CN104549544A - Method for preparing silver catalyst carrier, silver catalyst carrier obtained by method, silver catalyst and application thereof - Google Patents
Method for preparing silver catalyst carrier, silver catalyst carrier obtained by method, silver catalyst and application thereof Download PDFInfo
- Publication number
- CN104549544A CN104549544A CN201310522848.6A CN201310522848A CN104549544A CN 104549544 A CN104549544 A CN 104549544A CN 201310522848 A CN201310522848 A CN 201310522848A CN 104549544 A CN104549544 A CN 104549544A
- Authority
- CN
- China
- Prior art keywords
- carrier
- compound
- silver catalyst
- silver
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 76
- 239000004332 silver Substances 0.000 title claims abstract description 76
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008247 solid mixture Substances 0.000 claims abstract description 10
- 239000002210 silicon-based material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052702 rhenium Inorganic materials 0.000 claims description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 8
- 229940100890 silver compound Drugs 0.000 claims description 8
- 150000003379 silver compounds Chemical class 0.000 claims description 8
- 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 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 2
- 150000001553 barium compounds Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003438 strontium compounds Chemical class 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 4
- 238000006735 epoxidation reaction Methods 0.000 abstract description 4
- 238000004898 kneading Methods 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 abstract 1
- 150000004684 trihydrates Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- -1 ethylene glycols Chemical class 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 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 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940099259 vaseline Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 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
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002386 leaching Methods 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
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Abstract
The invention discloses a method for preparing a silver catalyst carrier. The method comprises the following steps: (I) providing a solid mixture, wherein the solid mixture comprises the following components in parts by weight: 20-90 parts of trihydrate alpha-Al2O3 with the granularity of 50-500 meshes, 5-70 parts of pseudo-hydrate Al2O3 of which the granularity can pass through a 200-mesh sieve, 0.05-7.0 parts of a fluoride mineralizer, 0.01-1.45 parts of an alkaline earth metal compound and 0.01-1.0 part of a silicon-containing compound, totaling 100 parts; (II) adding 0-3.5 parts of a titanium-containing aid compound into the solid mixture in the step (I); (III) adding 0.01-5.0 parts of a lubricating material into the mixture in the step (II); (IV) adding an adhesive into the mixture in the step (III) for kneading, extruding and forming; and (V) drying the product obtained in the step (IV), and roasting, thereby obtaining the silver catalyst carrier. The invention also provides a silver catalyst carrier obtained by the method, a silver catalyst prepared from the silver catalyst carrier, and application of the silver catalyst in the production of ethylene oxide by virtue of ethylene epoxidation.
Description
Technical field
The present invention relates to ethylene epoxidizing and produce oxirane silver catalyst field, be specifically related to a kind of preparation method of silver catalyst carrier, the silver catalyst carrier obtained by this preparation method and by the silver catalyst and the application thereof that comprise this silver catalyst carrier.
Background technology
Under silver catalyst effect, ethylene epoxidizing mainly generates oxirane (EO), and side reaction occurs simultaneously and generates carbon dioxide and water, wherein active, selective and stability is the main performance index of silver catalyst.Activity refers to the reaction temperature that process for ethylene oxide production reaches required when necessarily reacting load, and reaction temperature is lower, and the activity of catalyst is higher; Selectively refer to that in reaction, ethylene conversion becomes the ratio of the molal quantity of oxirane and the overall reaction molal quantity of ethene; Stability is then expressed as the fall off rate of activity and selectivity, and the stability of fall off rate more small catalyst is better.
Current silver catalyst has three kinds: one to be high activity silver catalyst, and this kind of catalyst activity is high, good stability, initial selectivity 80 ~ 82%, and service life, at 2-5, is applicable to all ethylene oxide/ethylene glycols (EO/EG) process units; Two is high selectivity silver catalysts, and this kind of catalyst is just selective reaches more than 88%, but requires CO in Reactor inlet reaction gas
2concentration, below 1.0%, is applicable to newly-built, that space-time yield is relatively low EO/EG process units; Three is intermediate selectivity silver catalyst (activity and selectivity silver catalysts between the former two), and the selective of this kind of catalyst can reach 83 ~ 85%, requires CO in the reaction gas of Reactor inlet
2concentration is below 3%.The selective of dissimilar catalyst can according to CO in reaction gas
2concentration and outlet EO concentration corresponding adjustment, the silver catalyst of high selectivity silver catalyst and intermediate selectivity to be widely used in industrial production and to instead of original high activity silver catalyst in recent years.
The performance of silver catalyst is except having important relationship with the composition of catalyst and preparation method, and the carrier property also used with catalyst and preparation method have important relationship.For with α-Al
2o
3for the carrier of key component, carrier physical property comprises compression strength, porosity, specific surface and pore size distribution etc., and a good catalyst carrier has outstanding compression strength, porosity and specific area.Higher porosity can reduce reactant and product gas diffusional resistance at reaction conditions; Specific surface requires a minimum, to ensure that catalyst component can be impregnated on carrier; Compression strength weighs a parameter of carrier physical integrity, stands operating condition, ensures that longer service life is necessary for catalyst.Study and found that new pore creating material has material impact to the physical property specification controlling carrier together with binding agent.Carrier has good specific surface and porosity, and compression strength may reduce; Contrary compression strength is high, can reduce specific surface and porosity.Balance between different physical property is very important for carrier.
US Patent No. 5512530 is by blend alpha-Al
2o
3, pore creating material and titanium dioxide prepares carrier, carrier has good compression strength while having good porosity and catalytic performance; US5929259 has set forth a kind of titania modified carrier, first by least one Al
2o
3, vitrified bonding and liquid medium shaping and make carrier through high temperature sintering, the carrier of high temperature sintering is dipped through again with the mixing material by TiO 2 sol and titanium-containing compound solution composition, carrier after dipping makes finished product through 450 ~ 700 DEG C of calcinings again, titanium dioxide is in the carrier dispersed, improves the structure of carrier; Chinese patent CN102553589A adopts a kind of compound titanium solution or the α-Al of sol impregnation after roasting that can be converted into titanium dioxide in roasting
2o
3carrier, then drying and 900-1380 DEG C of roasting obtain carrier finished product, and the catalyst that carrier is made thus demonstrates good activity and selectivity; US Patent No. 6603028 and US8124798 respectively describe the propylene ring oxidation reaction of the catalyst containing titanium in carrier under the existence of hydrogen and oxygen.
In addition, US Patent No. 2013006002A1 has set forth a kind of low surface area α phase Al
2o
3the preparation method of carrier, wherein α phase Al
2o
3content is greater than 90wt%, and silicone content is less than 6wt%, by α phase Al
2o
3and/or transitional face Al
2o
3, binding agent and solid pore forming agent, water-soluble titanium compound, adds water extrusion molding, drying and 1150 ~ 1600 DEG C of roastings and makes carrier, carrier pore volume 0.2 ~ 0.8ml/g after being dry mixed, preferably at 0.25 ~ 0.6ml/g; Specific surface is 0.4 ~ 4.0m
2/ g, is preferably 0.6 ~ 1.5ml/g; Crushing strength is greater than 8 pounds, is preferably and is greater than 10 pounds; US Patent No. 4200552 has been set forth by α-Al
2o
3with at least one compound, as SiO
2, TiO
2, ZrO
2with at least one in MgO etc., prepare Al as sintering aid
2o
3carrier, total pore volume 0.05 ~ 0.50ml/g, average pore size 0.05 ~ 5.0 μm, specific surface 3 ~ 60m
2/ g; US Patent No. 6908879 describes a kind of in acid α-Al
2o
3carrier, first the mixing of aluminum contained compound, silicon-containing compound and titanium-containing compound is added binding agent and water, through mediate, shaping after at 1000-2000 DEG C calcine, alundum (Al2O3) in carrier finished product, silica and titanium dioxide account for more than 99% of carrier gross weight, and the silica after calcining and titanium dioxide exist with amorphous state; US Patent No. 7060651B2, describes a kind of high silicon carrier, the content of silica more than 70%, specific surface 0.5-30m
2/ g, with at least one in the metal components such as platinum, palladium, silver, molybdenum, titanium, zirconium and copper or its oxide for active component, its content is not more than 2% in metal, active component in the form of a solution at 40-200 DEG C of dipping and load on carrier, then obtain catalyst through heat treatment and can be used for ethene or propylene ring oxidation reaction.
Summary of the invention
The present inventor has carried out research extensively and profoundly in silver catalyst carrier preparation field, finds with three water Al
2o
3with a water Al
2o
3for raw material is in carrier preparation process, adds silicon additive and specific surface can be made to increase; Adding titanium auxiliary agent can make carrier porosity increase; Two kinds of auxiliary agents add the carrier after high temperature sintering simultaneously, under the prerequisite keeping advantages of higher compressive strength, porosity increases, specific surface slightly increases, be less than the ratio increase that 0.5 μm of hole accounts for total pore volume, when the catalyst prepared of carrier is for ethylene epoxidizing epoxy ethane thus, catalyst activity and selectivity is obviously improved.
The invention provides a kind of preparation method of silver catalyst carrier, comprising:
I) provide solid mixture, described solid mixture comprises with 100 parts by weight:
II) in step I) solid mixture in add the first intermediate product that titaniferous auxiliary compound obtains, described titanium auxiliary compound is in titanium elements 0 ~ 3.5 weight portion, preferably 0.1 ~ 3.5 weight portion;
III) to Step II) add 0.01 ~ 5.0 weight portion lubriation material in the first intermediate product of obtaining and obtain the second intermediate product;
IV) to Step II I) add that binding agent carries out mediating, extruded moulding obtains the 3rd intermediate product in the second intermediate product of obtaining, wherein the consumption of binding agent is 25 ~ 60 weight portions;
V) by step IV) in the 3rd intermediate product that obtains dry and described silver catalyst carrier is made in roasting.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described three water α-Al
2o
3consumption be 50 ~ 80 weight portions.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, a described false water Al
2o
3consumption be 15 ~ 45 weight portions.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described fluoride-mineralization agent is selected from least one in following compound: hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal.The effect of described fluoride-mineralization agent is to accelerate Al
2o
3transformation of crystal, and reduce by the pore of less than 0.5 μm, its addition preferably 0.1 ~ 6.0wt%.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described alkaline earth metal compound is selected from the oxide of alkaline-earth metal, sulfate, acetate, nitrate and oxalates, is preferably strontium compound and/or barium compound.Its role is to improve carrier property, addition is preferably 0.2 ~ 0.9%.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described silicon-containing compound is selected from silicate and/or silica.The effect of described silicon compound is can make to increase lower than 0.5 μm of hole in carrier, and make the specific surface that carrier keeps higher, its addition is preferably 0.1 ~ 0.5%.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described titaniferous auxiliary compound is selected from least one in titanium dioxide, titanium tetrachloride and organic titanate.The effect of described titanium auxiliary compound is the porosity increasing carrier, and its addition is preferably 0.2 ~ 2.5%.
The silicon-containing compound added is solid silicate or silica, the interaction raised between organic titanium auxiliary agent along with temperature is very little, mainly silicon-containing compound and aluminium oxide and the interaction between titanium-containing compound and aluminium oxide, silicon-containing compound can make to increase lower than 0.5 μm of hole, and titanium-containing compound can increase the macropore in carrier, the pore size distribution that the ratio controlling silicon and titanium can make carrier reach suitable, thus make catalyst performance reach best.
In a preferred embodiment of the preparation method of above-mentioned silver catalyst carrier of the present invention, described lubriation material is selected from least one in petroleum coke, carbon dust, graphite and vaseline.Described lubriation material preferably can the lubriation material of after-flame, it adds is to make the material after kneading be easy to shaping and granulation, in material roasting process, there is oxidation reaction simultaneously, generation gas is overflowed, do not introduce when making carrier or introduce other impurity as few as possible, thus not affecting the performance of catalyst.Can after-flame lubriation material can be Powdered, paste according to the present invention, its consumption be preferably 0.05 ~ 4.0wt%.
In the preparation method of above-mentioned carrier, described three water α-Al
2o
3in high-temperature calcination process, dehydration turns brilliant one-tenth α-Al
2o
3, a false water Al
2o
3with acid reaction in acid adding kneading process, change into colloidal sol, play binding agent effect, in high-temperature calcination process, also change into stable α-Al
2o
3, become α-Al
2o
3a part for carrier.Three water α-Al
2o
3addition be preferably 50 ~ 80 weight portions; A false water Al
2o
3addition be preferably 15 ~ 45 weight portions.
In the preparation method of above-mentioned carrier, add the vacation one water Al in binding agent and mixture
2o
3generate Alumina gel, each component is bonded together, becoming can the paste of extrusion molding.Binding agent used comprises acid, as nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid etc.When using acid as binding agent, preferably nitre aqueous acid, wherein the weight ratio of nitric acid and water is 1:1.25 ~ 10.
In the preparation method of above-mentioned carrier, described binding agent and a false water Al
2o
3the all or part of replacement of Alumina gel can be used.In the present invention, because binding agent is acid, namely generates Alumina gel with a false Water oxidize reactive aluminum, same material should be belonged to the Alumina gel of ready-made suitable concentration, therefore can by binding agent and a false water Al
2o
3replace with Alumina gel.
In the preparation method of above-mentioned carrier, described solid mixture and binding agent carry out kneading and obtain a kind of paste, then can be dried to moisture less than 10 % by weight after paste extrusion molding, and support shapes can be annular, spherical, cylindricality or porous column shape.Baking temperature is 80 ~ 120 DEG C, and drying time controls at 1 ~ 24 hour according to moisture.
In the preparation method of above-mentioned carrier, described step V) in roasting time be 1 ~ 20 hour, preferably 2 ~ 15 hours, roasting made Al
2o
3all be converted into α-Al
2o
3.The sintering temperature of described roasting is preferably 1100-1450 DEG C.
The invention provides a kind of α-Al of ethylene epoxidizing silver catalyst
2o
3carrier, described carrier comprises α-Al
2o
3, wherein, described carrier hole distribution mesoporous accounts for 4 ~ 15% of total pore volume lower than the hole of 0.5 μm, and containing titanium and element silicon in described carrier, and the mass ratio of titanium elements and element silicon is 0 ~ 10, is preferably 0.5 ~ 4.5.
In above-mentioned carrier, described α-Al
2o
3mass content is more than 90%.
The crushing strength of described carrier is 60 ~ 210N/ grain, preferably 80 ~ 150N/ grain; Specific surface is 0.80 ~ 2.0m
2/ g, preferably 0.9 ~ 1.8m
2/ g; Porosity is greater than 60%; Pore volume 0.4 ~ 0.75ml/g, preferably 0.45 ~ 0.6ml/g.
In the present invention, the side crush intensity of carrier adopts DL II type intelligence detector for strength of particles, and choose support samples, averaging after measuring radial crushing strength obtains; Specific area adopts nitrogen physisorption BET method to measure; Porosity, pore volume and pore size distribution$ adopt pressure mercury method to measure.
Present invention also offers a kind of ethylene epoxidizing silver catalyst, comprising:
A) α-Al of the present invention
2o
3carrier;
B) silver compound;
C) alkali metal promoter;
D) base earth metal promoter;
E) rhenium auxiliary agent and coassist agent thereof.
Silver catalyst of the present invention can be prepared in the usual way, by the above-mentioned Al of solution impregnation with a kind of Ag-containing compound, organic amine, alkali metal promoter, base earth metal promoter and rhenium-containing auxiliary agent and optional coassist agent composition thereof
2o
3prepared by carrier.This organic amine compound can for being suitable for any organic amine compound preparing ethylene oxide silver catalyst, as long as this organic amine compound can form argent-amine complex with silver compound, as pyridine, butylamine, ethylenediamine, 1,3-propane diamine, monoethanolamine or its mixture, the mixture of preferred ethylenediamine and monoethanolamine.
Described silver compound also has no particular limits, as long as can argent-amine complex be formed with described organic amine compound, and preferred silver oxalate and/or silver nitrate.
Described alkali metal promoter can be at least one in the compound of lithium, sodium, potassium, rubidium or caesium, as their nitrate, sulfate or hydroxide, or two or more combination any of aforesaid compound, preferably sulfuric acid caesium and/or cesium nitrate.
Described base earth metal promoter can be at least one in the compound of magnesium, calcium, strontium or barium, as their oxide, oxalates, sulfate, acetate or nitrate, or two or more combination any of aforesaid compound, the compound of preferred barium or strontium, more preferably barium acetate and/or strontium acetate.Described base earth metal promoter can before dipping silver, also can be immersed on carrier after silver compound is reduced simultaneously or be applied to afterwards on carrier.
Described rhenium auxiliary agent can be oxide, perrhenic acid, the perrhenate of rhenium, or its mixture, preferred perrhenic acid and perrhenate, such as perrhenic acid, perrhenic acid caesium and ammonium perrhenate etc.; Described coassist agent can be the compound of arbitrary transition metal in the periodic table of elements, or the mixture of several transistion metal compound, metal in described coassist agent is preferably selected from group vib and VIIB race element, described coassist agent can comprise oxyacid and the salt thereof of group vib and VIIB race element, such as wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate etc., also can be the salt (as cerous sulfate) of rare earth element.Rhenium auxiliary agent and coassist agent thereof can before dipping silver, also can be immersed on carrier after silver compound is reduced simultaneously or be applied to afterwards on carrier.The stability of the activity of gained silver catalyst, selective and activity and selectivity can be improved further by adding rhenium auxiliary agent and coassist agent thereof.
In above-mentioned silver catalyst, be 100 % by weight with the gross weight of described catalyst, described catalyst comprises:
In specific embodiment, silver catalyst preparation method comprises the steps:
1) the above-mentioned porous α of the solution impregnation-Al of the silver compound, organic amine, alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent and the coassist agent thereof that contain q.s is used
2o
3carrier;
2) elimination maceration extract, dry impregnated carrier; With
3) containing in oxygen gas mixture to step 2) gained carrier activates, and makes described silver catalyst.
In the preparation of silver catalyst of the present invention, first dissolve silver oxalate with ethylenediamine and aqueous ethanolamine and make argentamine liquid, then add above-mentioned auxiliary agent and be made into maceration extract; Then above-mentioned α-Al is soaked with the maceration extract of preparation
2o
3carrier, drains, and is not more than 21%(as containing oxygen 8.0% at air stream or oxygen content) nitrogen oxygen atmosphere in keep 0.5 ~ 120 minute in 180 ~ 700 DEG C preferably temperature range of 200 ~ 500 DEG C, preferably within 1 ~ 60 minute, carry out thermal decomposition and make finished product silver catalyst.
Present invention also offers the application of a kind of described silver catalyst in ethylene epoxidizing production oxirane.Produce in oxirane at ethylene epoxidizing, described ethene is carried out epoxidation reaction in reaction unit under the existence of above-mentioned silver catalyst, described reaction unit import CO
2concentration is lower than 3mol%.Described reaction unit can be any device that can carry out epoxidation reaction.
Beneficial effect of the present invention:
Carrier of the present invention adds titaniferous auxiliary compound and siliceous auxiliary compound in preparation process, carrier obtained after high-temperature roasting has more preferably porosity, specific surface and pore structure, wherein account for 4 ~ 15%(of total pore volume by volume lower than the hole of 0.5 μm), compare with prior art, be applicable to reaction unit import CO according to the silver catalyst that carrier provided by the invention is made
2concentration is the epoxidation reaction lower than 3mol%, is specially adapted to the reaction that ethylene produces oxirane, has the advantage that activity and selectivity is high.
Detailed description of the invention
The present invention is described further below in conjunction with embodiment, but scope of the present invention is not limited to these embodiments.
Various silver catalyst laboratory reaction device of the present invention (following letter " micro-anti-") evaluating apparatus tests its initial performance and stability.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating jacket.The admission space of catalyst is 1ml, and inert filler is arranged at bottom, makes beds be positioned at the flat-temperature zone of heating jacket.
The condition determination of the activity and selectivity that the present invention uses is as follows:
The gas composition (mol%) of Reactor inlet: ethene (C
2h
4), 28.0 ± 1.0; Oxygen (O
2), 7.4 ± 0.2; Carbon dioxide (CO
2), < 3.0; Cause steady gas (N
2), surplus; Inhibitor dichloroethanes (in right amount), oxirane (EO) concentration, 2.50%.Reaction pressure, 2.1MPa; Air speed, 7000/h; Space-time yield, 344gEO/mlCat./h.
When stable reach above-mentioned reaction condition after METHOD FOR CONTINUOUS DETERMINATION reactor enter, exit gas composition.Measurement result calculates selective as follows after carrying out volume contraction correction:
Wherein, EO works off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, gets the result of the test of average as the same day of more than 10 groups test datas.
Embodiment 1
The preparation of carrier
By 50 ~ 500 object three water α-Al
2o
34800g, by the vacation one water Al of 200 mesh sieves
2o
31200g, NH
4f150g, barium nitrate 21g and silica 9.8g put into blender and mix, and proceed in kneader, add 42g vaseline and 2100ml dust technology (nitric acid: water=1:3, weight ratio), and being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.By above-mentioned kneaded and formed after carrier put into top-hat kiln, be elevated to 1280 DEG C through 33 hours from room temperature, under 1280 DEG C of conditions calcine 10 hours, obtain white silver catalyst carrier.The carrier physical property recorded and pore size distribution$ data are distinguished as shown in table 1 below.
The preparation of catalyst
980g ethylenediamine and 255g monoethanolamine are dissolved in 1500g deionized water, under agitation silver oxalate is slowly added in mixed liquor, temperature remains on less than 40 DEG C, silver oxalate is all dissolved, the addition of silver oxalate be in silver catalyst in the silver content of silver element for 13%(weight), adding 9.0g cesium nitrate, 7.8g calcium acetate, 4.4g perrhenic acid, 1.0g cerous sulfate and deionized water again makes solution gross mass reach 5000g, is mixed with maceration extract stand-by.
Get support samples 2500g, put into the container that can vacuumize, be evacuated to more than 10mmHg, introduce above-mentioned maceration extract, keep 30min, unnecessary solution is removed in leaching.Carrier after dipping heats 3min in the air stream of 450 DEG C, and cooling, namely makes silver catalyst.
Use microreactor evaluating apparatus under previous process condition, measure the activity and selectivity of catalyst sample, micro anti-evaluation the results are shown in table 2.
Comparative example 1
The preparation method of carrier is with embodiment 1, and difference is not add silica, and the carrier physical property obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
Embodiment 2
By 50 ~ 500 object three water α-Al
2o
34800g, by the vacation one water Al of 200 mesh sieves
2o
31200g, NH4F150g, barium nitrate 21g and silica 9.8g puts into blender and mixes, proceed in kneader, add 22.3g butyl titanate, 42g vaseline and 2100ml dust technology (nitric acid: water=1:3, weight ratio), being kneaded into can the paste of extrusion molding.Extrusion molding is the five hole columns of external diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, dries more than 2 hours, make free water content be reduced to less than 10% at 80 ~ 120 DEG C.By above-mentioned kneaded and formed after carrier put into top-hat kiln, be elevated to 1280 DEG C through 33 hours from room temperature, under 1280 DEG C of conditions calcine 10 hours, obtain white silver catalyst carrier.The carrier physical property recorded and pore size distribution$ data are distinguished as shown in table 1 below.
Embodiment 3
The preparation method of carrier is with embodiment 1, and difference is to add 42.7g butyl titanate, and the physical property of the silver catalyst carrier obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
Embodiment 4
The preparation method of carrier is with embodiment 1, and difference is to add 85.6g butyl titanate, and the physical property of the silver catalyst carrier obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
Embodiment 5
The preparation of carrier is with embodiment 1, and difference is to add 128.8g butyl titanate, and the physical property of the silver catalyst carrier obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
Comparative example 2
The preparation of carrier is with embodiment 1, and difference is add 128.8g butyl titanate but do not add silica, and the physical property of the silver catalyst carrier obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
Embodiment 6
The preparation of carrier is with embodiment 1, and difference is to add 213.8g butyl titanate, and the physical property of the silver catalyst carrier obtained and pore size distribution$ data are distinguished as shown in table 1 below; The preparation of catalyst is with embodiment 1, and the micro anti-evaluation of catalyst the results are shown in Table 2.
As can be seen from Table 1, the porosity of the catalyst carrier that the present invention obtains, pore volume and specific area have the catalyst carrier being better than comparative example and providing, in particularly pore size distribution structure, to account for the carrier that provides in the important comparison ratio of ratio of total pore volume high a lot of for 0-0.5 μm and 0.5-1.5 μm in aperture, illustrate that the average pore size of the carrier that the average pore size of the catalyst carrier that preparation method of the present invention obtains provides relative to comparative example is much smaller.
In addition, the catalytic effect of the silver catalyst using carrier of the present invention to prepare is as shown in table 2, under selective suitable condition, use the reaction temperature of silver catalyst of the present invention more much lower than the reaction temperature of the silver catalyst using comparative example, illustrate that the activity of the silver catalyst using the silver catalyst of method of the present invention to provide than comparative example is higher.
The physical property of table 1 carrier and pore size distribution$ data
The performance of table 2 catalyst
Claims (10)
1. a preparation method for silver catalyst carrier, comprising:
I) provide solid mixture, described solid mixture comprises with 100 parts by weight:
II) in step I) solid mixture in add the first intermediate product that titaniferous auxiliary compound obtains, described titanium auxiliary compound is in titanium elements 0 ~ 3.5 weight portion, preferably 0.1 ~ 3.5 weight portion;
III) to Step II) add 0.01 ~ 5.0 weight portion lubriation material in the first intermediate product of obtaining and obtain the second intermediate product;
IV) to Step II I) add that binding agent carries out mediating, extruded moulding obtains the 3rd intermediate product in the second intermediate product of obtaining, wherein the consumption of binding agent is 25 ~ 60 weight portions;
V) by step IV) in the 3rd intermediate product that obtains dry and described silver catalyst carrier is made in roasting.
2. method according to claim 1, is characterized in that, described three water α-Al
2o
3consumption be 50 ~ 80 weight portions; A described false water Al
2o
3consumption be 15 ~ 45 weight portions; Described fluoride-mineralization agent is selected from least one in following compound: hydrogen fluoride, aluminum fluoride, ammonium fluoride, magnesium fluoride and ice crystal; Described alkaline earth metal compound is selected from strontium compound and/or barium compound.
3. method according to claim 1 and 2, is characterized in that, described silicon-containing compound is selected from silicate and/or silica.
4. the method according to any one of claim 1-3, is characterized in that, described titaniferous auxiliary compound is selected from least one in titanium dioxide, titanium tetrachloride and organic titanate.
5. comprise the silver catalyst carrier that the preparation method according to any one of claim 1-4 obtains, described carrier comprises α-Al
2o
3, wherein, described carrier hole distribution mesoporous accounts for 4 ~ 15% of total pore volume lower than the hole of 0.5 μm, and containing titanium and element silicon in described carrier, and the mass ratio of titanium elements and element silicon is 0 ~ 10, is preferably 0.5 ~ 4.5.
6. catalyst carrier according to claim 5, is characterized in that, the crushing strength of described carrier is 60 ~ 210N/ grain, preferably 80 ~ 150N/ grain; Specific surface is 0.80 ~ 2.0m
2/ g, preferably 0.9 ~ 1.8m
2/ g; Porosity is greater than 60%; Pore volume 0.4 ~ 0.75ml/g, preferably 0.45 ~ 0.6ml/g.
7. a silver catalyst, comprising:
A) α-Al described in claim 5 or 6
2o
3carrier;
B) silver compound;
C) alkali metal promoter;
D) base earth metal promoter;
E) rhenium auxiliary agent and coassist agent thereof.
8. silver catalyst according to claim 7, is characterized in that, described silver compound is selected from silver oxalate and/or silver nitrate; Described alkali metal promoter is selected from least one in the compound of lithium, sodium, potassium, rubidium or caesium, preferably sulfuric acid caesium and/or cesium nitrate; Described base earth metal promoter is selected from least one in the compound of magnesium, calcium, strontium or barium, the compound of preferred barium and/or strontium, more preferably barium acetate and/or strontium acetate; Described rhenium auxiliary agent is selected from least one in the oxide of rhenium, perrhenic acid and perrhenate, preferred perrhenic acid caesium and/or ammonium perrhenate; Described coassist agent is selected from least one in wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate and cerous sulfate.
9. the silver catalyst according to claim 7 or 8, is characterized in that, be 100 % by weight parts in the gross weight of catalyst, described catalyst comprises:
10. the application of the silver catalyst according to any one of claim 7-9 in ethylene epoxidizing production oxirane.
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| CN201310522848.6A CN104549544B (en) | 2013-10-29 | 2013-10-29 | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application |
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| CN201310522848.6A CN104549544B (en) | 2013-10-29 | 2013-10-29 | Silver catalyst carrier preparation method, thus obtained silver catalyst carrier, silver catalyst and its application |
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| CN107960063A (en) * | 2015-08-28 | 2018-04-24 | 利安德化学技术有限公司 | Epoxidation process and catalysts used |
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