalyst:
It is identical as the silver catalyst preparation method in embodiment 1, only its Alpha-alumina is accordingly revised as making in embodiment 2
The alpha-alumina supports that standby number is Scar-2.
(3) evaluation of silver catalyst catalytic performance:
When measuring catalyst difference under the conditions of previous process using microreactor evaluating apparatus to manufactured catalyst
The activity and selectivity of phase, test result are listed in table 3.
Embodiment 3
(1) preparation of carrier:
Bayerite is roasted under the conditions of 900 DEG C, 10h, obtains the compound phase alumina of θ-aluminium oxide, Alpha-alumina, is claimed
The compound phase alumina of 200g, 360.0g zirlite, 240.0g boehmite, 8.0g ammonium fluoride, 5.0g barium sulfate are taken, is put into
It is uniformly mixed, is transferred in kneader in blender, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into and can squeeze
Molding paste out, pastes placed into banded extruder, is extruded into seven apertures in the human head column, dries more than for 24 hours, makes at 60-120 DEG C
Free water content is reduced to 10% hereinafter, then roasting dried seven apertures in the human head column, and maturing temperature is 1200 DEG C, constant temperature roasting
10h is burnt, room temperature is finally cooled to, obtains alpha-alumina supports.The alpha-alumina supports number of the embodiment 3 preparation is Scar-
3, related physical performance data is shown in Table 2.
(2) preparation of catalyst:
It is identical as the silver catalyst preparation method in embodiment 1, only its Alpha-alumina is accordingly revised as making in embodiment 3
The alpha-alumina supports that standby number is Scar-3.
(3) evaluation of silver catalyst catalytic performance:
When measuring catalyst difference under the conditions of previous process using microreactor evaluating apparatus to manufactured catalyst
The activity and selectivity of phase, test result are listed in table 3.
Embodiment 4
(1) preparation of carrier:
Zirlite is roasted under the conditions of 1050 DEG C, 10h, roasts bayerite under the conditions of 850 DEG C, 10h, in mass ratio
For 1:1 it is baking mixed after product, obtain κ-aluminium oxide, the compound phase alumina of θ-aluminium oxide, weigh the compound phase alumina of 300g,
360.0g zirlite, 240.0g boehmite, 8.0g ammonium fluoride, 5.0g barium sulfate are put into blender and are uniformly mixed, and turn
Enter into kneader, dust technology (nitric acid: water=1:3, volume ratio) is added until being kneaded into extrudable molding paste, by cream
Shape object is put into banded extruder, is extruded into seven apertures in the human head column, is dried more than for 24 hours at 60-120 DEG C, and free water content is reduced to
Then 10% hereinafter, roast dried seven apertures in the human head column, maturing temperature is 1400 DEG C, and constant temperature calcining 10h is finally cooled to
Room temperature obtains alpha-alumina supports.The alpha-alumina supports number of the embodiment 4 preparation is Scar-4, related physical performance number
According to being shown in Table 2.
(2) preparation of catalyst:
It is identical as the silver catalyst preparation method in embodiment 1, only its Alpha-alumina is accordingly revised as making in embodiment 4
The alpha-alumina supports that standby number is Scar-4.
(3) evaluation of silver catalyst catalytic performance:
When measuring catalyst difference under the conditions of previous process using microreactor evaluating apparatus to manufactured catalyst
The activity and selectivity of phase, test result are listed in table 3.
Comparative example 1
(1) preparation of carrier:
360.0g zirlite, 240.0g boehmite, 8.0g ammonium fluoride, 5.0g barium sulfate are weighed, blender is put into
In be uniformly mixed, be transferred in kneader, dust technology (nitric acid: water=1:3, volume ratio) be added until be kneaded into extrudable molding
Paste, paste placed into banded extruder, be extruded into seven apertures in the human head column, dried at 60-120 DEG C more than for 24 hours, make free contain
Water is reduced to 10% hereinafter, dried seven apertures in the human head column is then put into natural gas kiln kiln roasting, and maturing temperature is
1350 DEG C, constant temperature calcining 10h is finally cooled to room temperature, obtains alpha-alumina supports.The Alpha-alumina of the comparative example 1 preparation carries
Body number is Ccar-1, and related physical performance data is shown in Table 2.
(2) preparation of silver catalyst:
It is identical as the silver catalyst preparation method in embodiment 1, only its Alpha-alumina is accordingly revised as making in comparative example 1
The alpha-alumina supports that standby number is Ccar-1.
(3) evaluation of silver catalyst catalytic performance:
When measuring catalyst difference under the conditions of previous process using microreactor evaluating apparatus to manufactured catalyst
The activity and selectivity of phase, test result are listed in table 3.
Comparative example 2
(1) preparation of carrier:
460.0g zirlite, 240.0g boehmite, 8.0g ammonium fluoride, 5.0g barium sulfate are weighed, blender is put into
In be uniformly mixed, be transferred in kneader, dust technology (nitric acid: water=1:3, volume ratio) be added until be kneaded into extrudable molding
Paste, paste placed into banded extruder, be extruded into seven apertures in the human head column, dried at 60-120 DEG C more than for 24 hours, make free contain
Water is reduced to 10% hereinafter, dried seven apertures in the human head column is then put into natural gas kiln kiln roasting, and maturing temperature is
1350 DEG C, constant temperature calcining 10h is finally cooled to room temperature, obtains alpha-alumina supports.The Alpha-alumina of the comparative example 1 preparation carries
Body number is Ccar-2, and related physical performance data is shown in Table 2.
(2) preparation of silver catalyst:
It is identical as the silver catalyst preparation method in embodiment 1, only its Alpha-alumina is accordingly revised as making in comparative example 1
The alpha-alumina supports that standby number is Ccar-2.
(3) evaluation of silver catalyst catalytic performance:
When measuring catalyst difference under the conditions of previous process using microreactor evaluating apparatus to manufactured catalyst
The activity and selectivity of phase, test result are listed in table 3.
Table 2
| Bearer number | Specific surface area (m2/g) | Crushing strength (N/) | Water absorption rate (%) |
| Scar-1 | 1.41 | 130 | 50.9 |
| Scar-2 | 1.47 | 129 | 52.1 |
| Scar-3 | 1.59 | 120 | 50.3 |
| Scar-4 | 1.28 | 207 | 50.7 |
| Ccar-1 | 1.32 | 139 | 50.1 |
| Ccar-2 | 1.29 | 119 | 50.4 |
Table 3
It can be seen that the present invention in carrier preparation process by contrast table 2,3 data of table to take using compound phase alumina
Alpha-alumina supports are prepared for pore creating material and a variety of expensive auxiliary agents, the silver catalyst prepared by its carrier is in epoxidation of ethylene
In be demonstrated by good selectivity and stability, and activity does not reduce.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.
Claims (12)
1. a kind of alpha-alumina supports, which is characterized in that the alpha-alumina supports are prepared by a method comprising the following steps:
Step S1 prepares the solid, powdery object with following component: compound phase alumina, boehmite, alkaline-earth metal chemical combination
The solid, powdery object is mixed with binder and water, is mixed by object and the gibbsite optionally contained, fluorochemical
Close object；
The resulting mixture of step S1 is formed, obtains formed body by step S2；
The resulting formed body of step S2 is dried and is roasted, the alpha-alumina supports are made by step S3；
The alpha-alumina supports have spherical apparent form.
2. alpha-alumina supports according to claim 1, wherein the compound phase alumina includes gama-alumina, θ-oxygen
Change aluminium, κ-aluminium oxide, at least two in η-aluminium oxide and Alpha-alumina.
3. alpha-alumina supports according to claim 1 or 2, wherein the compound phase alumina is that aluminium hydroxide exists
Roasting obtains at 750-1100 DEG C, and the aluminium hydroxide is preferably zirlite and/or bayerite.
4. alpha-alumina supports according to claim 1 or 2, wherein on the basis of the total weight of the solid, powdery object,
The content of the compound phase alumina is 1-70 weight %, and the content of the boehmite is 20-50 weight %, the alkaline earth
The content of metallic compound is 0.1-5 weight %, and the content of the fluorochemical is 0-3 weight %；The gibbsite
Weight ratio with boehmite is 0-4:1；The weight ratio of the binder and water is 1:1-10；The binder and water it is total
Weight and the weight ratio of solid, powdery object are 1:2-10.
5. alpha-alumina supports according to claim 1 or 2, wherein the alkaline earth metal compound is selected from strontium and/or barium
One of oxide, nitrate, acetate, oxalates and sulfate or a variety of.
6. alpha-alumina supports according to claim 1 or 2, wherein the gibbsite is selected from promise diaspore, three water
One of aluminium ore and bayerite are a variety of.
7. alpha-alumina supports according to claim 1 or 2, wherein the fluorochemical is selected from hydrogen fluoride, fluorination
One of ammonium, magnesium fluoride and lithium fluoride are a variety of.
8. alpha-alumina supports according to claim 1 or 2, wherein the binder be selected from citric acid, nitric acid, hydrochloric acid,
One of formic acid and acetic acid are a variety of.
9. alpha-alumina supports according to claim 1 or 2, wherein the alpha-alumina supports have the feature that α-
Alumina component accounts for percentage >=98% of total weight of carrier, specific surface 0.5-3.5m2/ g, Kong Rongwei 0.3-1.0mL/g, most
Can several apertures be 0.1-30.0 μm, water absorption rate >=40%, crushing strength be 30-400N/.
10. a kind of alkene epoxidation silver catalyst, the silver catalyst includes the active group of carrier and load on this carrier
Divide silver, which is characterized in that the carrier is alpha-alumina supports described in any one of claim 1-9.
11. alkene epoxidation silver catalyst according to claim 10, wherein the silver catalyst also contains:
Alkali metal and/or alkaline-earth metal or compound based on alkali metal and/or alkaline-earth metal；
Rhenium metal and/or compound based on rhenium；And
Optionally, the coassist agent element of rhenium, selected from cerium, sulphur, molybdenum, chromium, salt or sour form one of oxygen anion or a variety of.
12. a kind of olefin epoxidation process, which is characterized in that this method includes the silver by alkene described in claim 10 or 11
Epoxidation reaction of olefines is carried out under the action of catalyst, obtains epoxide, it is preferable that the alkene is selected from styrene, third
One of alkene, ethylene and 1,3- butadiene are a variety of.
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