CN106311233A - Method for improving initial-stage selectivity of silver catalyst and olefin epoxidation method - Google Patents
Method for improving initial-stage selectivity of silver catalyst and olefin epoxidation method Download PDFInfo
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- CN106311233A CN106311233A CN201510383161.8A CN201510383161A CN106311233A CN 106311233 A CN106311233 A CN 106311233A CN 201510383161 A CN201510383161 A CN 201510383161A CN 106311233 A CN106311233 A CN 106311233A
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- China
- Prior art keywords
- catalyst
- silver
- high selectivity
- rhenium
- oxygen
- Prior art date
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 117
- 239000004332 silver Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 62
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 14
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005977 Ethylene Substances 0.000 claims abstract description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000012752 auxiliary agent Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 150000001340 alkali metals Chemical class 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 13
- 229910052792 caesium Inorganic materials 0.000 claims description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 10
- 229940100890 silver compound Drugs 0.000 claims description 9
- 150000003379 silver compounds Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- -1 chloroethenes Alkane Chemical class 0.000 claims description 5
- 229910052756 noble gas Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 150000003282 rhenium compounds Chemical class 0.000 claims description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000009286 beneficial effect 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
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- YOECZGZYTASTQO-UHFFFAOYSA-N ethane silver Chemical compound [Ag].CC YOECZGZYTASTQO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 210000000952 spleen Anatomy 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 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 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- UDFWUWKGBBKQAF-UHFFFAOYSA-N oxalic acid;silver Chemical compound [Ag].OC(=O)C(O)=O UDFWUWKGBBKQAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010959 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
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for improving initial-stage selectivity of a high-selectivity silver catalyst used for preparing ethylene oxide through ethylene oxidation. The method comprises the following steps: subjecting the high-selectivity silver catalyst to continuously contacting with raw materials containing propylene and oxygen in a temperature range of 200 to 270 DEG C for 0.5 to 50 hours, after contacting is completed, allowing the temperature of the catalyst not to be higher than 250 DEG C, and allowing the high-selectivity silver catalyst to contact with the raw materials containing ethylene and oxygen, wherein the high-selectivity silver catalyst comprises an alpha-alumina carrier, and a silver active component and a rhenium additive which are deposited on the alpha-alumina carrier. The invention also relates to an olefin epoxidation method and a method for production of 1,2-ethylene glycol.
Description
Technical field
The present invention relates to a kind of method improving catalyst performance, particularly relate to a kind of initial stage choosing improving catalyst
The method of selecting property.The invention still further relates to a kind of olefin epoxidation process and a kind of method producing 1,2-ethylene glycol.
Background technology
Under silver catalyst effect, direct oxidation of ethylene to mainly generates oxirane (EO), and side reaction occurs simultaneously
Generating carbon dioxide and water etc., wherein activity, selectivity and stability are the main performance index of silver catalyst.
So-called activity refers to process for ethylene oxide production to reach necessarily to react reaction temperature required during load.Reaction temperature
The lowest, the activity of catalyst is the highest.So-called selectivity refers to that in reaction, ethylene changes into the molal quantity of oxirane
Ratio with the overall reaction molal quantity of ethylene.So-called stability is then expressed as the fall off rate of activity and selectivity, under
The stability of reduction of speed rate more small catalyst is the best.Height is used to live during oxidation of ethylene produces oxirane
Property, high selectivity and the silver catalyst having good stability can be greatly improved economic benefit, therefore manufacture high activity,
The silver catalyst of high selectivity and good stability is the Main way of silver catalyst research.
The performance of silver catalyst, in addition to having important relationship with the composition of catalyst and preparation method, also makes with catalyst
Technique have important relationship.
Direct oxidation of ethylene to epoxy ethane silver catalyst is divided three classes: high selection in high activity silver catalyst
Property silver catalyst and high selectivity silver catalyst.The initial stage selectivity of high activity silver catalyst is 80-81mol%,
Latter stage, selectivity was 76-78mol%, and space-time yield can reach 280 grams of EO/ hour * and rise catalyst；Middle Gao Xuan
The initial stage selectivity of selecting property silver catalyst is 81-85mol%, and the highest selectivity is 85-86mol%, and latter stage selects
Property be 80-82mol%, space-time yield can reach 200-280 gram of EO/ hour * and rise catalyst；High selectivity silver
The initial stage selectivity of catalyst is 82-85mol%, and the highest selectivity is 87-92mol%, and latter stage, selectivity was
82-84mol%, space-time yield can reach 160-220 gram of EO/ hour * and rise catalyst.
The most surging along with oil price, current ethylene oxide production has developed into use high-selective ethylene
Epoxidation catalysts trend, it is relative to traditional high activity epoxidation catalyst, it is provided that reduce
The benefit of ethylene material consumption.But, for the productivity of a given oxirane, high-selectivity catalyst ratio is high
Active catalyst uses higher reaction temperature, and it demonstrates than traditional high activity epoxidation catalyst
Catalyst activity reduces speed faster.Therefore, in order to improve the activity of catalyst, selectivity and stability,
Ge great silver catalyst research company in these years, has not only carried out unremitting effort on carrier and preparation, and
Oxirane production technology and equipment are also carried out improve, to give full play to the performance of catalyst.
High selectivity silver catalyst is in the starting stage of epoxidation process, and catalyst experiences a so-called " breakthrough
Stage ".In this stage, selectivity of catalyst is the lowest, even if being also so in the presence of reaction control agent,
Take long enough in a commercial start-up to adjust and just can make the reaction can be in catalyst higher selectivity level
Lower operation.For this reason, it is necessary to the starting method research experiment to the catalyst initial stage.
Therefore, this area needs using high selectivity silver catalyst to be entered by the technique of oxidation of ethylene epoxy ethane
Row improves, and is beneficial to improve the initial performance of high selectivity silver catalyst.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present inventor is in silver catalyst field and second
Alkene oxidation epoxy ethane field has carried out research extensively and profoundly, it was found that existing technique is improved,
Service life of high selectivity silver catalyst can not be reduced and need not to improve the high selectivity silver catalyst initial stage anti-
Under conditions of answering temperature, it is greatly improved the selectivity at high selectivity silver catalyst initial stage, thus improves high selectivity
The average selectivity of silver catalyst.
Therefore, it is an advantage of the invention to provide a kind of raising oxidation of ethylene epoxy ethane Gao Xuan
The initial stage selective method of selecting property silver catalyst, described method includes:
High selectivity silver catalyst is made and containing propylene and the raw material of oxygen within the temperature range of 200 DEG C to 270 DEG C
Continuous contact 0.5 hour to 50 hours, contact makes catalyst temperature be not higher than 250 DEG C after terminating, and makes described
High selectivity silver catalyst contacts with the raw material containing ethylene and oxygen,
Wherein said high selectivity silver catalyst includes that carrier and the silver-colored active component and the rhenium that deposit on it help
Agent, described carrier is preferably alpha-alumina supports.
The present invention, by initial operating stage catalyst is carried out certain heat treatment, quickly improves oxidation of ethylene ring
Oxidative ethane is with high selectivity silver catalyst initial stage selectivity.
" initial operating stage " of high selectivity silver catalyst as used herein refers to that new production catalyst is when certain
Under the conditions of empty productivity, at most operation 12 months, in particular up to 6 months.
" heat treatment " as used herein is defined as at 200 DEG C to 270 DEG C (preferably 200 DEG C to 250 DEG C)
Under make catalyst contact with the raw material containing propylene and oxygen process catalyst process, this process duration is 0.5
Hour to 50 hours, and this process terminates to reduce afterwards catalyst temperature to not higher than 250 DEG C, the highest
In 220 DEG C.
" high selectivity silver catalyst " as used herein refers to that the initial stage selectivity of silver catalyst is more than 83mol%,
The highest selectivity is more than 88mol%, and average selectivity is more than 86mol%, and latter stage, selectivity was more than 82mol%,
And space-time yield is that 150-240 gram of EO/ hour * rises catalyst.
One of the present invention preferred embodiment in, in the described raw material containing propylene and oxygen, described third
The content of alkene is calculated as 0.1-1.0mol% relative to the raw material containing propylene and oxygen, and oxygen content is relative to containing propylene
It is calculated as 0.5-5.0mol% with the raw material of oxygen.
One of the present invention preferred embodiment in, in the described raw material containing propylene and oxygen, described third
The content of alkene is calculated as 0.2-0.5mol% relative to the raw material containing propylene and oxygen, and oxygen content is relative to containing propylene
It is calculated as 1.0-3.0mol% with the raw material of oxygen.
One of the present invention preferred embodiment in, within the temperature range of 200 DEG C to 270 DEG C, make height
Selectivity silver catalyst and the raw material continuous contact containing propylene and oxygen are before 0.5 hour to 50 hours, with purging
Beds is swept in air-blowing, and described purge gas is preferably noble gas, more preferably nitrogen, described purge time
It is preferably 12-96 hour.
One of the present invention preferred embodiment in, described high selectivity silver catalyst also includes rhenium auxiliary agent
Coassist agent, the most also includes alkali metal promoter, the most also includes base earth metal promoter.
In a preferred embodiment of the invention, described high selectivity silver catalyst comprises alpha-alumina supports
And the following component of deposition on it:
I) silver active component；
Ii) rhenium auxiliary agent；
Iii) optionally, the coassist agent of rhenium auxiliary agent；
Iv) optionally, alkali metal promoter；With
V) optionally, base earth metal promoter.
One of the present invention preferred embodiment in, the high selectivity silver catalyst preferably group that the present invention uses
Become as follows, gross weight based on high selectivity silver catalyst,
Silver content is calculated as 1-30 weight %, preferably 10-29 weight % with silver element；And/or rhenium content is with rhenium unit
Element is calculated as 5 weight ppm-2500 weight ppm, preferably 10 weight ppm-1500 weight ppm；And/or rhenium
If if the coassist agent of auxiliary agent is optionally present, its amount is calculated as 5 weight ppm-1000 weights with this coassist agent element
Amount ppm, preferably 10 weight ppm-500 weight ppm；And/or if if alkali metal promoter is optionally present,
Its amount is calculated as 5 weight ppm-2000 weight ppm, preferably 10 weight ppm-1500 weights with alkali metal
Amount ppm；If and/or if base earth metal promoter is optionally present, its amount is calculated as 5 weight with alkali earth metal
Ppm-2000 weight ppm, preferably 10 weight ppm-1200 weight ppm.
One of the present invention preferred embodiment in, in described high selectivity silver catalyst, described silver activity
Composition is argent and/or silver compound, preferably the one in argent, silver oxide, silver nitrate and silver oxalate
Or it is multiple.
One of the present invention preferred embodiment in, described rhenium auxiliary agent is rhenium metal and/or rhenium compound, institute
State one or more that rhenium compound is preferably in the oxide of rhenium, perrhenic acid and perrhenate, more preferably height
One or more in rehenic acid and/or perrhenate, more preferably perrhenic acid, perrhenic acid caesium and ammonium perrhenate.
One of the present invention preferred embodiment in, if described high selectivity silver catalyst is optionally present
The coassist agent of rhenium auxiliary agent, the coassist agent of described rhenium auxiliary agent is in chromium, molybdenum, tungsten, boron, cerium, sulfur and manganese
One or more elements or its compound.
One of the present invention preferred embodiment in, if described high selectivity silver catalyst is optionally present
Alkali metal promoter, described alkali metal promoter be one or more metals in lithium, sodium, potassium, rubidium and caesium or
Its compound, preferably lithium, potassium or caesium or its compound.
One of the present invention preferred embodiment in, if described high selectivity silver catalyst is optionally present
Base earth metal promoter, described base earth metal promoter be one or more metals in magnesium, calcium, strontium and barium or
Its compound, preferably barium or strontium or its compound.
As it has been described above, the high selectivity silver catalyst of the present invention is advantageously loaded catalyst.As being suitable to this
The carrier of catalyst, it can be any carrier being suitable to silver catalyst, and this can be mentioned that various oxide carrier
Or composite oxide carrier, such as silicon oxide, aluminium oxide (such as Alpha-alumina), aluminium oxide-silicon oxide combined oxidation
Thing carrier, in addition with zeolite, activated carbon etc..
The high selectivity silver catalyst being suitable to the present invention can be any high selectivity silver catalyst.This catalyst was both
Can be commercial, it is also possible to prepare according to methods known in the art.
Such as, the high selectivity silver catalyst that can be used for the present invention can be prepared by the method comprised the following steps:
1) help with silver compound, organic amine, rhenium auxiliary agent, the coassist agent of optional rhenium auxiliary agent, optional alkali metal
Agent and the solution impregnating carrier of optional base earth metal promoter；
2) impregnation liquid is filtered off；And
3) to step 2 in air or noble gas) resulting vehicle activates, and i.e. makes the catalysis of high selectivity silver
Agent.
One of the present invention preferred embodiment in, above-mentioned silver compound can be to be suitable to be prepared ring by ethylene
Any silver compound of oxidative ethane silver catalyst.Present invention preferably uses silver oxide, silver nitrate and/or silver oxalate.
Silver compound addition in impregnation liquid should be enough to argentiferous 1-30 weight % in the silver catalyst making finally to prepare,
Preferably 10-29 weight %, based on total catalyst weight in terms of silver atoms.
One of the present invention preferred embodiment in, above-mentioned organic amine compound can be to be suitable to prepare epoxy
Any organic amine compound of ethane silver catalyst for producing, as long as this organic amine compound can be with silver compound
Formation argent-amine complex.For the purpose of the present invention, be preferably used pyridine, butylamine, ethylenediamine, 1,3-the third two
Amine, ethanolamine or the mixture of its mixture, such as ethylenediamine and ethanolamine.
One of the present invention preferred embodiment in, in the above-mentioned method preparing silver catalyst, rhenium auxiliary agent
Can be the oxide of rhenium, perrhenic acid, perrhenate, or its mixture, preferably perrhenic acid and perrhenate,
Such as perrhenic acid, perrhenic acid caesium, ammonium perrhenate or its mixture etc..Rhenium auxiliary agent addition in impregnation liquid should
Making rhenium metal promoter content in terms of rhenium atom in the final catalyst is 5 weight ppm-2500 weight ppm,
It is preferably 10 weight ppm-1500 weight ppm, gross weight based on high selectivity silver catalyst.
One of the present invention preferred embodiment in, in the above-mentioned method preparing silver catalyst, optionally make
Alkali metal promoter can be that the compound of lithium, sodium, potassium, rubidium or caesium is (such as nitrate, sulfate and hydroxide
Thing) or its mixture, preferred as alkali auxiliary agent is one or more in the compound of lithium, potassium and caesium, as
Cesium sulfate, cesium nitrate, lithium nitrate, lithium sulfate and/or potassium hydroxide.Alkali metal promoter, if if Shi Yonging,
Addition in impregnation liquid advantageously should make described alkali metal promoter in terms of alkali metal atom in the final catalyst
Content be 5 weight ppm-2000 weight ppm, preferably 10 weight ppm-1500 weight ppm, based on
The gross weight of high selectivity silver catalyst.
One of the present invention preferred embodiment in, in the above-mentioned method preparing silver catalyst, optionally make
Base earth metal promoter can be magnesium, calcium, strontium and barium compound in one or more, such as described element
Oxide, oxalates, sulfate, acetate and nitrate in one or more, the preferably compound of barium
And/or the compound of strontium, such as barium acetate and/or strontium acetate.If if base earth metal promoter uses, it is at dipping
Addition in liquid should make base earth metal promoter total content in terms of alkaline earth metal atom in the final catalyst be 5
Weight ppm-2000 weight ppm, preferably 10 weight ppm-1200 weight ppm, based on high selectivity silver
The gross weight of catalyst.
One of the present invention preferred embodiment in, except silver compound, organic amine, rhenium in dipping solution
Beyond auxiliary agent, optional alkali metal promoter and optional base earth metal promoter, it is also possible to add helping altogether of rhenium auxiliary agent
Agent, to improve the activity of gained silver catalyst, selectivity and stability further.The coassist agent of rhenium auxiliary agent can
To be the compound of arbitrary transition metal in the periodic table of elements (such as chromium, molybdenum, tungsten, boron, cerium and manganese) or several
Plant the mixture of transistion metal compound, preferably group vib and the oxyacid of VIIB race element and salt thereof, such as
Wolframic acid, ammonium tungstate, wolframic acid caesium, molybdic acid, ammonium molybdate or its tetrahydrate, ammonium metatungstate, four hydrated sulfuric acid height
Cerium (Ce (SO4)2·4H2O) etc..Coassist agent as rhenium auxiliary agent, it is also possible to be sulfur.
One of the present invention preferred embodiment in, the coassist agent of rhenium auxiliary agent, if if Shi Yonging, its consumption
Should make the coassist agent of rhenium auxiliary agent in final catalyst is 5 weight with the weight content of this coassist agent elemental metal
Ppm-1000 weight ppm, preferably 10 weight ppm-500 weight ppm, based on high selectivity silver catalyst
Gross weight.The coassist agent of rhenium auxiliary agent can be before immersion silver, be applied on carrier simultaneously or after, it is also possible to
It is immersed on carrier after silver compound is reduced to.
One of the present invention preferred embodiment in, for ensureing the most even abundant load of silver, carrier, excellent
Selecting alumina support (such as Alpha-alumina), before impregnation, evacuation the most in advance, this vacuum is preferably shorter than
10mmHg.When impregnating with impregnation liquid, dip time is usually 10-60 minute.After leaching, will be through impregnation with
Carrier drying.Then, by resulting vehicle 100-700 DEG C, the moving air of preferred 160-500 DEG C or inertia
Activation more than 30 seconds in air-flow such as gas such as nitrogen, argon etc., such as 30 seconds-120 minutes, preferably 1-60 minute,
To activate, thus make high selectivity silver catalyst.
One of the present invention preferred embodiment in, as the initial action by oxidation of ethylene epoxy ethane
Gas, it generally comprises ethylene, oxygen, the steady gas of cause and reaction control agent.As causing steady gas, its purpose is to
Keep the content of ethylene and oxygen in reaction gas to operate in explosion limit, and cause steady gas itself and do not participate in instead
Should, reaction is not had negatively influencing.Cause steady gas and be usually nitrogen, methane or its mixture: methane is conducive to improving
Oxygen content and the molten value of air heat in unstripped gas, favourable to reaction, some producer limits due to process conditions, makes
With nitrogen as making steady gas.As reaction control agent, its purpose is to suppress the activity of silver catalyst, improve
Selectivity, for high selectivity silver catalyst, reaction control agent has the work improving silver catalyst stability simultaneously
With.Reaction control agent generally includes monochlorethane, dichloroethanes or its mixture.When reaction gas recycles,
May also accumulate certain carbon dioxide in reaction gas, the increase of carbon dioxide can affect high selectivity silver catalyst
Stability.Additionally, during factory uses, generally some foreign gases also can be there are in initial action gas,
Such as hydrogen, ethane, argon.Argon is noble gas, does not participate in reaction.
At present, this area it is generally acknowledged that the too high meeting of propylene content causes high activity silver catalyst activity to raise, and selects
Property decline to a great extent, after propylene content reaches certain value (such as larger than 0.7mol%), it may appear that reaction temperature raise,
Selectivity aggravation declines.
But, the present inventor through lot of experiments it was unexpectedly found that, through 200 DEG C extremely
After making the heat treatment that catalyst contacts with the raw material containing propylene and oxygen at 270 DEG C, high selectivity silver can be improved
Catalyst initial stage selectivity.
According to the present invention, catalyst is made to contact 0.5-50 with the raw material containing propylene and oxygen at 200 DEG C to 270 DEG C
Hour process catalyst.Generally can apply the temperature in the range of any 200 DEG C to 270 DEG C, more typically
At least 210 DEG C, it is at most 260 DEG C, usually at most 250 DEG C.The persistent period of heat treatment is generally at least
0.5 hour, preferably 1-50 hour, specifically for 2-40 hour.In heat treatment, adaptable raw material is permissible
Containing inertia or the annexing ingredient of non-inert.Noble gas such as helium, nitrogen or the mixture of saturated hydrocarbons.Relative to always
For raw material, in raw material, the content of propylene is preferably 0.1-1.0mol%, particularly 0.2-0.5mol%.In raw material
The content of oxygen is preferably 0.5-5.0mol%, particularly 1.0-3.0mol%.The method is to be higher than in general
Catalyst is made to contact with the raw material containing propylene and oxygen at 200 DEG C to 270 DEG C, through catalyst is carried out heat treatment
After, improve high selectivity silver catalyst initial stage selectivity.
At a temperature of of the present invention, high selectivity silver catalyst is carried out heat treated by application the inventive method
Cheng Zhong, propylene and oxygen there occurs complete oxidation in high selectivity silver catalyst bed, and product is basic
For carbon dioxide and water.Relatively low due to the propylene content in the raw material of use in heat treatment process again, and excess
Oxygen content so that without propylene in reaction tube exit flow after heat treatment, thus to heat treatment rear catalyst
Startup procedure does not affect again.
Present invention could apply to the high selectivity silver catalyst newly driven, it is also possible to be applied to initial operating stage due to
The high selectivity silver catalyst that device is driven after stopping again.
When being applied to raw catelyst, before implementing the present invention, keep the situation of uniform temperature at beds
Under, it is probably useful with purging beds.Such as purge gas can make nitrogen.Keep higher catalysis
What agent temperature can make in catalyst production process the organic nitrogen compound of application is largely converted into nitrogenous gas, this
A little nitrogenous gas are purged in gas stream and deviate from from catalyst.Furthermore it is possible to remove from catalyst
Arbitrary moisture.When loading catalyst in the reactor, by application heater, generally make the temperature of catalyst
Degree reaches 180-250 DEG C, and makes inert purge gas pass through catalyst, the driving of the catalyst applied
May require or not that application purging gas, but typically require application.Generally purge time is 12-96 hour.
After purge terminates, can apply the inventive method that high selectivity silver catalyst is carried out heat treatment, carry
High selectivity silver catalyst initial stage selectivity.
One of the present invention preferred embodiment in, carrying out the raising oxidation of ethylene epoxy second of the present invention
Alkane is with after the initial stage selective method of high selectivity silver catalyst, according to usual catalyst starting program, logical
Enter the reaction gas of oxidation of ethylene epoxy ethane.
One of the present invention preferred embodiment in, for new peak selectivity silver catalyst, by second
In the initial action gas of alkene oxidation epoxy ethane, ethylene contents is 20-40mol%, and oxygen content is
6-7mol% (nitrogen system is steady) or 7.5-8.5mol% (methane is steady), carbon dioxide content is ＜ 2mol%, and reaction is adjusted
The content of joint agent is 0.2-2ppm volume, and remaining is for causing steady gas.Reaction control agent is typically monochlorethane, dichloro
Ethane or its mixture.After the composition regulation of initial action gas is complete, by the temperature of high selectivity silver catalyst
Degree is increased to 180-250 DEG C, preferably 200-220 DEG C.Can suitably optimize reaction control agent according to reaction condition to contain
Amount, makes selectivity of catalyst reach desired value.
One of the present invention preferred embodiment in, the high selectivity again driven after initial reaction stage is stopped
Catalyst, it is also possible to the processing method of the application present invention carries out raising initial stage selective heat treatment to catalyst.
Then according to the startup procedure that catalyst is driven after stopping again is passed through the reaction gas of oxidation of ethylene epoxy ethane.
It is a further object of the invention to provide a kind of olefin epoxidation process, described method includes:
Catalyst and the raw material continuous contact 0.5 containing propylene and oxygen is made within the temperature range of 200 DEG C to 270 DEG C
Hour to 50 hours, contact makes catalyst temperature be not higher than 250 DEG C after terminating, and makes described high selectivity silver urge
Agent contacts with the raw material containing ethylene and oxygen.
One of the present invention preferred embodiment in, described catalyst is high selectivity silver catalyst.
One of the present invention preferred embodiment in, described alkene is ethylene.
One of the present invention preferred embodiment in, the described raw material containing propylene and oxygen also includes as instead
The organic chloride of regulator, described organic chloride is answered to be preferably dichloroethanes.
It is still another object of the present invention to provide a kind of method producing 1，2-ethandiol, described method includes:
1) oxyalkylene is obtained by the olefin epoxidation process described in claim 7；And
2) described oxyalkylene is made to be converted into 1,2-ethylene glycol.
The beneficial effects of the present invention is, method according to the invention it is possible to keeping high selectivity silver catalyst
Under conditions of initial reaction temperature is basically unchanged, it is greatly improved the selectivity at high selectivity silver catalyst initial stage, from
And it is effectively improved the average selectivity of high selectivity silver catalyst, thus improve the performance of silver catalyst, reduce raw
Produce cost of material.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but the scope of the present invention is not limited to
These embodiments.
The various high selectivity silver catalyst laboratory microreactor (hereinafter referred to as " micro-anti-") that the present invention uses
Evaluating apparatus tests its performance and stability.The reactor that micro anti-evaluation device uses is the stainless of internal diameter 4mm
Steel pipe, reactor is placed in heating mantle.The admission space of high-selectivity catalyst is 1ml, and bottom has inertia to fill out
Material, makes high-selectivity catalyst bed be positioned at the flat-temperature zone of heating mantle.
The condition determination of the activity and selectivity that the present invention uses is as follows:
Table 1: reacting gas composition (mol%)
METHOD FOR CONTINUOUS DETERMINATION reactor inlet, exit gas composition after stably reaching above-mentioned reaction condition.Measurement result
Selectivity is calculated as follows after carrying out volume contraction correction:
Selectivity
Wherein Δ EO is to work off one's feeling vent one's spleen and inlet gas ethylene oxide content difference, Δ CO2Be work off one's feeling vent one's spleen with in inlet gas
Carbon dioxide content is poor, takes the average result of the test as the same day of more than 10 groups test datas.
Embodiment 1
The preparation of high selectivity silver catalyst carrier
By 50-200 purpose three water α-A12O3The vacation one water A1 of 440g and 200-500 mesh2O3110g, puts into
Mix homogeneously in blender.Then proceed in kneader, add the dust technology that mass ratio is 1:3 of nitric acid and water
100 milliliters, being kneaded into can the paste of extrusion molding.Extrusion molding is external diameter 8.0mm, long 6.0mm, interior
The five hole columns of footpath 1.0mm, are dried 3 hours at 60-120 DEG C, make free water content be reduced to 10 weights
Amount below %, obtains green compact.Then green compact are put in electric furnace, be increased to from room temperature through 30 hours
1410-1450 DEG C, constant temperature 2 hours, obtain white α-A12O3Support samples.
Embodiment 2
The preparation of high selectivity silver catalyst
In the glass flask of band stirring, add 300g ethylenediamine, 110g ethanolamine and 375g deionized water, obtain
To mixed liquor.Being added by silver oxalate in gained mixed liquor under stirring, temperature is maintained at about 40 DEG C, makes oxalic acid
Silver all dissolves.Then it is added thereto to 0.69g ammonium perrhenate and 1.65g cesium sulfate, then adds deionized water and make
Solution gross mass reaches 2200g, gained solution mix homogeneously, obtains impregnation liquid, stand-by.In this impregnation liquid,
The content of silver is 29 weight %.
Take 100g white α-A1 prepared above2O3Support samples is put in the container of energy evacuation.It is evacuated to
Vacuum is less than 10mmHg, puts into above impregnation liquid, submergence carrier, keeps 30 minutes.Leaching removes many
Remaining solution.Carrier after dipping heats 8 minutes in the air stream of 300 DEG C, cooling, i.e. makes epoxy second
Alkane silver catalyst for producing.This catalyst is high selectivity silver catalyst, containing the silver of 20 weight %, 200 weights
The rhenium of amount ppm and the caesium of 500 weight ppm.
After measured, above-mentioned high selectivity silver catalyst uses the selectivity at initial stage to be 83mol%, the highest selectivity
For 89mol%, average selectivity is 87mol%, and latter stage, selectivity was 86mol%, and space-time yield is 220
* rose catalyst gram EO/ hour.
Comparative example 1-3 and embodiment 3-6
With microreactor evaluating apparatus, the fresh high selectivity silver catalyst of preparation in reference example 2 is entered
Row performance test.The catalyst sample that 0.6-1.0g pulverizes is loaded respectively in seven stainless steel tubes.Described pipe
It is positioned in the METAL HEATING PROCESS set of 180 DEG C, and the end of every pipe is all connected with air flow system.Gas mixes
Thing passes through beds with the mode of operation of " once by ".Regulate the catalyst weight and entrance applied
The flow of gas, making gas hour air speed is 4500h-1, inlet gas pressure is 1600kPa absolute pressure.Reaction tube
Inlet gas composition sees table 1.
Make the temperature of each beds rise to 220 DEG C with the speed of per hour 10 DEG C, then regulate temperature
To obtain the ethylene oxide content of 2.5mol% in each reaction tube outlet gas mixture.These regulations are protected
Holding 96 hours, now catalyst has reached balance in terms of reactivity worth, and table 2 gave through 96 hours
Time interval after measure with reaction temperature and the performance of each catalyst of selective presentation.
Then as shown in table 2, within the time period of 24 hours, make the different gas mixing shown in table 2
Thing passes through each beds, and makes raw up to 240 DEG C of the temperature of each beds.Through this section time
After between, those conditions that appreciation condition is applied before reverting to heat up, and regulate the temperature of each beds
Degree, so that recovering the ethylene oxide content of 2.5mol% in each reaction tube outlet gas mixture.
After measured, by the immediate catalyst reaction temperature of every kind of catalyst after admixture of gas heat treatment at 240 DEG C
Degree and selectivity are as shown in table 2.
Table 2
Comparative example 4-6 and embodiment 7-10
Use the high selectivity silver catalyst of preparation in embodiment 2, load in seven stainless steel tubes respectively
The catalyst sample that 0.6-1.0g pulverizes.Described pipe is positioned in the METAL HEATING PROCESS set of 180 DEG C, and every pipe
The end of son is all connected with air flow system.Admixture of gas passes through catalyst with the mode of operation of " once by "
Bed.Regulating the catalyst weight and the flow of inlet gas applied, making gas hour air speed is 4500h-1,
Inlet gas pressure is 1600kPa absolute pressure.The temperature of each beds is made with the speed of per hour 10 DEG C
Rising to 220 DEG C, then regulation temperature is to obtain 2.5mol%'s in each reaction tube outlet gas mixture
Ethylene oxide content.These regulations being kept 90 days, table 3 gives to be measured after the time interval of 90 days
With reaction temperature and the performance of each catalyst of selective presentation.
Then as shown in table 3, within the time period of 24 hours, make different admixture of gas be urged by each
Agent bed, and make raw up to 240 DEG C of the temperature of each beds.After during this period of time, evaluate bar
Those conditions that part is applied before reverting to heat up, and regulate the temperature of each beds, so that often
Individual reaction tube outlet gas mixture recovers the ethylene oxide content of 2.5mol%.
After measured, by the immediate catalyst reaction temperature of every kind of catalyst after admixture of gas heat treatment at 240 DEG C
Degree and selectivity are as shown in table 3.
Table 3
Embodiment 3-6 is compared with comparative example 1-3 or embodiment 7-10 is compared with comparative example 4-6, experimental result
All show, after making catalyst contact a period of time with the mixed gas containing propylene and oxygen at 240 DEG C, when
When it is applied subsequently in the course of normal operation of epoxidizing method, this catalyst shows the selectivity of improvement,
The temperature of catalyst keeps being basically unchanged (i.e. activity is basically unchanged) simultaneously.Meanwhile, the raising catalysis of the present invention
The selective method of agent can be incorporated in epoxidizing method, such as embodiment 3-10 as a step.
Claims (11)
1. improve an initial stage selective method for the high selectivity silver catalyst of oxidation of ethylene epoxy ethane,
Described method includes:
High selectivity silver catalyst is made and containing propylene and the raw material of oxygen within the temperature range of 200 DEG C to 270 DEG C
Continuous contact 0.5 hour to 50 hours, contact makes catalyst temperature be not higher than 250 DEG C after terminating, and makes described
High selectivity silver catalyst contacts with the raw material containing ethylene and oxygen,
Wherein said high selectivity silver catalyst includes that carrier and the silver-colored active component and the rhenium that deposit on it help
Agent, described carrier is preferably alpha-alumina supports.
Method the most according to claim 1, it is characterised in that in the described raw material containing propylene and oxygen,
The content of described propylene is calculated as 0.1-1.0mol% relative to the raw material containing propylene and oxygen, preferably 0.2-0.5
Mol%, oxygen content is calculated as 0.5-5.0mol% relative to the raw material containing propylene and oxygen, preferably 1.0-3.0
mol%。
Method the most according to claim 1 and 2, it is characterised in that the temperature of 200 DEG C to 270 DEG C
High selectivity silver catalyst and the raw material continuous contact 0.5 hour to 50 hours containing propylene and oxygen is made in the range of degree
Before, purging beds by purge gas, described purge gas is preferably noble gas, more preferably nitrogen,
Described purge time is preferably 12-96 hour.
4. according to the method described in any one in claim 1-3, it is characterised in that described high selectivity silver
Catalyst also includes the coassist agent of rhenium auxiliary agent, the most also includes alkali metal promoter, the most also includes alkaline-earth metal
Auxiliary agent.
5. according to the method described in any one in claim 1-4, it is characterised in that based on high selectivity silver
The gross weight of catalyst, silver content is calculated as 1-30 weight %, preferably 10-29 weight % with silver element；With/
Or rhenium content is calculated as 5 weight ppm-2500 weight ppm, preferably 10 weight ppm-1500 weights with rhenium element
Amount ppm；If and/or if the coassist agent of rhenium auxiliary agent is optionally present, its amount is calculated as 5 weights with this coassist agent element
Amount ppm-1000 weight ppm, preferably 10 weight ppm-500 weight ppm；If and/or alkali metal promoter
If being optionally present, its amount is calculated as 5 weight ppm-2000 weight ppm with alkali metal, and preferably 10
Weight ppm-1500 weight ppm；If and/or if base earth metal promoter is optionally present, its amount is with alkaline earth gold
Belong to element and be calculated as 5 weight ppm-2000 weight ppm, preferably 10 weight ppm-1200 weight ppm.
6. according to the method described in any one in claim 1-5, it is characterised in that described high selectivity silver
In catalyst, described silver active component is argent and/or silver compound, preferably argent, silver oxide, nitre
One or more in acid silver and silver oxalate；
Described rhenium auxiliary agent is rhenium metal and/or rhenium compound, and described rhenium compound is preferably the oxide of rhenium, high rhenium
Acid and perrhenate in one or more, more preferably perrhenic acid and/or perrhenate, more preferably perrhenic acid,
One or more in perrhenic acid caesium and ammonium perrhenate；
If described high selectivity silver catalyst is optionally present the coassist agent of rhenium auxiliary agent, helping altogether of described rhenium auxiliary agent
Agent is one or more elements in chromium, molybdenum, tungsten, boron, cerium, sulfur and manganese or its compound；
If being optionally present alkali metal promoter in described high selectivity silver catalyst, described alkali metal promoter is to be selected from
One or more metals in lithium, sodium, potassium, rubidium and caesium or its compound, preferably lithium, potassium or caesium or its change
Compound；
If being optionally present base earth metal promoter in described high selectivity silver catalyst, described base earth metal promoter is
One or more metals in magnesium, calcium, strontium and barium or its compound, preferably barium or strontium or its compound.
7. an olefin epoxidation process, described method includes:
Catalyst and the raw material continuous contact 0.5 containing propylene and oxygen is made within the temperature range of 200 DEG C to 270 DEG C
Hour to 50 hours, contact makes catalyst temperature be not higher than 250 DEG C after terminating, and makes described high selectivity silver urge
Agent contacts with the raw material containing ethylene and oxygen.
Method the most according to claim 7, it is characterised in that described catalyst is that high selectivity silver is urged
Agent.
9. according to the method described in claim 7 or 8, it is characterised in that described alkene is ethylene.
10. according to the method described in any one in claim 7-9, it is characterised in that described containing propylene with oxygen
The raw material of gas also includes that the organic chloride as reaction control agent, described organic chloride are preferably two chloroethenes
Alkane.
11. 1 kinds of methods producing 1，2-ethandiol, described method includes:
1) oxyalkylene is obtained by the olefin epoxidation process described in claim 7；And
2) described oxyalkylene is made to be converted into 1,2-ethylene glycol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724116A (en) * | 2018-07-16 | 2020-01-24 | 东营市海科新源化工有限责任公司 | Preparation method and production system of vicinal diol compound |
| CN114057669A (en) * | 2020-07-29 | 2022-02-18 | 中国石油化工股份有限公司 | Ethylene epoxidation constant-temperature driving method |
| CN114436998A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Ethylene epoxidation start-up method |
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|---|---|---|---|---|
| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| CN1665594A (en) * | 2002-06-28 | 2005-09-07 | 国际壳牌研究有限公司 | A method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
| US20070185339A1 (en) * | 2006-02-03 | 2007-08-09 | Jian Lu | Process for treating a catalyst, the catalyst, and use of the catalyst |
-
2015
- 2015-07-02 CN CN201510383161.8A patent/CN106311233B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1665594A (en) * | 2002-06-28 | 2005-09-07 | 国际壳牌研究有限公司 | A method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
| CN1511632A (en) * | 2002-12-31 | 2004-07-14 | 中国石油化工股份有限公司北京燕山分 | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use |
| US20070185339A1 (en) * | 2006-02-03 | 2007-08-09 | Jian Lu | Process for treating a catalyst, the catalyst, and use of the catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724116A (en) * | 2018-07-16 | 2020-01-24 | 东营市海科新源化工有限责任公司 | Preparation method and production system of vicinal diol compound |
| CN110724116B (en) * | 2018-07-16 | 2023-10-24 | 东营市海科新源化工有限责任公司 | Preparation method and production system of vicinal diol compound |
| CN114057669A (en) * | 2020-07-29 | 2022-02-18 | 中国石油化工股份有限公司 | Ethylene epoxidation constant-temperature driving method |
| CN114057669B (en) * | 2020-07-29 | 2023-12-08 | 中国石油化工股份有限公司 | Ethylene epoxidation constant-temperature driving method |
| CN114436998A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Ethylene epoxidation start-up method |
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| CN106311233B (en) | 2019-05-31 |
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