CN108607533A - Alumina support, catalyst and application - Google Patents
Alumina support, catalyst and application Download PDFInfo
- Publication number
- CN108607533A CN108607533A CN201611127131.1A CN201611127131A CN108607533A CN 108607533 A CN108607533 A CN 108607533A CN 201611127131 A CN201611127131 A CN 201611127131A CN 108607533 A CN108607533 A CN 108607533A
- Authority
- CN
- China
- Prior art keywords
- carrier
- water
- catalyst
- ethylene
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052709 silver Inorganic materials 0.000 claims abstract description 41
- 239000004332 silver Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000008247 solid mixture Substances 0.000 claims abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 11
- 229940099259 vaseline Drugs 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims 8
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 39
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 229910052702 rhenium Inorganic materials 0.000 description 15
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000002803 maceration Methods 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229940100890 silver compound Drugs 0.000 description 4
- 150000003379 silver compounds Chemical class 0.000 description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- -1 amine compound Chemical class 0.000 description 3
- 150000001412 amines Chemical class 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
- 229910052792 caesium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- AOOCSKCGZYCEJX-OCNDCOMTSA-N argentamine Chemical compound C([C@H]1C[C@@H]2CN3CCC(C[C@H]31)O)N1C2=CC=CC1=O AOOCSKCGZYCEJX-OCNDCOMTSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 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
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- CUPFNGOKRMWUOO-UHFFFAOYSA-N hydron;difluoride Chemical compound F.F CUPFNGOKRMWUOO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001404 mediated effect Effects 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
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a kind of alumina support producing ethylene oxide silver catalyst for ethylene and the silver catalysts made from the carrier, further relate to application of this catalyst in ethylene produces ethylene oxide.The carrier is prepared by the method comprised the steps of：S1. it prepares with the solid mixture formed as follows：A) three water α A12O3, b) and one water A1 of vacation2O3, c) and α A1 of the median particle diameter less than 2 μm2O3Crystal seed, d) α A12O3Particle, e) can after-flame lubriation material, f) alkaline-earth metal compound, then by the solid mixture and g) binder and h) water is mixed to get mixture；S2. the mixture finally obtained in S1 is uniformly mixed, mediates simultaneously extrusion molding；S3. the product obtained in S2 is dried, then roasts, α A1 is made2O3Carrier.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of alumina support and preparation method thereof, and thus carrier
Manufactured silver catalyst and its application.
Background technology
Ethylene oxide is a kind of important petrochemical materials, mainly for the production of ethylene glycol.Ethylene glycol is a kind of oil
Elementary Chemical Industry Organic Ingredients can derive more than 100 kinds of chemical products by it and chemicals, purposes are very extensive.So far,
Silver catalyst is the sole catalyst of industrial production ethylene oxide.Under silver catalyst effect, ethylene mainly generates epoxy
Ethane, while side reaction occurs and generates carbon dioxide and water etc..Activity, selectivity and stability are the main performances of silver catalyst
Index.Wherein activity generally refers to the reaction temperature that process for ethylene oxide production reaches required when certain reaction load, reaction temperature
Degree is lower, and the activity of catalyst is higher；Selectivity refer to reaction in ethylene be converted to ethylene oxide molal quantity and ethylene it is total
React the ratio between molal quantity；And stability is then expressed as the fall off rate of activity and selectivity, fall off rate is smaller, catalyst it is steady
It is qualitative better.Silver catalyst can be mainly divided into three kinds at present, respectively high activity, highly selective and intermediate selectivity is silver-colored urges
Agent.Since petroleum resources scarcity and energy-efficient requirement, highly selective in recent years and intermediate selectivity silver catalyst increasingly are wide
It is general to be applied in industrial production and instead of original high activity silver catalyst.
The performance of silver catalyst is also used with catalyst in addition to having important relationship with the composition of catalyst and preparation method
Carrier property and preparation method have important relationship.For at present, silver catalyst generally selects Alpha-alumina to do carrier.Weigh α-oxygen
The index for changing alumina supporter performance mainly includes specific surface area, Kong Rong, water absorption rate, the crushing strength etc. of carrier.Alpha-alumina supports
Suitable specific surface area provides position for the deposition of active component and auxiliary agent；Suitable pore volume provides suitably for ethylene
Space makes heat of reaction distribute in time；It is negative on carrier that suitable water absorption rate can control active component, catalyst aid
Carrying capacity；Suitable crushing strength can ensure that long-lasting catalytic bears reaction pressure.
The primary raw material for preparing alumina support in the prior art is the hydrate of aluminium oxide, i.e. aluminium hydroxide.Hydroxide
Binder and various additives etc. is added in aluminium, through batch mixing and mediates uniformly, then extrusion molding is most roasted through dry and high temperature afterwards
It burns, the alpha-alumina supports of porous heat-resistant is made.Fluoride-mineralization agent is added in carrier preparation process can promote to roast
Transformation of the transition aluminas to Alpha-alumina in journey.For example, patent CN103566981A adds when prepared by alpha-alumina supports
Enter fluoride-mineralization agent, not only reduces aluminium oxide and turn brilliant temperature, reaming can also be played the role of, obtain macroporous Alpha-alumina
Carrier.Although the above method can improve the performance of alpha-alumina supports, and then improve the performance of silver catalyst, fluoride
Hydrogen fluoride gas is thermally decomposed and is discharged, it is harmful to human body and environment.In addition, patent US2003162984 adds when prepared by carrier
Enter two kinds of Alpha-alumina components, respectively a) the first particle Alpha-alumina of 50-90wt%, average particle size particle size (d50) are
10-100 microns and b) the second particle Alpha-alumina of 10-50wt%, average particle size particle size (d50) are 1-10 microns, are passed through
The microparticle material of particular particle size is selected, the carrier with Advantageous dimensions distribution is prepared.
In view of the situation of the above-mentioned prior art, the present inventor carries out in silver catalyst and its carrier preparation field
Research extensively and profoundly, as a result, it has been found that, under the premise of being added without the mineralizers such as fluoride, alpha-alumina supports are added when preparing
The Alpha-alumina of another particulate forms is added as crystal seed in appropriate Alpha-alumina, can significantly reduce aluminium oxide and turn crystalline substance
Temperature, while the crystalline size and pore structure of finished product carrier are adjusted, ethylene system is used for by silver catalyst prepared by the carrier
When ethylene oxide, activity or selectivity be improved significantly.
Invention content
The object of the present invention is to provide a kind of catalyst carrier, silver is made in load silver and various active components in the carrier
After catalyst, good activity and selectivity is shown during ethylene produces ethylene oxide.The present invention also provides
A kind of application of the silver catalyst and above-mentioned silver catalyst of the carrier in ethylene produces ethylene oxide.
According to an aspect of the invention, there is provided a kind of alpha-oxidation of ethylene production ethylene oxide silver catalyst
Alumina supporter is prepared by the method comprised the steps of：
S1. it prepares with the solid mixture formed as follows：A) the three water α-A1 that median particle diameter is 25-200 μm2O3, b) in
It is worth the one water A1 of vacation that grain size is less than 75 μm2O3, c) and α-A1 of the median particle diameter less than 2 μm2O3Crystal seed, d) median particle diameter be 40-200 μ
α-the A1 of m2O3Particle, e) can after-flame lubriation material, f) alkaline-earth metal compound；
Then by the solid mixture and g) binder and h) water is mixed to get mixture；
S2. the mixture finally obtained in S1 is uniformly mixed, mediates simultaneously extrusion molding；
S3. the product obtained in S2 is dried, then roasts, α-A1 is made2O3Carrier.
According to the present invention, under the premise of being added without the mineralizers such as fluoride, appropriate Alpha-alumina is added when preparing in carrier
As crystal seed, while the Alpha-alumina of another particulate forms is added, aluminium oxide can be significantly reduced and turn brilliant temperature, adjusted simultaneously
The crystalline size and pore structure of finished product carrier.Ring is produced to ethylene according to silver catalyst made of carrier provided by the invention
The reaction of oxidative ethane improves selectivity, and active higher advantage.
According to the present invention, the three water α-A12O3Dehydration turns crystalline substance into α-A1 in high-temperature calcination process2O3.Three water α-A12O3
Addition be 10-85wt%, such as 15-55wt%.
According to the present invention, one water A1 of vacation2O3It is reacted with acid in acid adding kneading process, is converted to colloidal sol, played binder and make
With being also translated into stable α-A1 in high-temperature calcination process2O3, become α-A12O3A part for carrier.With solid mixture
A)-f) total weight, one water A1 of vacation2O3Addition is 5-55wt%, such as 30-40wt%.
According to the present invention, α-A12O3Crystal grain and α-A12O3Aluminium oxide can be reduced by, which being added while particle, turns brilliant temperature, together
When adjust finished product carrier crystalline size and pore structure.α-the A12O3The median particle diameter of crystal seed is less than 2 μm, preferably smaller than 1 μm.
With solid mixture a)-f) total weight, the α-A12O3The addition of crystal seed be 0.1-10wt%, preferably 0.5-5wt%,
Such as it is 2.5-5wt%.α-the A1 that the particulate forms are added2O3Median particle diameter is 40-200 μm, preferably 40~150 μm.With solid
Body mixture a)-f) total weight, α-A12O3The addition of particle is 5-40wt%, preferably 10-40wt%, such as 10-
20wt%.In above-mentioned range, the catalyst of obtained carrier preparation has higher selectivity.Wherein, in the α-
A12O3Seed charge is 2.5-5wt%, α-A12O3When the dosage of particle is 10-20wt%, the catalysis of obtained carrier preparation
Agent has the selectivity of lower reaction temperature and raising, namely improves reactivity and selectivity simultaneously.The α-
A12O3Uniform particle is dispersed in carrier matrix.
According to the present invention, can after-flame lubriation material be added to make the material after kneading be easy to be molded and be granulated, together
When occur oxidation reaction in material roasting process, generate gas effusion, do not introduce when carrier is made or draw as few as possible
Into impurity, to not influence the performance of catalyst.It is described can after-flame lubriation material preferably be selected from petroleum coke, carbon dust, graphite, vaseline
One or more of mixtures.It is described can after-flame lubriation material addition be solid mixture total weight 0.01-
5.0wt%, preferably 0.01-4.0wt%, such as 1-2wt%.
According to the present invention, the effect of the compound of the alkaline-earth metal is to be improved carrier property.The alkaline earth
The compound of metal can be oxide, nitrate, acetate, oxalates or the sulfate of strontium and/or barium.The alkaline-earth metal
Compound addition be solid mixture gross mass 0.01-5.0wt%, preferably 0.05-2.0wt%.
According to the present invention, the one water A1 of vacation in binder and mixture is added2O3Aluminum sol is generated, each component is bonded in
Together, become extrudable molding paste.Binder used includes acid, preferably aqueous solution of nitric acid, the aqueous solution of nitric acid
The weight ratio of middle nitric acid and water is 1:1.25-1:10.It is to make mixing, kneading etc. be more prone to carry out that water, which is added, and amount is suitable
Amount.The amount of water is also finally in the water of aqueous solution of nitric acid.
A preferred embodiment according to the present invention, the binder and one water A1 of vacation2O3Can with Aluminum sol all or
Part replaces.Instead of when, by control Aluminum sol in aluminium oxide aluminium content to control the addition of Aluminum sol.
According to the present invention, the solid mixture is mediated to obtain a kind of paste with binder, and then paste squeezes
It can be dried to aqueous 10% after going out molding hereinafter, support shapes can be annular, spherical, cylindricality or porous column shape.Drying temperature
It it is 80-120 DEG C, drying time controls according to moisture at 1-24 hours.
According to the present invention, the roasting in the step S3 makes aluminium oxide be completely converted into α-A12O3.The roasting time is
1-20 hours, preferably 2-15 hours.The calcination temperature is 900-1500 DEG C.
In the present invention, the α-A1 of carrier2O3Content is measured by XRD；Side crush intensity uses II type intelligence particles of DL
Intensity measuring device chooses support samples, is averaged to obtain after measuring radial crushing strength；Water absorption rate is measured by densimetry；
Specific surface area is measured using nitrogen physisorption BET methods；Kong Rong is measured using pressure mercury method；Crystalline size refers to passing through scanning
Electron microscope estimates size of the alumina support by sol-gel technology generating portion.Carrier according to the present invention,
α-A12O3Content >=95%, crushing strength are 30-240N/, specific surface 0.3-3.0m2/ g, water absorption rate >=30%, Kong Rongwei
0.30-0.90ml/g, average crystalline size are 0.2-10 μm.
According to the carrier that the present invention obtains, including two kinds of Alpha-aluminas, wherein the first Alpha-alumina component pass through addition
The sol-gel technology of the Alpha-alumina crystal seed of appropriate small size generates, and the sol-gel is by a water aluminium oxide and three water oxygens
Change aluminium to be formed；And second of Alpha-alumina component then exists in the form of alpha-alumina particle, is dispersed in carrier matrix.
According to another aspect of the present invention, a kind of ethylene production ethylene oxide silver catalyst is additionally provided,
Include loading silver or load silver and auxiliary agent in the alpha-alumina supports and being made.The auxiliary agent can be this field
Interior auxiliary agent used, such as alkali metal or alkaline-earth metal, the compound based on alkali metal and/or alkaline-earth metal, rhenium metal, is based on
It is one or more in compound of rhenium etc..When the auxiliary agent rhenium-containing, the collaboration auxiliary element of rhenium can also be included simultaneously, such as
One or more metals in chromium, molybdenum, tungsten and manganese, and/or selected from based on one or more members in chromium, molybdenum, tungsten and manganese
The compound of element.
In a specific example, the ethylene epoxidizing silver catalyst, including：A) above-mentioned Alpha-alumina carries
Body；B) silver of deposition on this carrier；C) alkali metal and/or alkaline-earth metal or the chemical combination based on alkali metal and/or alkaline-earth metal
Object；D) rhenium metal and/or the compound based on rhenium；And e) the collaboration auxiliary element of rhenium, one in chromium, molybdenum, tungsten and manganese
Kind or various metals, and/or selected from the compound based on one or more elements in chromium, molybdenum, tungsten and manganese.In silver catalyst,
The mass content of total weight based on catalyst, the silver is 5~37%, preferably 8~32%；Alkali metal mass content be 5~
3000ppm, preferably 10~2000ppm；The mass content of alkaline-earth metal is 50~20000ppm, preferably 100~15000ppm；Rhenium
The mass content of metal is 10~2000ppm, preferably 100~1500ppm；Coassist agent content is calculated as 0 with the metal in coassist agent
~1500ppm, preferably 0~1000ppm.
The present invention silver catalyst can prepare in the usual way, by with a kind of Ag-containing compound, organic amine, auxiliary agent (such as
Alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent and its optional coassist agent) solution impregnate above-mentioned alumina support to make
It is standby.The organic amine compound can be any organic amine compound suitable for preparing ethylene oxide silver catalyst, as long as
The organic amine compound can with silver compound formed argent-amine complex, as pyridine, butylamine, ethylenediamine, 1,3- propane diamine,
Or mixtures thereof ethanol amine.The alkali metal promoter can be compound or its change of any one of lithium, sodium, potassium, rubidium or caesium
Object is closed, such as the arbitrary group of two or more of their nitrate, sulfate or hydroxide or aforesaid compound
It closes, preferably sulfuric acid caesium and/or cesium nitrate.The base earth metal promoter can be the compound of magnesium, calcium, strontium or barium, such as them
The arbitrary combination of two or more of oxide, oxalates, sulfate, acetate or nitrate or aforesaid compound,
It is preferred that the compound of barium or strontium, more preferable barium acetate and/or strontium acetate.The base earth metal promoter can before immersion silver, it is same
When or be applied on carrier later, can also be immersed on carrier after silver compound is reduced.The rhenium auxiliary agent can be
Or mixtures thereof oxide, perrhenic acid, the perrhenate of rhenium, preferably perrhenic acid and perrhenate, such as perrhenic acid, perrhenic acid
Caesium and ammonium perrhenate etc..The coassist agent of the rhenium auxiliary agent can be the compound of any transition metal or several in the periodic table of elements
The mixture of transistion metal compound, one or more metals in preferred chromium, molybdenum, tungsten and manganese are planted, and/or are based on chromium, molybdenum, tungsten
With the compound of one or more elements in manganese, such as chromic acid, chromic nitrate, wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate, mangaic acid and
Potassium permanganate etc..Rhenium auxiliary agent and its coassist agent can be applied to prior to, concurrently with, or after immersion silver on carrier, can also be in silver
Compound is immersed in after being reduced on carrier.Gained silver can be further improved by the way that rhenium auxiliary agent and its coassist agent is added to be catalyzed
The activity of agent, the stability of selectivity and activity and selectivity.
In a specific embodiment, silver catalyst preparation method includes the following steps：
1) with silver compound, organic amine, auxiliary agent (such as alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent containing sufficient amount
And its coassist agent) solution impregnate above-mentioned porous alpha-alumina supports；
2) maceration extract, dry impregnated carrier are filtered off；With
3) step 2) resulting vehicle is activated in containing oxygen gas mixture, the silver catalyst is made.
In the preparation of silver catalyst of the present invention, is mixed with ammonium oxalate solution with silver nitrate generate silver oxalate, oxalic acid first
Silver is dissolved in organic amine and argentamine liquid is made, and adds above-mentioned auxiliary agent and is made into maceration extract；Then it is impregnated with the maceration extract prepared above-mentioned
Alpha-alumina supports drain, in air stream or oxygen content no more than 21% (in 180 in the nitrogen oxygen atmosphere of such as oxygen-containing 8.0%)
It is kept within the temperature range of~700 DEG C preferably 200~500 DEG C 0.5~120 minute, carries out within preferably 1~60 minute thermal decomposition and be made
Finished product silver catalyst.
According to another aspect of the present invention, a kind of method of ethylene production ethylene oxide is additionally provided, it is described
Ethylene carries out epoxidation reaction in reaction unit in the presence of above-mentioned carrier or silver catalyst, generates ethylene oxide.Institute
It can be any device that can carry out epoxidation reaction to state reaction unit.
According to the present invention, under the premise of being added without the mineralizers such as fluoride, appropriate Alpha-alumina is added when preparing in carrier
As crystal seed, while the Alpha-alumina of another particulate forms is added, aluminium oxide can be significantly reduced and turn brilliant temperature, adjusted simultaneously
The crystalline size and pore structure of finished product carrier.Compared with the prior art, according to silver catalyst made of carrier provided by the invention
The advantages of reaction to ethylene production ethylene oxide, active and high selectivity.
Specific implementation mode
The present invention is described further with reference to embodiment, but the scope of the invention is not limited to these embodiments.
It is primality that the various silver catalysts of the present invention with laboratory reactor (following letter " micro- anti-") evaluating apparatus test its
Energy and stability.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating mantle.It urges
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 is as follows：
Reaction gas forms (mol%)
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity as follows after shrinking correction：
Wherein Δ EO is to work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, takes the average conduct of 10 groups or more test datas
The test result on the same day.
Carrier prepares comparative example 1
By 25~200 μm of three water α-A12O32400g is less than 75 μm of one water A1 of vacation2O31500g, NH4F 122g and
Barium nitrate 40g is put into blender and is uniformly mixed, and is transferred in kneader, and 60g vaseline and 2100ml dust technology (nitric acid is added：
Water=1：5, weight ratio), it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter
The seven apertures in the human head column of 1.0mm is dried 2 hours or more at 80~120 DEG C, and free water content is made to be reduced to 10% or less.It will be upper
State it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1100 DEG C from room temperature through 33 hours, 5 calcined under the conditions of 1100 DEG C
Hour, obtain white support.The carrier physical property measured is as shown in table 1 below.
Carrier prepares comparative example 2
By 25~200 μm of three water α-A12O31600g is less than 75 μm of one water A1 of vacation2O31500g, 40~200 μm
α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred in kneader, and 60g vaseline and 2100ml is added
Dust technology (nitric acid：Water=1：5, weight ratio), it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, length
The seven apertures in the human head column of 6.0mm, internal diameter 1.0mm are dried 2 hours or more at 80~120 DEG C, and free water content is made to be reduced to 10%
Below.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, 1100 DEG C were increased to from room temperature through 33 hours, in 1100 DEG C of items
It is calcined 5 hours under part, obtains white support.The carrier physical property measured is as shown in table 1 below.Under conditions of being not added with mineralizer, adopt
With low calcination temperature, the content of the Alpha-alumina in carrier is very low, and obtained catalyst performance is very poor, can not be used as normal
Catalyst carrier uses, therefore does not provide the surface property parameter of carrier again.
Carrier prepares comparative example 3
By 25~200 μm of three water α-A12O31600g is less than 75 μm of one water A1 of vacation2O31500g, 40~200 μm
α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred in kneader, and 60g vaseline and 2100ml is added
Dust technology (nitric acid：Water=1：5, weight ratio), it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, length
The seven apertures in the human head column of 6.0mm, internal diameter 1.0mm are dried 2 hours or more at 80~120 DEG C, and free water content is made to be reduced to 10%
Below.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, 1400 DEG C were increased to from room temperature through 36 hours, in 1400 DEG C of items
It is calcined 5 hours under part, obtains white support.The carrier physical property measured is as shown in table 1 below.
Carrier prepares comparative example 4
By 25~200 μm of three water α-A12O31580g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 20g, 2~10 μm of α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneader
In, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste.
Extrusion molding is the seven apertures in the human head column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, is dried 2 hours or more at 80~120 DEG C,
Free water content is set to be reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature
1100 DEG C are increased to, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.The carrier physical property measured is as shown in table 1 below.
Carrier prepares embodiment 1
By 25~200 μm of three water α-A12O31580g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 20g, 40~200 μm of α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneader
In, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste.
Extrusion molding is the seven apertures in the human head column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, is dried 2 hours or more at 80~120 DEG C,
Free water content is set to be reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room temperature
1100 DEG C are increased to, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.The carrier physical property measured is as shown in table 1 below.
Carrier prepares embodiment 2
By 25~200 μm of three water α-A12O31500g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 100g, 40~200 μm of α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneading
In machine, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste
Object.Extrusion molding be outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm seven apertures in the human head column, dried at 80~120 DEG C 2 hours with
On, so that free water content is reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room
Temperature is increased to 1100 DEG C, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.Following 1 institute of table of carrier physical property measured
Show.
Carrier prepares embodiment 3
By 25~200 μm of three water α-A12O31400g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 200g, 40~200 μm of α-A12O3800g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneading
In machine, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste
Object.Extrusion molding be outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm seven apertures in the human head column, dried at 80~120 DEG C 2 hours with
On, so that free water content is reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room
Temperature is increased to 1100 DEG C, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.Following 1 institute of table of carrier physical property measured
Show.
Carrier prepares embodiment 4
By 25~200 μm of three water α-A12O31900g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 100g, 40~200 μm of α-A12O3400g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneading
In machine, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste
Object.Extrusion molding be outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm seven apertures in the human head column, dried at 80~120 DEG C 2 hours with
On, so that free water content is reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room
Temperature is increased to 1100 DEG C, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.Following 1 institute of table of carrier physical property measured
Show.
Carrier prepares embodiment 5
By 25~200 μm of three water α-A12O3700g is less than 75 μm of one water A1 of vacation2O31500g is less than 2 μm of α-
A12O3Crystal seed 100g, 40~200 μm of α-A12O31600g and barium nitrate 40g is put into blender and is uniformly mixed, and is transferred to kneading
In machine, 60g vaseline and 2100ml dust technology (nitric acid is added：Water=1：5, weight ratio), it is kneaded into extrudable molding paste
Object.Extrusion molding be outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm seven apertures in the human head column, dried at 80~120 DEG C 2 hours with
On, so that free water content is reduced to 10% or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours from room
Temperature is increased to 1100 DEG C, is calcined 5 hours under the conditions of 1100 DEG C, obtains white support.Following 1 institute of table of carrier physical property measured
Show.
The preparation of catalyst
Silver catalyst is prepared as carrier using comparative example 1,3,4 and embodiment 1-5, preparation method is as follows：Wherein, it compares
The content of example 2, the Alpha-alumina in carrier is very low.Those skilled in the art know that the content of the Alpha-alumina in carrier is low, obtain
The performance of the catalyst arrived is excessively poor, therefore does not provide the specific performance data of the comparative example catalyst that 2 carrier obtains again.
It weighs 140g silver nitrates to be dissolved in 150ml deionized waters, weighs 64g ammonium oxalate and be dissolved in 520ml deionized waters, fill
Divide dissolving, obtain silver nitrate solution and ammonium oxalate solution, mix two kinds of solution with vigorous stirring, generates white silver oxalate and sink
It forms sediment, aging 30 minutes or more, filtering is washed with deionized and is precipitated to no nitrate ion.Filter cake argentiferous about 60%, it is aqueous about
15%.
70.0g ethylenediamines are dissolved in 75.0g deionized waters, silver oxalate filter cake prepared by the above method is added, persistently stirs
Mixing makes silver oxalate all dissolve, and sequentially adds 2.58g cesium nitrates, 6.22g barium acetates, 0.86g ammonium perrhenates and deionized water
So that solution gross mass is reached 400g, it is for use to be configured to maceration extract.
Support samples 20g is taken, is put into the container that can be vacuumized, is evacuated to 10mmHg or more, introduces above-mentioned maceration extract,
30min, leaching is kept to remove extra solution.Carrier after dipping heats 3min in 450 DEG C of air stream, cooling, that is, is made
Silver catalyst.Silver catalyst number is consistent with corresponding carrier.
The activity and selectivity of catalyst sample is measured under the conditions of previous process using microreactor evaluating apparatus, it is micro-
Anti- evaluation result is listed in table 2.
The physical data of 1 carrier of table
The performance of 2 catalyst of table
From the prior art it is known that under conditions of being not added with mineralizer it can be seen from data in table 1 and 2, need
High calcination temperature (comparative example 2 and 3).However technique can obtain the load under lower calcination temperature in the application
Body.Meanwhile according to using the carrier in the application, Kong Rong and water absorption rate is improved, the crystal that sol-gel method obtains is reduced
Partial average crystalline size；Meanwhile carrier has high specific surface area and crushing strength.In other words, according to the present invention,
Under the premise of being added without the mineralizers such as fluoride, appropriate Alpha-alumina is added as crystal seed when preparing in carrier, while being added another
The Alpha-alumina of kind of particulate forms can significantly reduce aluminium oxide and turn brilliant temperature, at the same adjust finished product carrier crystalline size and
Pore structure.In addition, catalyst made from support according to the present invention, substantially increases the selectivity of catalyst.Meanwhile reacting temperature
Degree is fine, and illustrating catalyst still has preferable activity.
Any numerical value mentioned in the present invention, if between any minimum and any of the highest value be there are two
The interval of unit includes then each all values for increasing a unit from minimum to peak.For example, if statement is a kind of
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
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.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (12)
1. a kind of alpha-alumina supports of ethylene production ethylene oxide silver catalyst, pass through the side comprised the steps of
It is prepared by method：
S1. it prepares with the solid mixture formed as follows：A) the three water α-Al that median particle diameter is 25-200 μm2O3, b) and intermediate value grain
Diameter is less than 75 μm of one water Al of vacation2O3, c) and α-Al of the median particle diameter less than 2 μm2O3Crystal seed, d) median particle diameter is 40-200 μm
α-Al2O3Particle, e) can after-flame lubriation material, f) alkaline-earth metal compound, then by the solid mixture and g) binder
And h) water is mixed to get mixture；
S2. the mixture finally obtained in S1 is uniformly mixed, mediates simultaneously extrusion molding；
S3. the product obtained in S2 is dried, then roasts, α-Al is made2O3Carrier.
2. carrier according to claim 1, which is characterized in that with the total weight of solid mixture, three water α-Al2O3's
Dosage is 10-85wt%, one water Al of vacation2O3Dosage be 5-55wt%；α-Al2O3The dosage of crystal seed is 0.1-10wt%；α-
Al2O3The dosage of particle is 5-40wt%；Can after-flame lubriation material dosage be 0.01-5.0wt%；The compound of alkaline-earth metal
Dosage be 0.01-5.0wt%；The addition of binder is 25-60wt%.
3. carrier as claimed in claim 1 or 2, which is characterized in that the α-Al2O3The median particle diameter of crystal seed is less than 1 μm；It is excellent
Select the α-Al2O3Seed charge is the 0.5-5wt%, further preferably 2.5-5wt% of solid mixture total weight.
4. the carrier as described in any one of claim 1-3, which is characterized in that the α-Al2O3The median particle diameter of particle is excellent
It is selected as 40-150 μm；And/or with the total weight of solid mixture, the α-Al2O3The dosage of particle is preferably 10-40wt%,
Further preferably 10-20wt%.
5. the carrier as described in any one of claim 1-4, which is characterized in that it is described can after-flame lubriation material be oil
One or more of mixtures of coke, carbon dust, graphite and vaseline, preferably its addition are solid mixture total weight
0.01-4.0wt%.
6. the carrier as described in any one of claim 1-5, which is characterized in that the compound of the alkaline-earth metal is strontium
And/or oxide, nitrate, acetate, oxalates or the sulfate of barium, preferably its addition is solid mixture total weight
0.05-2.0wt%.
7. the carrier as described in any one of claim 1-6, which is characterized in that the binder is acid, preferably nitric acid aqueous solution
Solution, the weight ratio of nitric acid and water is 1 in the aqueous solution of nitric acid:1.25-1:10.
8. the carrier as described in any one of claim 1-7, which is characterized in that be free of mine in mixture prepared by step S1
Agent；And/or the calcination temperature is 900-1500 DEG C.
9. the carrier as described in any one of claim 1-8, which is characterized in that the binder and one water Al of vacation2O3It can use
Aluminum sol completely or partially replaces.
10. carrier as claimed in any one of claims 1-9 wherein, which is characterized in that α-Al2O3Content >=95%, crushing strength are
30-240N/, specific surface 0.3-3.0m2/ g, water absorption rate >=30%, Kong Rongwei 0.30-0.90ml/g, average crystalline size
It is 0.2-10 μm.
11. a kind of ethylene produces ethylene oxide silver catalyst, it is included in described in any one of claim 1-10
Silver or load silver and auxiliary agent are loaded in alpha-alumina supports and are made.
12. a kind of method of ethylene production ethylene oxide, including ethylene in ethylene in reaction unit, in claim 1-
Oxidation reaction is carried out under the action of the catalyst described in carrier or claim 11 described in any one of 10, obtains epoxy second
Alkane.
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| CN201611127131.1A CN108607533B (en) | 2016-12-09 | 2016-12-09 | Alumina carrier, catalyst and application |
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| CN201611127131.1A CN108607533B (en) | 2016-12-09 | 2016-12-09 | Alumina carrier, catalyst and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437887A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | α -alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN114433045A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
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| US5929259A (en) * | 1996-06-05 | 1999-07-27 | Shell Oil Company | Preparation of ethylene oxide and catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437887A (en) * | 2019-01-16 | 2020-07-24 | 中国石油化工股份有限公司 | α -alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN111437887B (en) * | 2019-01-16 | 2023-03-14 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN114433045A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN114433045B (en) * | 2020-11-05 | 2023-07-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
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| CN108607533B (en) | 2020-12-18 |
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