CN108607533B - Alumina carrier, catalyst and application - Google Patents
Alumina carrier, catalyst and application Download PDFInfo
- Publication number
- CN108607533B CN108607533B CN201611127131.1A CN201611127131A CN108607533B CN 108607533 B CN108607533 B CN 108607533B CN 201611127131 A CN201611127131 A CN 201611127131A CN 108607533 B CN108607533 B CN 108607533B
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- Prior art keywords
- carrier
- alpha
- amount
- mixture
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 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 56
- 229910052709 silver Inorganic materials 0.000 claims abstract description 50
- 239000004332 silver Substances 0.000 claims abstract description 50
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005977 Ethylene Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000008247 solid mixture Substances 0.000 claims abstract description 18
- 150000004684 trihydrates Chemical class 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 230000001050 lubricating effect Effects 0.000 claims abstract description 7
- 238000004898 kneading Methods 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000013598 vector Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims 2
- 239000004264 Petrolatum Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 229940066842 petrolatum Drugs 0.000 claims 1
- 235000019271 petrolatum Nutrition 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 description 23
- 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 16
- 229910052702 rhenium Inorganic materials 0.000 description 14
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 13
- 239000000969 carrier Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 10
- 229940099259 vaseline Drugs 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- -1 rhenium metals Chemical class 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 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
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 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 4
- 239000000047 product Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 3
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 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
- 238000003556 assay Methods 0.000 description 1
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 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
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 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
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling 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
- 239000008187 granular material Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 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
- 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
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 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
- 239000012495 reaction gas Substances 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
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
-
- 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
-
- 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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to an alumina carrier of a silver catalyst for producing ethylene oxide by oxidizing ethylene, a silver catalyst prepared from the alumina carrier, and application of the catalyst in producing ethylene oxide by oxidizing ethylene. The carrier prepared by a process comprising the steps of: s1, preparing a solid mixture with the following composition: a) trihydrate alpha-A12O3B) pseudo-water A12O3C) a-A1 having a median particle diameter of less than 2 μm2O3Seed crystals, d) alpha-A12O3Particles, e) burnable lubricating material, f) compound of alkaline earth metal, then mixing the solid mixture with g) binder and h) water to obtain a mixture; s2, uniformly mixing, kneading and extruding the mixture finally obtained in the step S1 to form; s3, drying the product obtained in the S2, and then roasting to prepare alpha-A12O3And (3) a carrier.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an alumina carrier and a preparation method thereof, and a silver catalyst prepared from the carrier and application thereof.
Background
Ethylene oxide is an important petrochemical raw material and is mainly used for producing ethylene glycol. Ethylene glycol is a basic organic raw material of petrochemical industry, more than 100 chemical products and chemicals can be derived from the ethylene glycol, and the application is very wide. To date, silver catalysts have been the only catalyst for the commercial production of ethylene oxide. Under the action of silver catalyst, ethylene is oxidized to produce ethylene oxide, and side reaction to produce carbon dioxide, water, etc. Activity, selectivity and stability are the main performance indicators of silver catalysts. Wherein the activity generally refers to the reaction temperature required when the ethylene oxide production process reaches a certain reaction load, and the lower the reaction temperature is, the higher the activity of the catalyst is; selectivity refers to the ratio of moles of ethylene converted to ethylene oxide in the reaction to the total reacted moles of ethylene; stability is expressed as the rate of decline of activity and selectivity, the smaller the rate of decline, the better the catalyst stability. At present, the silver catalyst can be mainly divided into three types, namely, the silver catalyst with high activity, high selectivity and medium selectivity. Because of the increasing shortage of petroleum resources and the requirement of energy conservation, silver catalysts with high selectivity and medium selectivity are widely applied to industrial production in recent years and replace the original high-activity silver catalysts.
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 by the catalyst and the preparation method. Currently, alpha-alumina is generally used as a carrier for silver catalysts. The indexes for measuring the performance of the alpha-alumina carrier mainly comprise the specific surface area, the pore volume, the water absorption, the crushing strength and the like of the carrier. The appropriate specific surface area of the alpha-alumina carrier provides a position for deposition of active components and auxiliaries; the appropriate pore volume provides appropriate space for ethylene oxidation, so that the reaction heat can be dissipated in time; the appropriate water absorption rate can control the loading amount of the active component and the catalytic promoter on the carrier; the appropriate crush strength ensures that the catalyst will withstand the reaction pressure for a long period of time.
The main raw material for preparing the alumina carrier in the prior art is alumina hydrate, namely aluminum hydroxide. Adding a binder, various additives and the like into aluminum hydroxide, mixing and kneading uniformly, then extruding and molding, and finally drying and roasting at high temperature to prepare the porous heat-resistant alpha-alumina carrier. The addition of fluoride mineralizers during the preparation of the support may promote the transition phase alumina to alpha-alumina conversion during calcination. For example, patent CN103566981A adds a fluoride mineralizer during the preparation of α -alumina carrier, not only reducing the temperature of alumina crystal transition, but also playing the role of pore-enlarging, so as to obtain a large-pore α -alumina carrier. Although the above method can improve the performance of the α -alumina carrier and thus the silver catalyst, the fluoride is decomposed by heat and releases hydrogen fluoride gas, which is harmful to the human body and the environment. In addition, patent US2003162984 adds two alpha-alumina components in the preparation of the support, a) 50-90% by weight of a first particulate alpha-alumina having an average particle size (d50) of 10-100 microns, and b) 10-50% by weight of a second particulate alpha-alumina having an average particle size (d50) of 1-10 microns, by selecting particulate materials of a particular particle size, a support having an advantageous size distribution is prepared.
In view of the above-mentioned state of the art, the inventors of the present invention have conducted extensive and intensive studies in the field of preparation of silver catalysts and carriers thereof, and as a result, have found that, on the premise of not adding mineralizers such as fluoride, when an α -alumina carrier is prepared, an appropriate amount of α -alumina is added as a seed crystal, and at the same time, another particle form of α -alumina is added, the crystal transition temperature of alumina can be significantly reduced, and simultaneously the crystal size and pore structure of the finished carrier are adjusted, and when the silver catalyst prepared from the carrier is used for preparing ethylene oxide by oxidizing ethylene, the activity or selectivity is significantly improved.
Disclosure of Invention
The invention aims to provide a catalyst carrier which shows good activity and selectivity in the process of producing ethylene oxide by oxidizing ethylene after a silver catalyst is prepared by loading silver and various active components. The invention also provides a silver catalyst of the carrier and application of the silver catalyst in producing ethylene oxide by oxidizing ethylene.
According to one aspect of the present invention, there is provided an α -alumina support for a silver catalyst for ethylene oxidation to produce ethylene oxide, prepared by a method comprising the steps of:
s1, preparing a solid mixture with the following composition: a) trihydrate alpha-A1 with median particle size of 25-200 mu m2O3B) pseudo-monohydrate A1 having a median particle size of less than 75 μm2O3C) a-A1 having a median particle diameter of less than 2 μm2O3Seed crystal, d) alpha-A1 having a median particle diameter of 40 to 200 [ mu ] m2O3Particles, e) burnable lubricating material, f) compounds of alkaline earth metals;
then mixing the solid mixture with g) a binder and h) water to obtain a mixture;
s2, uniformly mixing, kneading and extruding the mixture finally obtained in the step S1 to form;
s3, drying the product obtained in the S2, and then roasting to prepare alpha-A12O3And (3) a carrier.
According to the invention, on the premise of not adding mineralizers such as fluoride and the like, a proper amount of alpha-alumina is added as a seed crystal during the preparation of the carrier, and simultaneously, the alpha-alumina in another particle form is added, so that the crystal transformation temperature of the alumina can be obviously reduced, and the crystal size and the pore structure of the finished carrier can be adjusted. The silver catalyst prepared by the carrier provided by the invention improves the selectivity of the reaction for producing ethylene oxide by oxidizing ethylene and has the advantage of higher activity.
According to the invention, the trihydrate a-a 12O3Dehydration and crystal transformation into alpha-A1 in the high-temperature roasting process2O3. Trihydrate alpha-A12O3Is added in an amount of 10-85wt%, such as 15-55 wt%.
According to the invention, pseudo-water A12O3Reacting with acid during acid kneading to obtain sol, and stickingThe binder is also converted into stable alpha-A1 in high-temperature roasting process2O3To alpha-A12O3A portion of a carrier. Pseudo-monohydrate A1 based on the total weight of the solid mixtures a) to f)2O3The amount added is 5-55wt%, such as 30-40 wt%.
According to the invention, alpha-A12O3Grain and alpha-A12O3The simultaneous addition of the particles can reduce the crystal transformation temperature of the alumina and simultaneously adjust the crystal size and the pore structure of the finished product carrier. The alpha-A12O3The median particle size of the seed crystals is less than 2 μm, preferably less than 1 μm. The alpha-A1 being based on the total weight of the solid mixture a) to f)2O3The seed crystals are added in an amount of 0.1 to 10 wt.%, preferably 0.5 to 5 wt.%, e.g., 2.5 to 5 wt.%. alpha-A1 added in the form of particles2O3The median particle diameter is 40-200 μm, preferably 40-150 μm. Based on the total weight of the solid mixtures a) to f), a-A12O3The particles are added in an amount of 5-40 wt.%, preferably 10-40 wt.%, such as 10-20 wt.%. Within the above range, the resulting supported catalyst has higher selectivity. Wherein, in the alpha-A12O3The crystal seed addition is 2.5-5wt%, alpha-A12O3When the amount of the particles is 10 to 20wt%, the catalyst prepared from the obtained carrier has lower reaction temperature and improved selectivity, namely, the reaction activity and the selectivity are improved at the same time. The alpha-A12O3The particles are uniformly dispersed in the carrier matrix.
According to the invention, the combustible lubricating material is added to make the kneaded material easy to form and granulate, meanwhile, oxidation reaction occurs during the roasting process of the material, generated gas escapes, and impurities are not introduced or introduced as little as possible during the preparation of the carrier, so that the performance of the catalyst is not influenced. The burnout lubricating material is preferably one or a mixture of petroleum coke, carbon powder, graphite and vaseline. The burnout lubricating material is added in an amount of 0.01 to 5.0wt%, preferably 0.01 to 4.0wt%, such as 1 to 2 wt%, based on the total weight of the solid mixture.
According to the invention, the compound of the alkaline earth metal serves to improve the properties of the support. The compound of the alkaline earth metal may be an oxide, nitrate, acetate, oxalate or sulfate of strontium and/or barium. The alkaline earth metal compound is added in an amount of 0.01 to 5.0wt%, preferably 0.05 to 2.0wt%, based on the total mass of the solid mixture.
According to the invention, pseudo-monohydrate A1 is added to the binder and the mixture2O3Generating aluminum sol, and bonding the components together to form paste which can be extruded and molded. The binder used comprises an acid, preferably an aqueous nitric acid solution, the weight ratio of nitric acid to water in the aqueous nitric acid solution being from 1:1.25 to 1: 10. Water is added in an appropriate amount to facilitate mixing, kneading, etc. The amount of water can also be calculated in water of aqueous nitric acid.
According to a preferred embodiment of the invention, said binder and pseudo-monohydrate A12O3The aluminum sol can be used in place of all or part of the aluminum sol. Instead, the amount of alumina sol added is controlled by controlling the alumina content in the alumina sol.
According to the invention, the solid mixture is kneaded with a binder to give a paste, which is then extruded and dried to a moisture content of less than 10%, the support being in the form of a ring, sphere, cylinder or porous cylinder. The drying temperature is 80-120 deg.C, and the drying time is controlled at 1-24 hr according to the water content.
According to the invention, the calcination in said step S3 converts all the alumina to alpha-A12O3. The calcination time is 1 to 20 hours, preferably 2 to 15 hours. The roasting temperature is 900-1500 ℃.
In the present invention, the alpha-A1 of the carrier2O3The content is measured by XRD; selecting a carrier sample by adopting a DL II type intelligent particle strength tester for the lateral crushing strength, measuring the radial crushing strength, and then averaging to obtain the radial crushing strength; the water absorption is measured by a density method; the specific surface area is measured by adopting a nitrogen physical adsorption BET method; the pore volume is measured by a mercury intrusion method; the crystal size refers to the size of the portion of the alumina support produced by the sol-gel process as estimated by scanning electron microscopy. According to the inventionThe vector, alpha-A12O3The content is more than or equal to 95 percent, the crushing strength is 30-240N/grain, and the specific surface is 0.3-3.0m2The water absorption is more than or equal to 30 percent, the pore volume is 0.30 to 0.90ml/g, and the average crystal size is 0.2 to 10 mu m.
The support obtained according to the invention comprises two alpha-aluminas, wherein the first alpha-alumina component is produced by a sol-gel process with the addition of a suitable amount of small-sized alpha-alumina seeds, said sol-gel being formed from alumina monohydrate and alumina trihydrate; and the second alpha-alumina component is present as alpha-alumina particles, uniformly dispersed in the carrier matrix.
According to another aspect of the invention, the silver catalyst for producing ethylene oxide by ethylene oxidation is prepared by loading silver or silver and an auxiliary agent on the alpha-alumina carrier. The promoter may be one or more of the promoters used in the art, such as alkali metals, alkali earth metals, alkali metal and/or alkali earth metal based compounds, rhenium metals, rhenium based compounds, and the like. When the promoter contains rhenium, it may also contain rhenium co-promoter elements, such as one or more metals selected from chromium, molybdenum, tungsten and manganese, and/or from compounds based on one or more elements of chromium, molybdenum, tungsten and manganese.
In a specific example, the silver catalyst for ethylene epoxidation comprises: a) the above-mentioned α -alumina carrier; b) silver deposited on the carrier; c) alkali and/or alkaline earth metals or compounds based on alkali and/or alkaline earth metals; d) rhenium metal and/or rhenium-based compounds; and e) a co-promoter element of rhenium, selected from one or more metals of chromium, molybdenum, tungsten and manganese, and/or from compounds based on one or more elements of chromium, molybdenum, tungsten and manganese. In the silver catalyst, the mass content of the silver is 5-37%, preferably 8-32% based on the total weight of the catalyst; the mass content of alkali metal is 5-3000 ppm, preferably 10-2000 ppm; the mass content of the alkaline earth metal is 50-20000 ppm, preferably 100-15000 ppm; the mass content of rhenium metal is 10-2000 ppm, preferably 100-1500 ppm; the content of the co-promoter is 0-1500 ppm, preferably 0-1000 ppm, calculated as the metal in the co-promoter.
The silver catalysts of the present invention may be prepared in conventional manner by impregnating the above-described alumina support with a solution containing a silver compound, an organic amine, and an auxiliary agent (e.g., an alkali metal auxiliary agent, an alkaline earth metal auxiliary agent, a rhenium-containing auxiliary agent, and optionally a co-auxiliary agent). The organic amine compound may be any organic amine compound suitable for preparing a silver catalyst for ethylene oxide production, as long as the organic amine compound is capable of forming a silver amine complex with a silver compound, such as pyridine, butylamine, ethylenediamine, 1, 3-propylenediamine, ethanolamine, or a mixture thereof. The alkali metal promoter may be a compound of lithium, sodium, potassium, rubidium or caesium or a compound of any of these, such as a nitrate, sulphate or hydroxide thereof, or a combination of any two or more of the foregoing, preferably caesium sulphate and/or nitrate. The alkaline earth metal promoter may be a compound of magnesium, calcium, strontium or barium, such as an oxide, oxalate, sulphate, acetate or nitrate thereof, or a combination of any two or more of the foregoing compounds, preferably a barium or strontium compound, more preferably barium acetate and/or strontium acetate. The alkaline earth metal promoter may be applied to the support before, simultaneously with, or after impregnation of the silver, or may be impregnated on the support after the silver compound has been reduced. The rhenium promoter may be an oxide, perrhenic acid, perrhenate, or mixtures thereof, preferably perrhenic acid and perrhenate, such as, for example, perrhenic acid, cesium perrhenate, ammonium perrhenate, and the like. The co-promoter for the rhenium promoter may be a compound of any one of the transition metals of the periodic table of the elements, or a mixture of several transition metal compounds, preferably one or more metals of chromium, molybdenum, tungsten and manganese, and/or compounds based on one or more elements of chromium, molybdenum, tungsten and manganese, such as chromic acid, chromium nitrate, tungstic acid, cesium tungstate, molybdic acid, ammonium molybdate, manganic acid, potassium permanganate and the like. The rhenium promoter and its 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 activity, selectivity, and stability of activity and selectivity of the resulting silver catalyst can be further improved by the addition of a rhenium promoter and its co-promoter.
In one particular embodiment, the silver catalyst preparation method comprises the steps of:
1) impregnating the porous alpha-alumina carrier with a solution containing a sufficient amount of a silver compound, an organic amine, and an auxiliary (such as an alkali metal auxiliary, an alkaline earth metal auxiliary, a rhenium-containing auxiliary, and a co-auxiliary thereof);
2) filtering to remove the impregnation solution, and drying the impregnated carrier; and
3) activating the carrier obtained in the step 2) in oxygen-containing mixed gas to prepare the silver catalyst.
In the preparation of the silver catalyst, silver nitrate and ammonium oxalate solution are mixed to generate silver oxalate, the silver oxalate is dissolved in organic amine to prepare silver amine solution, and then the auxiliary agent is added to prepare impregnation liquid; then soaking the alpha-alumina carrier by using the prepared impregnation liquid, draining, and carrying out thermal decomposition in air flow or nitrogen-oxygen mixed gas with oxygen content not more than 21 percent (such as oxygen content of 8.0 percent) at the temperature of 180-700 ℃, preferably 200-500 ℃ for 0.5-120 minutes, preferably 1-60 minutes to prepare the finished product of the silver catalyst.
According to another aspect of the present invention, there is provided a process for the oxidation of ethylene to produce ethylene oxide, said ethylene being subjected to an epoxidation reaction in the presence of the above-mentioned carrier or silver catalyst in a reaction apparatus to produce ethylene oxide. The reaction apparatus may be any apparatus capable of carrying out an epoxidation reaction.
According to the invention, on the premise of not adding mineralizers such as fluoride and the like, a proper amount of alpha-alumina is added as a seed crystal during the preparation of the carrier, and simultaneously, the alpha-alumina in another particle form is added, so that the crystal transformation temperature of the alumina can be obviously reduced, and the crystal size and the pore structure of the finished carrier can be adjusted. Compared with the prior art, the silver catalyst prepared by the carrier provided by the invention has the advantages of high activity and selectivity for the reaction of producing ethylene oxide by oxidizing ethylene.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to these examples.
Various silver catalysts of the present invention were tested for their initial performance and stability using a laboratory reactor (hereinafter referred to simply as "micro-reactor") evaluation apparatus. The reactor used in the microreaction evaluation apparatus was a stainless steel tube having an inner diameter of 4mm, and the reactor was placed in a heating mantle. The filling volume of the catalyst is 1ml, and the lower part of the catalyst is provided with inert filler, so that a catalyst bed layer is positioned in a constant temperature area of the heating sleeve.
The assay conditions for activity and selectivity used in the present invention are as follows:
reaction gas composition (mol%)
When the reaction conditions are stably achieved, the gas composition at the inlet and outlet of the reactor is continuously measured. The selectivity was calculated after volume shrinkage correction of the measurement results according to the following formula:
where Δ EO is the difference in the ethylene oxide concentration of the outlet gas and the inlet gas, and the average of more than 10 sets of test data was taken as the test result on the same day.
Support preparation comparative example 1
Mixing 25-200 μm trihydrate alpha-A12O32400g of pseudo-monohydrate A1 smaller than 75 μm2O3 1500g，NH4F122 g and barium nitrate 40g are put into a blender and mixed evenly, and then transferred into a kneader, and 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added and kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln and was raised from room temperature to 11 hours over 33 hoursCalcining at 00 ℃ for 5 hours at 1100 ℃ to obtain the white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Comparative example 2 Carrier preparation
Mixing 25-200 μm trihydrate alpha-A12O31600g, less than 75 μm pseudo-monohydrate A12O31500g of alpha-A1 with the particle size of 40-200 mu m2O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below. Under the condition of no mineralizer, the low calcination temperature is adopted, the content of alpha-alumina in the carrier is very low, the performance of the obtained catalyst is very poor, and the catalyst cannot be used as a normal catalyst carrier, so that the surface performance parameters of the carrier are not provided.
Support preparation comparative example 3
Mixing 25-200 μm trihydrate alpha-A12O31600g, less than 75 μm pseudo-monohydrate A12O31500g of alpha-A1 with the particle size of 40-200 mu m2O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier is put into a bell jar kiln, and is heated from room temperature to 1400 ℃ over 36 hours, and is calcined at 1400 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Comparative example 4 Carrier preparation
Mixing 25-200 μm trihydrate alpha-A12O31580g, pseudo-monohydrate A1 less than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 20g, 2-10 μm alpha-A12O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Support preparation example 1
Mixing 25-200 μm trihydrate alpha-A12O31580g, pseudo-monohydrate A1 less than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 20g, alpha-A1 of 40-200 μm2O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Support preparation example 2
Mixing 25-200 μm trihydrate alpha-A12O31500g of pseudo-monohydrate A1 smaller than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 100g, alpha-A1 of 40-200 μm2O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Is extruded and molded intoDrying the seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm at the temperature of 80-120 ℃ for more than 2 hours to reduce the free water content to below 10 percent. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Support preparation example 3
Mixing 25-200 μm trihydrate alpha-A12O31400g of pseudo-monohydrate A1 smaller than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 200g, alpha-A1 of 40-200 μm2O3800g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Support preparation example 4
Mixing 25-200 μm trihydrate alpha-A12O31900g, pseudo-monohydrate A1 less than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 100g, alpha-A1 of 40-200 μm2O3400g and 40g of barium nitrate are put into a blender and mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Support preparation example 5
Mixing 25-200 μm trihydrate alpha-A12O3700g, pseudo-monohydrate A1 less than 75 μm2O31500g, less than 2 μm of alpha-A12O3Seed crystal 100g, alpha-A1 of 40-200 μm2O31600g and 40g of barium nitrate are put into a mixer to be mixed evenly, and then transferred into a kneader, 60g of vaseline and 2100ml of dilute nitric acid (nitric acid: water: 1: 5 by weight) are added, and the mixture is kneaded into paste which can be extruded and molded. Extruding to form a seven-hole column with the outer diameter of 8.0mm, the length of 6.0mm and the inner diameter of 1.0mm, and drying at 80-120 ℃ for more than 2 hours to reduce the free water content to below 10%. The kneaded and molded carrier was put into a bell jar kiln, and was heated from room temperature to 1100 ℃ over 33 hours, and calcined at 1100 ℃ for 5 hours to obtain a white carrier. The physical properties of the carriers were measured as shown in Table 1 below.
Preparation of the catalyst
Silver catalysts were prepared on the carriers of comparative examples 1,3, 4, and examples 1-5 by the following methods: of these, comparative example 2, the content of α -alumina in the carrier was very low. Those skilled in the art know that the catalyst obtained from the carrier of comparative example 2 has a low content of alpha-alumina and the performance of the obtained catalyst is very poor.
Weighing 140g of silver nitrate and dissolving in 150ml of deionized water, weighing 64g of ammonium oxalate and dissolving in 520ml of deionized water, fully dissolving to obtain a silver nitrate solution and an ammonium oxalate solution, mixing the two solutions under vigorous stirring to generate a white silver oxalate precipitate, aging for more than 30 minutes, filtering, and washing the precipitate with deionized water until no nitrate ions exist. The filter cake contained about 60% silver and about 15% water.
70.0g of ethylenediamine is dissolved in 75.0g of deionized water, the silver oxalate filter cake prepared by the method is added, the stirring is continued to completely dissolve the silver oxalate, and then 2.58g of cesium nitrate, 6.22g of barium acetate, 0.86g of ammonium perrhenate and deionized water are sequentially added to make the total mass of the solution reach 400g, so as to prepare impregnation liquid for later use.
Taking 20g of carrier sample, placing into a vacuum vessel, vacuumizing to above 10mmHg, introducing the above immersion liquid, holding for 30min, and leaching to remove excessive solution. And heating the impregnated carrier in air flow at 450 ℃ for 3min, and cooling to obtain the silver catalyst. The silver catalyst numbers are consistent with the corresponding carriers.
The activity and selectivity of the catalyst samples were measured using a microreactor evaluation unit under the aforementioned process conditions, and the results of the microreaction evaluation are shown in Table 2.
TABLE 1 physical Properties of the vectors
TABLE 2 Properties of the catalysts
As can be seen from the data in tables 1 and 2, it can be seen from the prior art that a high calcination temperature is required without the addition of mineralizer (comparative examples 2 and 3). However, the process of the present application is capable of obtaining the support at lower calcination temperatures. Meanwhile, according to the carrier in the application, the pore volume and the water absorption are improved, and the average crystal size of a crystal part obtained by a sol-gel method is reduced; at the same time, the carrier has a high specific surface area and crush strength. In other words, according to the present invention, on the premise of not adding mineralizer such as fluoride, the proper amount of alpha-alumina is added as seed crystal during the preparation of the carrier, and simultaneously, the alpha-alumina in another particle form is added, so that the crystal transition temperature of the alumina can be significantly reduced, and the crystal size and the pore structure of the finished carrier can be adjusted. In addition, the catalyst prepared by the carrier greatly improves the selectivity of the catalyst. Meanwhile, the reaction temperature is still right, which shows that the catalyst still has better activity.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (16)
1. An alpha-alumina support for a silver catalyst for the oxidation of ethylene to produce ethylene oxide, prepared by a process comprising the steps of:
s1, preparing a solid mixture with the following composition: a) trihydrate alpha-A1 with median particle size of 25-200 mu m2O3B) pseudo-monohydrate A1 having a median particle size of less than 75 μm2O3C) a-A1 having a median particle diameter of less than 2 μm2O3Seed crystal, d) alpha-A1 having a median particle diameter of 40 to 200 [ mu ] m2O3Particles, e) burnable lubricating material, f) compounds of alkaline earth metals; then mixing the solid mixture with g) a binder and h) water to obtain a mixture;
s2, uniformly mixing, kneading and extruding the mixture finally obtained in the step S1 to form;
s3, drying the product obtained in the S2, and then roasting to prepare alpha-A12O3A carrier, a carrier and a water-soluble polymer,
wherein the roasting temperature is 900-1100 ℃,
alpha-A1 trihydrate, based on the total weight of the solid mixture2O3In an amount of 10-85wt%, pseudomonohydrate A12O3The dosage of the compound is 5-55 wt%; alpha-A12O3The dosage of the seed crystal is 0.5-5 wt%; alpha-A12O3The amount of the particles is 5-40 wt%; the using amount of the burnout lubricating material is 0.01-5.0 wt%; the amount of the alkaline earth metal compound is 0.01-5.0 wt%; the addition amount of the binder is 25-60 wt%.
2. The vector of claim 1, wherein said α -a12O3The median particle size of the seed crystals is less than 1 μm.
3. The vector of claim 1, wherein said α -a12O3The amount of seed crystals added is 2.5-5wt% of the total weight of the solid mixture.
4. The vector of any one of claims 1-3, wherein a-A12O3The median diameter of the particles is 40-150 μm; and/or the alpha-A1 based on the total weight of the solid mixture2O3The amount of the particles is 10-40 wt%.
5. The carrier of claim 4 wherein the α -A1 is present based on the total weight of the solid mixture2O3The amount of the particles is 10-20 wt%.
6. The carrier of any of claims 1-3 wherein the burnout lubricant is one or a mixture of petroleum coke, carbon powder, graphite, and petrolatum.
7. The carrier of claim 6 wherein the burnout lubricant is added in an amount of 0.01 to 4.0wt% based on the total weight of the solid mixture.
8. The carrier according to any one of claims 1 to 3 wherein the compound of an alkaline earth metal is an oxide, nitrate, acetate, oxalate or sulphate of strontium and/or barium.
9. The carrier of claim 8 wherein the compound of an alkaline earth metal is added in an amount of 0.05 to 2.0wt% based on the total weight of the solid mixture.
10. The carrier of any one of claims 1-3 wherein the binder is an acid.
11. The support according to any one of claims 1 to 3, wherein the binder is an aqueous nitric acid solution having a weight ratio of nitric acid to water of from 1:1.25 to 1: 10.
12. The vector of any one of claims 1-3, wherein the mixture prepared in step S1 is free of mineralizers.
13. The carrier of any of claims 1-3 wherein the adhesive and pseudo-monohydrate A12O3And is replaced by aluminum sol in whole or in part.
14. The vector of any one of claims 1-3, wherein step S3 produces α -A12O3In a carrier, alpha-A12O3The content is more than or equal to 95 percent, the crushing strength is 30-240N/grain, and the specific surface is 0.3-3.0m2The water absorption rate is more than or equal to 30 percent, the pore volume is 0.30-0.90ml/g, and the average crystal size is 0.2-10 mu m.
15. A silver catalyst for ethylene oxidation to produce ethylene oxide, which is prepared by supporting silver or silver and an auxiliary agent on an α -alumina carrier as claimed in any one of claims 1 to 14.
16. A process for the production of ethylene oxide by oxidation of ethylene, comprising subjecting ethylene to oxidation reaction in a reaction unit under the action of the catalyst of claim 15 to obtain ethylene oxide.
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| 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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| CN1133571A (en) * | 1993-09-08 | 1996-10-16 | 国际壳牌研究有限公司 | Epoxidation catalyst and process |
| CN1642637A (en) * | 2002-02-25 | 2005-07-20 | 国际壳牌研究有限公司 | Supported silver catalyst and an epoxidation process using the catalyst |
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| WO1997046317A1 (en) * | 1996-06-05 | 1997-12-11 | Shell Internationale Research Maatschappij B.V. | Epoxidation catalyst and process |
| CN102145285A (en) * | 2010-02-05 | 2011-08-10 | 中国石油化工股份有限公司 | Carrier of silver catalyst for producing epoxy ethane, preparation method and application of carrier of silver catalyst |
| CN102463141B (en) * | 2010-11-02 | 2015-05-06 | 中国石油化工股份有限公司 | Alumina carrier, preparation method, silver catalyst prepared by alumina carrier, and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1133571A (en) * | 1993-09-08 | 1996-10-16 | 国际壳牌研究有限公司 | Epoxidation catalyst and process |
| CN1642637A (en) * | 2002-02-25 | 2005-07-20 | 国际壳牌研究有限公司 | Supported silver catalyst and an epoxidation process using the catalyst |
Non-Patent Citations (1)
| Title |
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| α-Al2O3晶种对氧化铝转相温度的影响;刘大鹏等;《材料导报》;20001031;第14卷;文章摘要，第40页前言，第41页第3节 * |
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