CN107812542B - Alpha-alumina carrier and preparation method and application thereof - Google Patents
Alpha-alumina carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN107812542B CN107812542B CN201610827330.7A CN201610827330A CN107812542B CN 107812542 B CN107812542 B CN 107812542B CN 201610827330 A CN201610827330 A CN 201610827330A CN 107812542 B CN107812542 B CN 107812542B
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- carrier
- alumina
- alpha
- solid mixture
- compound
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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 92
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052709 silver Inorganic materials 0.000 claims abstract description 57
- 239000004332 silver Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 43
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001773 titanium mineral Inorganic materials 0.000 claims abstract description 5
- 239000008247 solid mixture Substances 0.000 claims description 39
- 229910052702 rhenium Inorganic materials 0.000 claims description 35
- 239000011230 binding agent Substances 0.000 claims description 29
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 19
- 239000011707 mineral Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 16
- -1 rhenium metal compound Chemical class 0.000 claims description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 241000877463 Lanio Species 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000004682 monohydrates Chemical class 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000002671 adjuvant Substances 0.000 claims description 2
- 150000004684 trihydrates Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 11
- 239000012752 auxiliary agent Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 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
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 2
- 229910002340 LaNiO3 Inorganic materials 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 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
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 239000000843 powder 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
-
- 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
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Abstract
The invention relates to an alpha-alumina carrier and a preparation method and application thereof. The alpha-alumina carrier is prepared by adding a certain amount of calcium-titanium mineral substances in the preparation process, so that the crushing strength and the water absorption of the carrier can be effectively improved, and the macroporous content of the carrier can be increased, thereby finally improving the performance of the catalyst. The silver catalyst prepared by the porous alumina carrier prepared by the method has stable performance and higher activity, and is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
Description
Technical Field
The invention belongs to the technical field of catalyst carriers, and relates to an alpha-alumina carrier, and a preparation method and application thereof.
Background
Under the action of silver catalyst, ethylene is oxidized to produce ethylene oxide and side reaction to produce carbon dioxide, water, etc. with activity, selectivity and stability as the main performance indexes of silver catalyst. By activity is meant the reaction temperature required for the ethylene oxide production process to reach a certain reaction load. The lower the reaction temperature, the higher the activity of the catalyst. By selectivity is meant the ratio of the moles of ethylene converted to ethylene oxide in the reaction to the total moles of ethylene reacted. The stability is expressed as the rate of decrease in activity and selectivity, and the smaller the rate of decrease, the better the stability of the catalyst. The silver catalyst with high activity, high selectivity and good stability is used in the process of producing ethylene oxide by oxidizing ethylene, so that the economic benefit can be greatly improved, and the preparation of the silver catalyst with high activity, high selectivity and good stability is the main direction of research on the silver catalyst. The performance of the silver catalyst is not only important in relation to the composition of the catalyst and the preparation method, but also important in relation to the performance of the carrier used in the catalyst and the preparation method.
The preparation method of the silver catalyst mainly comprises two processes of preparing a porous carrier (such as alumina) and applying an active component and an auxiliary agent to the carrier. The carrier is alpha-alumina with small specific surface area. The alumina has more than ten crystal forms, wherein the common crystal forms include alpha, gamma, theta, eta, and the like. Among these phases, the alpha phase is a stable phase, directly affecting the performance of the silver catalyst.
The main raw material for preparing the alumina carrier is aluminum hydroxide, and the alumina is a dehydration product of alumina oxide, so that the physical properties of the alumina and the aluminum hydroxide are closely related, and the physical properties of the aluminum hydroxide are influenced by the preparation conditions thereof, which mainly include raw material, neutralization pH temperature, aging pH and temperature, and the like. In the process of preparing the alumina carrier, various different alumina powder raw materials (and/or) are selected and added with pore-forming agents, binders, various additives and the like, the materials are mixed and kneaded uniformly, then the mixture is extruded and molded into blanks (Raschig rings, spherical particles, porous columns, saddle shapes and the like) with different shapes, and finally the blanks are sintered at the temperature of 1200-1700 ℃ to prepare the porous heat-resistant alpha-alumina carrier product, so that the proportion of the alumina raw materials with different types and particle sizes, the dosage of the pore-forming agents, the molding mode, the calcining system and the like can influence the pore structure and the physical performance of the silver catalyst carrier, and further influence the performance of the catalyst.
It is an important research direction to add other components to the alumina carrier to improve the carrier performance of the silver catalyst, and meanwhile, an auxiliary agent is often added in the preparation process of the silver catalyst carrier to improve the carrier performance. Although the prior art adopts methods of adding alkaline earth metal compounds into alumina raw materials to improve alumina carriers, and the like, to bring different degrees of improvement on the activity and selectivity of the catalyst, the requirements on the performance of the alumina carriers are continuously increased along with the large-scale industrial application of high-selectivity silver catalysts, but the improvement on the performance of the carriers and the activity and selectivity of the catalysts caused by singly adding the alkaline earth metal compounds is limited.
Therefore, there is a problem in that research and development of a method capable of improving the activity and selectivity of the catalyst to a greater extent are required.
Disclosure of Invention
One of the purposes of the invention is to provide an alpha-alumina carrier which is prepared by a carrier modification method different from the prior art, has good crushing strength and lower wear rate, and has higher specific surface area compared with the carrier prepared by the prior art, thereby improving the dispersibility of the active components of the catalyst on the carrier and further improving the catalytic performance of the catalyst.
The invention also aims to provide a preparation method of the alpha-alumina carrier.
The invention also provides the application of the alpha-alumina carrier.
To this end, the invention provides, in a first aspect, an α -alumina carrier prepared by calcining an α -alumina carrier precursor mixture containing alumina and a perovskite-type mineral.
According to the present invention, the perovskite-like mineral includes a complex oxide perovskite compound and/or a perovskite-like compound.
In some preferred embodiments of the invention, the complex oxide perovskite compound includes, but is not limited to, lanthanum manganate (LaMnO)3) An oxide.
In other preferred embodiments of the present invention, the perovskite-like compound comprises lanthanum nickelate (LaNiO)3) And/or lanthanum cobaltate (LaCoO)3)。
In some embodiments of the invention, the crush strength of the carrier>25N, preferably 45-210N; the specific surface area is 0.4-4.5m2A/g, preferably from 1.0 to 2.5m2(ii)/g; the water absorption is not lower than 30 percent, and preferably not lower than 45 percent; the pore volume of the alpha-alumina carrier is 0.35-0.85mL/g, preferably 0.40-0.80 mL/g.
In other embodiments of the present invention, the α -alumina is preferably present in the support in an amount of 90 wt% or more based on the total weight of the α -alumina support, and more preferably in an amount of 95 wt% or more based on the total weight of the α -alumina support.
In a second aspect, the present invention provides a method of preparing a vector according to the first aspect of the present invention, comprising:
step L, mixing alpha-alumina trihydrate, pseudo-alumina monohydrate, a perovskite mineral and optional additives to prepare a solid mixture;
step M, adding a binder and water into the solid mixture to obtain an alpha-alumina carrier precursor mixture;
and step N, kneading, molding, drying and roasting the alpha-alumina carrier precursor mixture to obtain the alpha-alumina carrier.
According to the method of the present invention, the perovskite mineral is contained in the solid mixture in an amount of 0.02 wt% to 5.0 wt%, preferably the perovskite mineral is contained in an amount of 0.05 wt% to 4.0 wt%, and more preferably the perovskite mineral is contained in an amount of 1.20 wt% to 2.0 wt%, based on the total weight of the solid mixture.
In some embodiments of the invention, the amount of alpha-alumina trihydrate in the solid mixture is from 50 wt% to 90 wt%, based on the total weight of the solid mixture.
In other embodiments of the present invention, the pseudo-monohydrate alumina is present in an amount of from 5 wt% to 50 wt%, based on the total weight of the solid mixture.
According to the method of the invention, the content of the auxiliary agent in the solid mixture is 0-5 wt% based on the total weight of the solid mixture.
In some embodiments of the invention, the adjuvant is one or more of silicon, a silicon-containing compound, and an alkaline earth metal compound.
In the present invention, it is preferable that the silicon-containing compound is silica and/or silicate.
In the present invention, the alkaline earth metal compound includes one or more of magnesium oxide, calcium oxide, strontium oxide, and barium oxide, sulfate, acetate, nitrate, and oxalate, and preferably the alkaline earth metal compound includes one or more of strontium oxide, barium oxide, sulfate, acetate, nitrate, and oxalate.
According to the method of the invention, the binder is added in the form of an aqueous binder solution, and the aqueous binder solution is added in an amount of 15 to 60 wt.%, based on the total weight of the solid mixture.
In some embodiments of the present invention, the weight ratio of the binder to water in the aqueous binder solution is 1 (1.25-10), preferably the weight ratio of the binder to water is 1 (4-5).
In other embodiments of the present invention, the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
In a third aspect, the present invention provides a silver catalyst comprising:
component a, a carrier according to the first aspect of the invention or a carrier prepared according to the method of the second aspect of the invention;
component b, silver simple substance;
component c, an alkaline earth metal simple substance and/or an alkaline earth metal compound;
component d, elemental rhenium metal and/or a rhenium metal compound.
According to the process of the invention, the catalyst also comprises a co-promoter of rhenium and/or an organic amine.
In some embodiments of the present invention, the rhenium co-promoter includes one or more of elemental chromium, elemental molybdenum, elemental tungsten, elemental boron, a chromium metal compound, a molybdenum metal compound, a tungsten metal compound, and a boron compound.
In other embodiments of the present invention, the organic amine comprises one or more of pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine, and triethylamine
In a fourth aspect, the present invention provides the use of a carrier according to the first aspect of the present invention or a carrier prepared by a process according to the second aspect of the present invention or a silver catalyst according to the third aspect of the present invention in the oxidation of ethylene to produce ethylene oxide.
The alpha-alumina carrier is prepared by adding a certain amount of calcium-titanium mineral substances in the preparation process, so that the crushing strength and the water absorption of the carrier can be effectively improved, and the macroporous content of the carrier can be increased, thereby finally improving the performance of the catalyst. The silver catalyst prepared by the porous alumina carrier prepared by the method has stable performance, higher activity and better selectivity, and is particularly suitable for the reaction of producing ethylene oxide by oxidizing ethylene.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below.
As mentioned above, the mere addition of alkaline earth metal compounds has limited improvement in the support properties and the activity and selectivity of the catalyst. In order to improve the performance of the alpha-alumina carrier, the inventor has made a great deal of research on the alpha-alumina carrier, and the inventor finds that a catalyst with higher activity and better selectivity can be prepared on the basis of the carrier prepared by adding a certain amount of perovskite minerals in the preparation process of the alumina carrier. The present invention has been made based on the above findings.
Therefore, the α -alumina carrier according to the first aspect of the present invention is prepared by adding a certain amount of a perovskite mineral during the preparation thereof, and has the following characteristics as a supported porous carrier: crush strength>25N, preferably 45-210N; the specific surface area is 0.4-4.5m2A/g, preferably from 1.0 to 2.5m2(ii)/g; the water absorption is not lower than 30 percent, and preferably not lower than 45 percent; the pore volume of the alpha-alumina carrier is 0.35-0.85mL/g, preferably 0.40-0.80 mL/g; in the carrier, the content of alpha-alumina is more than 90 wt%, preferably more than 95 wt% based on the total weight of the alpha-alumina carrier; the total weight of the assistants such as alkaline earth metal, silicon and the like is 0-5% of the total weight of the carrier; preferably, the total weight of the assistants such as alkaline earth metal, silicon and the like is 0.01-5% of the total weight of the carrier.
According to some embodiments of the invention, the perovskite-like mineral comprises a complex oxide perovskite compound and/or a perovskite-like compound.
In some preferred embodiments of the invention, the complex oxide perovskite compound includes, but is not limited to, lanthanum manganate (LaMnO)3) An oxide. Preferably, the perovskite compound of the composite oxide is lanthanum manganate (LaMnO)3) An oxide.
In other preferred embodiments of the present invention, the perovskite-like compound comprises lanthanum nickelate (LaNiO)3) And/or lanthanum cobaltate (LaCoO)3)。
The preparation method of the alpha-alumina carrier related to the second aspect of the invention comprises the following steps:
step L, mixing alpha-alumina trihydrate, pseudo-alumina monohydrate, a perovskite mineral and optional additives to prepare a solid mixture;
step M, adding a binder and water into the solid mixture to obtain an alpha-alumina carrier precursor mixture;
and step N, kneading, molding, drying and roasting the alpha-alumina carrier precursor mixture to obtain the alpha-alumina carrier.
In the preparation method of the alpha-alumina carrier, the alpha-alumina trihydrate and the pseudo-alumina monohydrate are all converted into the alpha-alumina after being calcined as an aluminum source. For example, the solid mixture may have a trihydrate content of alpha-alumina in the range of 50 wt% to 90 wt%, based on the total weight of the solid mixture. As another example, the amount of pseudo-monohydrate alumina in the solid mixture is from 5 wt% to 50 wt%, based on the total weight of the solid mixture.
The inventor researches and discovers that perovskite and perovskite-like compounds have stable crystal structures and higher oxidation-reduction performance and enhance the interaction between double metals, so that the invention can effectively improve the crushing strength and water absorption of the carrier and increase the macroporous content of the carrier by adding a certain amount of calcium-titanium mineral substances in the preparation process of the alpha-alumina carrier, thereby finally improving the performance of the catalyst.
It should be noted that in the preparation method of the alpha-alumina carrier, the added calcium-titanium mineral is a bimetal composite oxide with a molecular formula ABO3Wherein A is a metal cation of larger radius (radius)>0.09nm), mainly alkali metals, alkaline earth metals or rare earth metals (La, Ca, Ce, etc.); b is a metal cation of smaller radius (radius)>0.05nm), mainly transition metal elements (Mn, Fe, Co, Ni, titanium), Al and the like. For example, the perovskite-like mineral includes a complex oxide perovskite compound and/or a perovskite-like compound. The perovskite compound of the composite oxide is lanthanum manganate (LaMnO)3) An oxide; as another example, the perovskite-like compound is lanthanum nickelate (LaNiO)3) And/or lanthanum cobaltate (LaCoO)3). For the purposes of the present invention, the perovskite-type mineral is added in an amount of 0.02 to 5.0% by weight, preferably 0.05 to 4.0% by weight, and more preferably 1.20 to 2.0% by weight, based on the total weight of the solid mixture, i.e. based on the total weight of the solid mixture prepared in step L, based on the content of element a.
The inventors have found that in some embodiments of the invention, the addition of the perovskite lanthanum nickelate to the support increases the crush strength and water absorption of the support as compared to the addition of the oxides of nickel and lanthanum alone. The macropores in the support were increased (> 10 μm) by mercury intrusion tests.
The inventors have found that in other embodiments of the invention, the addition of the perovskite lanthanum cobaltate to the support increases the crush strength and increases the specific surface area of the support as compared to the addition of the oxides of cobalt and lanthanum alone.
In the preparation method of the alpha-alumina carrier, the addition of the auxiliary agent can improve the pore structure and the mechanical strength of the alumina carrier. The auxiliary agent is one or more of silicon, a silicon-containing compound and an alkaline earth metal compound.
In some embodiments, for example, the silicon-containing compound is silica and/or a silicate.
In other embodiments, for example, the alkaline earth metal compound includes one or more of oxides of magnesium, calcium, strontium, and barium, sulfates, acetates, nitrates, and oxalates. Preferably the alkaline earth metal compound comprises one or more of strontium oxide, barium oxide, sulphate, acetate, nitrate and oxalate.
According to some embodiments of the present invention, in the above method for preparing an α -alumina support, the solid mixture may further include a thermally decomposable burnout material in addition to the above-mentioned components. The thermally decomposable burnout material comprises one or more of polyethylene, polypropylene, petroleum coke, carbon powder and graphite, and the mass of the thermally decomposable burnout material accounts for 0-20.0% of the total mass of the solid mixture.
The preparation method of the alpha-alumina carrier of the inventionThe binder is used for mixing pseudo-water A1 in solid powder2O3Generating aluminum sol, and bonding the components together to form paste which can be extruded and molded. The binder is added as an aqueous binder solution and the aqueous binder solution is added in an amount of 15 wt% to 60 wt%, preferably 15 wt% to 45 wt%, more preferably 15 wt% to 35 wt%, even more preferably 15 wt% to 25 wt%, based on the total weight of the solid mixture.
In some embodiments, for example, in the aqueous binder solution, the weight ratio of the binder to water is 1 (1.25-10), preferably the weight ratio of the binder to water is 1 (4-5).
In other embodiments, for example, the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid, preferably the binder is nitric acid.
In the present invention, the addition of the solid mixture and the binder solution does not need to be performed sequentially, for example, the auxiliary agent in the solid mixture may be added to the solid mixture together with the binder solution at the end.
In order to mix the precursor mixture uniformly, the precursor mixture is kneaded in a kneader for 5-90 min. After the precursor mixture is sufficiently kneaded, the carrier may be formed into a certain shape, for example, a honeycomb cylindrical particle having seven, five or three holes with an outer diameter of 7 to 9mm and a honeycomb hole diameter of 1 to 3 mm; single-hole circular ring-shaped granules with the outer diameter of 7-9mm and the inner diameter of 3-6mm, and the like, and the molding is carried out in a molding machine.
Drying the formed product after the precursor mixture is formed, wherein the drying is carried out at the temperature of 80-130 ℃, the water content in the formed product is controlled to be below 10 percent, and the drying time is determined according to the water content; in some embodiments of the invention, the drying time may be, for example, 1-24 hours.
According to some embodiments of the present invention, in order to facilitate extrusion of the molded object, a molding aid may be added to the solid mixture, the molding aid including one or more of vaseline, graphite, paraffin, and vegetable oil.
In order to obtain an alpha-alumina carrier having suitable characteristics, the present invention calcines the dried molded product. The roasting comprises the processes of temperature programming and constant-temperature roasting, wherein the temperature of the constant-temperature roasting is 1000-1600 ℃, and the preferable temperature of the constant-temperature roasting is 1100-1500 ℃; the constant-temperature roasting time is 2-24 h.
The silver catalyst according to the third aspect of the present invention is a silver catalyst for producing ethylene oxide by the vapor phase catalytic oxidation of ethylene, comprising:
component a, a carrier according to the first aspect of the invention or a carrier prepared according to the method of the second aspect of the invention; component b, silver simple substance, which is loaded on a carrier; and the following auxiliary components:
component c, an alkaline earth metal simple substance and/or an alkaline earth metal compound; and
component d, elemental rhenium metal and/or a rhenium metal compound.
According to some preferred embodiments of the invention, the catalyst further comprises a co-promoter of rhenium and/or an organic amine.
In some embodiments, the rhenium co-promoter includes one or more of elemental chromium, elemental molybdenum, elemental tungsten, elemental boron, a chromium metal compound, a molybdenum metal compound, a tungsten metal compound, and a boron compound.
The silver catalyst of the present invention can be prepared in a conventional manner, for example, by impregnating the above-mentioned α -alumina carrier provided by the present invention with an impregnation mixture solution containing a silver compound, an alkaline earth metal assistant, a rhenium metal assistant or a rhenium metal compound, and optionally a rhenium co-assistant and/or an organic amine.
According to a specific embodiment of the present invention, the silver catalyst is prepared by the following method:
step I, impregnating the provided alpha-alumina carrier with an impregnating mixed solution containing sufficient silver-containing compound, alkaline earth metal auxiliary agent, rhenium metal auxiliary agent or rhenium metal compound, and optional rhenium co-auxiliary agent and/or organic amine;
step II, filtering the impregnation solution, and drying the impregnated carrier; and
and III, activating the carrier obtained in the step II in oxygen-containing mixed gas to prepare the silver catalyst.
In some embodiments of preparing the silver catalyst of the present invention, first, an aqueous solution of silver nitrate is reacted with an aqueous solution of ammonium oxalate or oxalic acid to precipitate a silver oxalate precipitate, after filtration, the precipitate is washed with deionized water until no nitrate ions are present, then the silver oxalate is dissolved in an aqueous solution of organic amine, and then other additives (alkaline earth metal simple substance and/or alkaline earth metal compound, rhenium metal simple substance and/or rhenium metal compound) and a rhenium co-additive are added to prepare a dipping mixed solution. The above alpha-alumina carrier is then impregnated with the impregnation mixture solution, drained and maintained in an air stream or a mixed gas of nitrogen and oxygen having an oxygen content of not more than 21 v% (e.g., containing 8.0 v%) at a temperature in the range of 180-700 deg.C, preferably 200-500 deg.C for 20 seconds to 150 minutes, preferably 1 minute to 80 minutes, to effect thermal decomposition. Silver oxide can be used to replace silver nitrate, and silver oxalate can also be directly complexed with organic amine without leaching, and then the carrier is impregnated. The amount of the silver compound used in the impregnation process of the present invention is sufficient to obtain a silver catalyst having an elemental silver content of 1 wt% to 30 wt%, preferably 5 wt% to 26 wt%, based on the total weight of the silver catalyst.
In some embodiments of the invention, the organic amine comprises one or more of pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine, and triethylamine.
In some embodiments of the present invention, the alkaline earth metal promoter may be one or more of compounds containing magnesium, calcium, strontium and barium, such as one or more of oxides, oxalates, sulfates, acetates or nitrates containing magnesium, calcium, strontium and barium. In some examples, the finally prepared silver catalyst has an increased content of alkaline earth metal (excluding alkaline earth metal added during preparation of the support) in the silver catalyst preparation process of 5 to 2000ppm, preferably 10 to 1200ppm, based on the total weight of the silver catalyst. 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 addition to the above-mentioned alkaline earth metal promoters, other promoters added during the preparation of the silver catalyst, such as rhenium promoters and optionally rhenium co-promoters, can further improve the activity, selectivity and stability of the activity and selectivity of the silver catalyst.
In some embodiments of the present invention, the rhenium promoter is elemental rhenium metal and/or a rhenium metal compound. The rhenium metal compound comprises one or more of ammonium perrhenate and other rhenium compounds. In the present invention, the rhenium element content in the finally obtained silver catalyst is, for example, 5 to 1500ppm, preferably 10 to 1000ppm, based on the total weight of the silver catalyst. 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.
In some embodiments of the present invention, the rhenium co-promoter includes one or more of elemental chromium, elemental molybdenum, elemental tungsten, elemental boron, a chromium metal compound, a molybdenum metal compound, a tungsten metal compound, and a boron compound. In the present invention, the rhenium co-promoter content in the finally obtained silver catalyst is, for example, 5 to 1000ppm, preferably 10 to 500ppm, based on the total weight of the silver catalyst. The rhenium co-promoter may be applied to the carrier before, simultaneously with, or after impregnation of the silver, or may be impregnated on the carrier after the silver compound has been reduced.
The use of a carrier according to the first aspect of the present invention or a carrier prepared by the process according to the second aspect of the present invention or a silver catalyst according to the third aspect of the present invention in the production of ethylene oxide by the oxidation of ethylene according to the fourth aspect of the present invention is also understood to be a process for the production of ethylene oxide by the oxidation of ethylene, which process is carried out in the presence of a carrier according to the first aspect of the present invention or a carrier prepared by the process according to the second aspect of the present invention or a silver catalyst according to the third aspect of the present invention.
The term "optional" as used herein means either with or without, and with or without the addition of.
The term "water" as used herein refers to one or more of deionized water, distilled water and ultrapure water, unless otherwise specified or indicated.
The term "M compound" or "M metal compound" or "M-containing compound" as used herein refers to a compound containing an M element, wherein M represents a certain metal or nonmetal, such as silver metal, rhenium metal, alkali metal, alkaline earth metal, or boron.
The term "rhenium co-promoter" as used in the present invention is also referred to as "rhenium co-promoter" or rhenium co-promoter.
The molecular formula of the term "alumina" described in the present invention is Al2O3。
Examples
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention.
The method for detecting the physical properties of the alpha-alumina carrier comprises the following steps:
the specific surface area of the support is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.
The crushing strength of the carrier can be obtained by, for example, randomly selecting 30 carrier samples and measuring the radial crushing strength and then averaging the samples by using a DL II type intelligent particle strength measuring instrument produced by the institute of chemical engineering and design of the large-scale continuous chemical industry.
The term "water absorption" as used in the present invention refers to the volume of saturated adsorbed water per unit mass of the carrier, in mL/g. The determination method comprises the following steps: first, a certain amount of carrier (assuming its mass m) is weighed1) Boiling in boiling water for 1 hr, taking out the carrier, standing on wet gauze with moderate water content to remove excessive water on the surface of the carrier, and weighing the mass of the carrier after water adsorption (assuming that m is m)2) The water absorption of the carrier was calculated by the following formula.
Where ρ isWater (W)Is to measure the density of water under the conditions of temperature and atmospheric pressureAnd (4) degree.
The evaluation method of the catalyst performance of the invention is as follows:
various silver catalysts involved in the present invention were tested for their initial activity and selectivity using a laboratory microreactor (hereinafter referred to as "microreaction") evaluation device. The reactor used in the microreaction evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reaction tube was placed in a heating mantle. The filling volume of the catalyst is 1mL, and the lower part of the catalyst is provided with an inert filler, so that a catalyst bed layer is positioned in a constant temperature area of a heating sleeve.
The measurement conditions for the activity and selectivity of the catalyst used in the present invention are shown in table 1:
TABLE 1 determination of catalyst Activity and selectivity
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The measurement results were corrected for volume shrinkage and the selectivity S was calculated as follows:
where Δ EO is the difference in ethylene oxide concentration between the reactor outlet gas and the inlet gas, Δ CO2The carbon dioxide concentration difference between the outlet gas and the inlet gas of the reactor is determined, and the average of more than 10 groups of test data is taken as the test result of the day.
In the following examples, examples 1 to 4 are carrier examples, comparative examples 1 to 3 are carrier comparative examples, examples 6 to 8 are silver catalyst examples, and comparative examples 4 to 6 are silver catalyst comparative examples.
Example 1:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g of perovskite LaNiO30.52g of the mixture is put into a mixer to be mixed evenly, the mixture is transferred into a kneader, 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) is added, and the mixture is kneaded into paste which can be extruded and moldedA compound (I) is provided. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this example are shown in table 2.
Example 2:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g of perovskite LaNiO312.4g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added thereto and kneaded into an extrudable paste. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this example are shown in table 2.
Example 3:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g of perovskite LaCoO30.5g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added and kneaded into a paste which could be extruded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this example are shown in table 2.
Example 4:
50-500 meshAlpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g perovskite LaMnO34.8g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added and kneaded into a paste which could be extruded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this example are shown in table 2.
Comparative example 1:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added and kneaded into a paste which could be extruded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this comparative example are shown in table 2.
Comparative example 2:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g、La(NO3)30.86g and Ni (NO)3)20.58g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added and kneaded into a paste which could be extruded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into the furnaceRaising the temperature from room temperature to 1250 ℃ in a furnace for about 18 hours, and keeping the temperature for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this comparative example are shown in table 2.
Comparative example 3:
mixing 50-500 mesh alpha-trihydrate A12O3400g of pseudo-monohydrate A1 larger than 200 meshes2O3100g、SiO20.5g、La(NO3)30.86g and Co (NO)3)20.58g of the mixture was put into a blender and mixed uniformly, and then transferred into a kneader, and 90 ml of dilute nitric acid (nitric acid: water: 1:5, weight ratio) was added and kneaded into a paste which could be extruded. Extruding into a five-hole column with an outer diameter of 8.0mm, a length of 6.0mm and an inner diameter of 1.0mm, and drying at 80-120 deg.C for more than 2 hr to reduce the free water content to below 10%. Then the green body is put into an electric furnace and is raised from room temperature to 1250 ℃ for about 18 hours, and the temperature is kept for 4 hours to obtain white alpha-A12O3A carrier sample. The relevant physical property data for the alpha-alumina support prepared in this comparative example are shown in table 2.
TABLE 2 data of physical properties in the alpha-alumina carriers of examples 1-4 and comparative examples 1-3
As can be seen by comparing the data in table 2, the addition of a certain amount of perovskite minerals in the preparation of the carrier can significantly improve the crushing strength of the α -alumina carrier; meanwhile, the water absorption rate, the specific surface area and the like of the alpha-alumina carrier are improved to a certain extent.
Examples 5-8 and comparative examples 4-6:
700g of silver nitrate was dissolved in 750ml of deionized water. 325g of ammonium oxalate was dissolved in 250ml of deionized water at 50 ℃. The two solutions were mixed under vigorous stirring to form a white silver oxalate precipitate. Aging for more than 30 minutes, filtering, and washing the precipitate with deionized water until the precipitate is free of nitrate ions. The filter cake contained about 60 wt% silver and about 15 wt% water.
300g of ethylenediamine, 110g of ethanolamine and 375g of deionized water were added to a stirred glass flask. Slowly adding the prepared silver oxalate paste into the mixed solution under stirring, keeping the temperature below 45 ℃ to completely dissolve the silver oxalate, wherein the adding amount of the silver oxalate ensures that the prepared impregnation solution contains 23-25 wt% of silver. Adding 2.2g of cesium sulfate and 1.0g of ammonium perrhenate, and adding deionized water to make the total mass of the solution reach 2000g, thereby preparing an impregnation mixed solution.
50g of each of the carrier samples of examples 1 to 4 and comparative examples 1 to 3 was taken and placed in a vessel capable of being evacuated. Vacuumizing to over 10mmHg, putting 100g of the prepared impregnation mixed solution into each part of the carrier, and immersing the carrier for 30 minutes. The excess solution is leached away. The impregnated carrier is heated in air flow at 275 deg.C for 10 minutes and cooled to obtain the silver epoxyethane catalyst.
Analyzing the content of silver and the auxiliary agent of the prepared catalyst, wherein the content is calculated by metal; the activity and selectivity of the catalyst samples were measured using a microreactor evaluation unit under the aforementioned process conditions, and the test results are shown in Table 3.
TABLE 3 results of tests on catalysts of examples 5 to 8 and comparative examples 4 to 6 for oxidizing ethylene to ethylene oxide
| Sample source | Source of vector | Silver content (%) | Initial reaction temperature (. degree. C.) | EO(％) | Selectivity (%) |
| Example 5 | Example 1 | 17.9 | 214 | 2.5 | 84.3 |
| Example 6 | Example 2 | 18.4 | 219 | 2.5 | 85.2 |
| Example 7 | Example 3 | 18.6 | 217 | 2.5 | 84.7 |
| Example 8 | Example 4 | 18.7 | 211 | 2.5 | 85.0 |
| Comparative example 4 | Comparative example 1 | 18.4 | 227 | 2.5 | 83.1 |
| Comparative example 5 | Comparative example 2 | 18.6 | 220 | 2.5 | 83.8 |
| Comparative example 6 | Comparative example 3 | 18.4 | 218 | 2.5 | 83.5 |
Injecting: the selective EO yield is up to 300T/M3Average value in catalyst.
As can be seen from comparing the data in table 3, the selectivity of the catalyst prepared by adding the perovskite mineral is improved by 0.5% -1% compared with the catalyst prepared by independently adding oxides of lanthanum, nickel and cobalt, which indicates that the performance of the silver catalyst is remarkably improved.
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 (25)
1. An alpha-alumina carrier is prepared by roasting an alpha-alumina carrier precursor mixture containing alumina and a perovskite mineral;
wherein the calcium-titanium mineral packageComprising a complex oxide perovskite compound and/or a perovskite-like compound, the complex oxide perovskite compound comprising lanthanum manganate (LaMnO)3) An oxide, the perovskite-like compound comprising lanthanum nickelate (LaNiO)3) And/or lanthanum cobaltate (LaCoO)3)。
2. The carrier of claim 1, wherein the crush strength of the carrier>25N, and the specific surface area is 0.4-4.5m2The water absorption rate is not lower than 30 percent; the pore volume of the alpha-alumina carrier is 0.35-0.85 mL/g.
3. The carrier according to claim 2, wherein the carrier has a crush strength of 45 to 210N and a specific surface area of 1.0 to 2.5m2The water absorption rate is not lower than 45 percent; the pore volume of the alpha-alumina carrier is 0.40-0.80 mL/g.
4. The carrier of claim 2, wherein the content of α -alumina in the carrier is not less than 90 wt% based on the total weight of the α -alumina carrier.
5. The carrier as claimed in claim 4, wherein the content of α -alumina in the carrier is not less than 95 wt% based on the total weight of the α -alumina carrier.
6. A method of making the vector of any one of claims 1-5, comprising:
step L, mixing alpha-alumina trihydrate, pseudo-alumina monohydrate, a perovskite mineral and optional additives to prepare a solid mixture;
step M, adding a binder and water into the solid mixture to obtain an alpha-alumina carrier precursor mixture;
and step N, kneading, molding, drying and roasting the alpha-alumina carrier precursor mixture to obtain the alpha-alumina carrier.
7. The method of claim 6, wherein the amount of the perovskite mineral in the solid mixture is 0.02 wt% to 5.0 wt% based on the total weight of the solid mixture.
8. The method of claim 7, wherein the amount of the perovskite mineral in the solid mixture is 0.05 wt% to 4.0 wt% based on the total weight of the solid mixture.
9. The method of claim 8, wherein the amount of the perovskite mineral in the solid mixture is 1.20 wt% to 2.0 wt% based on the total weight of the solid mixture.
10. The method of claim 6, wherein the solid mixture comprises between 50 wt% and 90 wt% of the trihydrate based on the total weight of the solid mixture.
11. The method of claim 10, wherein the pseudo-monohydrate alumina is present in an amount of from 5 wt% to 50 wt% based on the total weight of the solid mixture.
12. The method of claim 6, wherein the adjuvant is present in the solid mixture in an amount of 0 to 5 wt%, based on the total weight of the solid mixture.
13. The method of claim 12, wherein the promoter comprises one or more of silicon, a silicon-containing compound, and an alkaline earth metal compound.
14. The method according to claim 13, wherein the silicon-containing compound is silica and/or a silicate.
15. The method of claim 13, wherein the alkaline earth metal compound comprises one or more of an oxide of magnesium, an oxide of calcium, an oxide of strontium, an oxide of barium, a sulfate, an acetate, a nitrate, and an oxalate.
16. The method of claim 15, wherein the alkaline earth metal compound comprises one or more of an oxide of strontium, an oxide of barium, a sulfate, an acetate, a nitrate, and an oxalate.
17. The method of any one of claims 6 to 16, wherein the binder is added as an aqueous binder solution in an amount of 15 wt% to 60 wt% based on the total weight of the solid mixture.
18. The method according to claim 17, wherein the weight ratio of the binder to water in the aqueous binder solution is 1 (1.25-10).
19. The method according to claim 18, wherein the weight ratio of the binder to water in the aqueous binder solution is 1 (4-5).
20. The method of claim 18, wherein the binder comprises one or more of nitric acid, formic acid, acetic acid, propionic acid, and hydrochloric acid.
21. A silver catalyst, comprising:
component a, a vector according to any one of claims 1 to 5 or a vector prepared by a process according to any one of claims 6 to 20;
component b, silver simple substance;
component c, an alkaline earth metal simple substance and/or an alkaline earth metal compound;
component d, elemental rhenium metal and/or a rhenium metal compound.
22. The silver catalyst according to claim 21, characterized in that the catalyst further comprises a co-promoter of rhenium and/or an organic amine.
23. The silver catalyst of claim 22 wherein the rhenium co-promoter comprises one or more of elemental chromium, elemental molybdenum, elemental tungsten, elemental boron, a chromium metal compound, a molybdenum metal compound, a tungsten metal compound, and a boron compound.
24. The silver catalyst of claim 22, wherein the organic amine comprises one or more of pyridine, butylamine, ethylenediamine, 1, 3-propanediamine, ethanolamine, and triethylamine.
25. Use of a carrier according to any one of claims 1 to 5 or a carrier prepared by a process according to any one of claims 6 to 20 or a silver catalyst according to any one of claims 21 to 24 in the oxidation of ethylene to ethylene oxide.
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