CN115739177B - Acetyloxidation catalyst, preparation method thereof and method for preparing vinyl acetate - Google Patents
Acetyloxidation catalyst, preparation method thereof and method for preparing vinyl acetate Download PDFInfo
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- CN115739177B CN115739177B CN202211571974.6A CN202211571974A CN115739177B CN 115739177 B CN115739177 B CN 115739177B CN 202211571974 A CN202211571974 A CN 202211571974A CN 115739177 B CN115739177 B CN 115739177B
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- catalyst
- potassium
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- oxygen
- active component
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 21
- -1 methyl indigo red Chemical compound 0.000 claims description 15
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229940097275 indigo Drugs 0.000 claims description 14
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 14
- CRDNMYFJWFXOCH-BUHFOSPRSA-N Couroupitine B Natural products N\1C2=CC=CC=C2C(=O)C/1=C1/C2=CC=CC=C2NC1=O CRDNMYFJWFXOCH-BUHFOSPRSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- CRDNMYFJWFXOCH-YPKPFQOOSA-N (3z)-3-(3-oxo-1h-indol-2-ylidene)-1h-indol-2-one Chemical compound N/1C2=CC=CC=C2C(=O)C\1=C1/C2=CC=CC=C2NC1=O CRDNMYFJWFXOCH-YPKPFQOOSA-N 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- CRDNMYFJWFXOCH-UHFFFAOYSA-N indirubin Chemical compound N1C2=CC=CC=C2C(=O)C1=C1C2=CC=CC=C2NC1=O CRDNMYFJWFXOCH-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000001508 potassium citrate Substances 0.000 claims description 5
- 229960002635 potassium citrate Drugs 0.000 claims description 5
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 5
- 235000011082 potassium citrates Nutrition 0.000 claims description 5
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 claims description 5
- MLCPSWPIYHDOKG-BUHFOSPRSA-N (3e)-3-(2-oxo-1h-indol-3-ylidene)-1h-indol-2-one Chemical compound O=C\1NC2=CC=CC=C2C/1=C1/C2=CC=CC=C2NC1=O MLCPSWPIYHDOKG-BUHFOSPRSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000001472 potassium tartrate Substances 0.000 claims description 4
- 229940111695 potassium tartrate Drugs 0.000 claims description 4
- 235000011005 potassium tartrates Nutrition 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 claims description 3
- 239000001415 potassium malate Substances 0.000 claims description 3
- 235000011033 potassium malate Nutrition 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 33
- 239000011591 potassium Substances 0.000 abstract description 23
- 229910052700 potassium Inorganic materials 0.000 abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 22
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 27
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 24
- 229960003975 potassium Drugs 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000000741 silica gel Substances 0.000 description 21
- 229910002027 silica gel Inorganic materials 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000008188 pellet Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 10
- 229910001414 potassium ion Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an acetyl oxidation catalyst, a preparation method thereof and a method for preparing vinyl acetate, wherein the catalyst comprises a carrier, an additive, an active component and an auxiliary agent; the main chemical component of the carrier is SiO 2 、Al 2 O 3 、Fe 2 O 3 Or a mixture thereof; the additive is an indigoid compound or a derivative thereof; the active component comprises at least one of (a) Pd element and (b) Cu, au and Sn element; the auxiliary agent is potassium polycarboxylic acid. The invention mainly solves the problem of low catalyst activity and selectivity in the prior art, and can be industrially applied to C 2 ‑C 4 Alkene, acetic acid and oxygen are subjected to acetyl oxidation reaction to prepare the vinyl acetate.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to an acetyl oxidation catalyst, a preparation method thereof and a method for preparing vinyl acetate.
Background
Vinyl acetate is an important organic synthetic intermediate, and typical vinyl acetate is vinyl acetate, allyl acetate, methallyl alcohol acetate, and the like. The allyl acetate is colorless inflammable liquid, is slightly soluble in water, is easy to dissolve in alcohol and ether, and can dissolve in acetone, and is used as one important chemical material for producing important organic synthetic material, such as allyl alcohol, epoxy chloropropane, glycerin, etc. and for synthesizing resin and adhesive.
In the 80 s of the 20 th century, japanese Zhaogao electricians realized the industrial production of allyl acetate for the first timeThe method is characterized in that an acetyl oxidation technology is developed, propylene, oxygen and acetic acid are used as raw materials in the presence of palladium and a cocatalyst, a fixed bed gas phase reaction is adopted to prepare allyl acetate, and an acetyl oxidation catalyst is adopted to prepare the allyl acetate by SiO 2 、Al 2 O 3 Or SiO 2 And Al 2 O 3 The mixture is used as a carrier and is loaded with palladium, copper and potassium acetate, and the palladium and copper active components are distributed in an eggshell shape.
Patent publication No. CN 104107722B describes an allyl acetate catalyst, which is prepared by adding a oxynitride as an auxiliary agent to solve the problem of low catalyst activity and selectivity, and the auxiliary agent solves the problem of low catalyst activity and selectivity, but has the problems of loss and difficult addition in industrial production, so that the service life of the catalyst in industry is limited.
Publication CN 1131199C describes an oxyacylation catalyst for the preparation of allyl acetate which is added during the preparation process with metallic tin or a mixture of tin and an additional promoter metal, by which the catalyst life is maintained without the addition of water to the feed. Since water is generated in the acetyl oxidation reaction and the generated water removes part of the heat generated by the acetyl oxidation reaction, the method of adding no water has no industrial application advantage.
Patent publication No. CN 103120961B describes an allyl acetate catalyst and a process for preparing the same. The catalyst is prepared by SiO 2 、Al 2 O 3 Or a mixture thereof is used as a carrier, the loaded active components comprise metal palladium, metal copper and alkali metal acetate, and the average grain diameter of palladium copper grains is 5-7nm; in the preparation process of the catalyst, liquid carbon dioxide is used as impregnating solution, the palladium compound is acetyl acetonyl as ligand, and the raw materials adopted in the preparation method are expensive, so that the production cost is too high, and the industrial application economy is not realized.
Patent publication No. CN 104437622B describes an allyl acetate catalyst, wherein the carrier of the catalyst comprises a carrier, an active component and a cocatalyst, the catalyst is prepared by ultrasonic treatment of the carrier in the presence of organic amine in the preparation process, the price of the organic amine is expensive, the ultrasonic treatment is unfavorable for industrialized large-scale production, and the catalyst is unfavorable for industrialized large-scale application.
Therefore, development of a catalyst having high activity and good industrial application prospect is required.
Disclosure of Invention
The invention aims to provide a catalyst for acetyl oxidation and a preparation method of the catalyst, wherein an indigo compound or a derivative thereof is added in the acetyl oxidation catalyst, so that the dispersibility of an active component is better, and the activity and the selectivity of the catalyst are higher; the indigoid compound or the derivative thereof can interact with the auxiliary agent potassium polycarboxylic acid, so that the loss of auxiliary agent potassium ions is reduced, the activity and selectivity of the catalyst are maintained, and the service life of the catalyst is longer.
The invention also aims to provide a method for preparing the allyl acetate compound, in particular to a method for preparing the allyl acetate compound, and the allyl acetate is prepared under the action of the catalyst provided by the invention, and has the characteristics of high activity and high selectivity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an acetyl oxidation catalyst comprising a support, an additive, an active component and an adjunct;
the main chemical component of the carrier is SiO 2 、Al 2 O 3 、Fe 2 O 3 Or a mixture thereof;
the additive is at least one of indigoid compounds or derivatives thereof;
the active component comprises at least one of (a) Pd element and (b) Cu, au and Sn element;
the auxiliary agent is potassium polycarboxylic acid.
Preferably, the specific surface area of the carrier is 100-600m 2 Per g, pore volume of 0.3-1.2mL/g, average pore diameter of 5-20nm, and bulk density of 300-900g/L.
Further, the specific surface area of the carrier is 120-400m 2 /g，More preferably 150-300m 2 /g; pore volume is 0.4-1.0mL/g, more preferably 0.6-0.9mL/g; the average pore diameter is 6 to 19nm, more preferably 9 to 18nm; the bulk density is 350 to 800g/L, more preferably 400 to 700g/L.
Preferably, the content of the indigo compound or derivative thereof is 0.05 to 10g/L, preferably 0.2 to 8g/L, more preferably 0.5 to 6g/L; the indigo compound or the derivative thereof is at least one selected from indigo, isoindigo, isatin, indirubin, methyl indirubin, hydroxyl indirubin, allylindirubin, benzyl indirubin, thioindigo and thioindigo.
The active component comprises a component (a) and a component (b), wherein the component (a) is palladium, the component (b) is at least one of elemental copper, gold and tin, and preferably, the content of the palladium in the active component is 0.5-15g/L, more preferably 0.6-10g/L; the content of (b) in the active component is 0.1 to 10g/L, more preferably 0.2 to 6g/L.
The auxiliary agent is potassium polycarboxylic acid, preferably, the potassium polycarboxylic acid is at least one of potassium tartrate, potassium malate, potassium oxalate and potassium citrate, more preferably, potassium citrate and potassium tartrate; the content of potassium polycarboxylic acid is 5 to 80g/L, more preferably 10 to 70g/L.
The preparation method of the catalyst provided by the invention comprises the following steps:
1) Roasting a carrier: roasting the carrier at a certain temperature by taking oxygen-containing gas as carrier gas to obtain a treated carrier;
2) Additive loading: preparing a solution containing an indigo compound or a derivative thereof, slowly adding the prepared additive solution into the carrier obtained in the step 1), aging for a period of time, and drying at a certain temperature to obtain a catalyst precursor 1;
3) Active component loading and fixing: preparing a salt solution containing active component elements, slowly adding the prepared active component solution into the precursor 1 obtained in the step 2), and then placing the catalyst precursor 1 impregnated with the active component into alkali liquor for fixing the active component to obtain a catalyst precursor 2;
4) Reduction of active components: carrying out reduction treatment on the catalyst precursor 2 obtained in the step 3) and a reducing agent, washing and drying to obtain a catalyst precursor 3;
5) Addition of auxiliary agent: preparing a certain amount of potassium polycarboxylic acid solution, immersing the potassium polycarboxylic acid solution into the catalyst precursor 3, and drying to obtain a catalyst finished product.
Further, the oxygen-containing carrier gas in the step 1) is at least one of air, oxygen, a mixture of oxygen and nitrogen, and preferably air; the calcination temperature is 300-900 ℃, preferably 350-750 ℃.
Further, in the step 2, the aging time is 0.5-6h, and the drying temperature is 100-300 ℃.
The inventor researches and discovers that the addition of the indigo compound or the derivative thereof affects the dispersion of palladium and other metal elements in the active component, compared with a catalyst prepared without adding the indigo compound or the derivative thereof, the addition of the indigo compound or the derivative thereof can obviously promote the dispersion of the active component, the dispersity of the active component is higher, the exposed palladium active site is more, the raw materials participating in the reaction are more easily activated, and the activity and the selectivity of the catalyst are higher.
Further, in the step 3, the palladium salt is at least one of sodium chloride, potassium chloride, palladium acetate, palladium nitrate and palladium sulfate, preferably sodium chloride and palladium chloride; the salt containing the element (b) is at least one of soluble chloride, nitrate, acetate, sulfide and the like of copper, gold and tin, preferably soluble chloride; the alkali liquor is at least one of sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide aqueous solution, preferably sodium silicate and/or sodium hydroxide aqueous solution, and the alkali liquor is used for completely precipitating the free active components (a) and (b).
Further, the reducing agent in step 4 includes at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene, and isobutene, preferably hydrazine hydrate and hydrogen. The reducing agent is used in an amount sufficient to completely reduce the active components (a) and (b) in the oxidized state.
The inventor researches find that compared with potassium monocarboxylate, the potassium monocarboxylate is more beneficial to improving the activity of the oxyacylation reaction and inhibiting the side reaction for generating carbon dioxide, and improves the catalytic activity and the selectivity of target products; and the potassium polycarboxylic acid can form interaction with the indigoid compound or the derivative thereof, so that the potassium ions of the auxiliary agent are not easy to run off, the activity and the selectivity of the catalyst can be maintained, and the service life of the catalyst is long.
A process for preparing vinyl acetate in the presence of catalyst of the present invention with acetic acid, oxygen and C 2 -C 4 Alkene is used as raw material, and the vinyl acetate is prepared through the acetyl oxidation reaction.
Further, the method for preparing vinyl acetate comprises the following steps:
acetic acid, oxygen and C 2 -C 4 Feeding olefin raw material into a reactor filled with the catalyst of the invention, wherein the raw material is C in mole ratio 2 -C 4 The alkene is acetic acid, oxygen=1, (0.1-0.5) and (0.1-0.5), acetyl oxidation reaction is carried out at 120-180 ℃ and 0.1-1.5MPaG, and the volume space velocity is 1000-3000h -1 Preparing vinyl acetate;
preferably, the C 2 -C 4 The olefin raw material is propylene;
further, the method for preparing allyl acetate comprises the steps of (1) acetic acid, water=1 (0.1-0.5) (0.1-1), performing acetyl oxidation reaction at 120-180 ℃ and 0.1-1.5MPaG, wherein the volume space velocity is 1000-3000h -1 Allyl acetate is prepared.
The invention has the following beneficial effects:
1) The invention provides an acetyl oxidation catalyst and a preparation method thereof, wherein an indigo compound or a derivative thereof is added in the acetyl oxidation catalyst, so that the dispersibility of an active component is better, the catalytic activity and the selectivity are higher, and the problem that the activity and the selectivity of an acetate catalyst synthesized in the prior art are not high is solved.
2) Compared with potassium monocarboxylate, the catalyst auxiliary agent is more beneficial to improving the activity of the oxyacylation reaction and inhibiting side reaction generating carbon dioxide, and improves the catalytic activity and the selectivity of target products; and the potassium polycarboxylic acid can form interaction with the indigoid compound or the derivative thereof, so that the potassium ions of the auxiliary agent are not easy to run off, the activity and selectivity of the catalyst are maintained, and the service life of the catalyst is long.
3) Compared with the existing catalyst preparation technology, the acetyl oxidation catalyst provided by the invention has the advantages of simple steps, low raw material cost, production cost saving and industrial application competitiveness.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The calculation method and test method used in the examples or comparative examples are as follows:
1. the content of each component in the reaction product was analyzed by using a gas chromatography using an Agilent GC 8890A chromatograph, and the activity and selectivity of the catalyst were calculated according to the following formula
2. Method for measuring specific surface area and pore structure information of catalyst
Pore structure of the catalyst through N 2 The specific surface area is measured by a physical adsorption method, the BET method and the pore volume are obtained by a BJH desorption method, and the model of a testing instrument is Micromeritics ASAP 2460.
3. Determination of the particle size of the catalyst active component
A certain amount of the catalyst was pulverized with a mortar to obtain a uniform powder, and then the catalyst powder was ultrasonically dispersed in absolute ethanol, which was measured using a JEOL 2100plus Transmission Electron Microscope (TEM).
4. Catalyst promoter elemental loss analysis
A sample obtained by a certain amount of reaction was taken, and the potassium element contained therein was measured by an inductively coupled plasma spectrometer (ICP) type of SieiCAP PRO.
[ example 1 ]
1) Preparation of the catalyst
1L of silicon is takenRubber small ball (average grain size 5mm, specific surface area 221 m) 2 Per g, pore volume of 0.86mL/g, average pore diameter of 14.5nm, bulk density of 504 g/L), and roasting in a muffle furnace at 500 ℃ for 4h under air atmosphere;
296mL of aqueous solution containing 2.1g of indigo is prepared, fully and uniformly stirred, uniformly sprayed on silica gel pellets, and kept stand for 4 hours, and then thoroughly dried in a baking oven at 150 ℃;
preparing 420mL of aqueous solution containing 4.8g Pd and 1.0g Cu of sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 53.5g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A;
then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, fully washing with deionized water until no chloride ions are detected, and putting into a baking oven for baking to obtain a catalyst precursor B;
400mL of a solution containing 55g of potassium citrate was impregnated onto the catalyst precursor B and dried sufficiently to obtain a catalyst finished product. The active component has an average particle size of 3.2nm as analyzed.
2) Catalyst Performance test
Putting 500mL of catalyst into a fixed bed reactor with an inner diameter of 3cm and a height of 150cm, filling inert porcelain balls at the upper end and the lower end of the catalyst, detecting leakage by nitrogen, heating a reaction system, introducing reaction raw materials, wherein the reaction temperature is 145 ℃, the reaction pressure is 0.75MPaG, and the volume space velocity is 2000h -1 The raw materials comprise propylene, acetic acid and oxygen, wherein water=1:0.3:0.25:0.35, the mixture obtained by the reaction is cooled and separated from gas and liquid after being stabilized for 100 hours, and then the mixture is analyzed by gas chromatography. According to analysis, the initial activity of the catalyst is 436 g/L.h, and the selectivity of allyl acetate is 96.8%; after continuous evaluation for 3000 hours, no potassium ions are detected in the reaction liquid, the catalyst activity is 373 g/L.h, the allyl acetate selectivity is 96.3%, and the catalyst activity and selectivity can still meet the industrial use requirements.
[ example 2 ]
1) Preparation of the catalyst
1L of silica gel beads (average particle size 5.5mm, specific surface area 168 m) 2 Per g, pore volume of 0.73mL/g, average pore diameter of 16.3nm, bulk density of 522 g/L), and placing into a muffle furnace to bake for 2h at 700 ℃ under air atmosphere;
preparing 320mL of aqueous solution containing 0.5g of thioindigo red, fully and uniformly stirring, uniformly spraying the aqueous solution to silica gel pellets, standing for 4h, and then thoroughly drying in a 200 ℃ oven;
preparing 420mL of aqueous solution containing 6.0g Pd and 0.6g Cu of sodium chloropalladate and copper acetate, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 46g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A;
then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, then fully washing with deionized water until no chloride ions are detected, putting into a baking oven for baking to obtain a catalyst precursor B, dipping 400mL of solution containing 60g of potassium tartrate into the catalyst precursor B, and fully drying to obtain a catalyst finished product. The active component has an average particle size of 3.0nm as analyzed.
2) Catalyst Performance test
The catalyst evaluation conditions were the same as in example 1, and after the reaction was stabilized for 100 hours, the mixture obtained by the reaction was cooled, gas-liquid separated, and then analyzed by gas chromatography. The activity of the catalyst was 424g/L/h and the allyl acetate selectivity was 96.1% by analysis. After continuous evaluation for 3000 hours, no potassium ions are detected in the reaction liquid, the catalyst activity is 348g/L/h, the allyl acetate selectivity is 95.6%, and the catalyst activity and selectivity can still meet the industrial use requirements.
[ example 3 ]
1) Preparation of the catalyst
1L of silica gel beads (average particle size 5mm, specific surface area 289 m) 2 Per g, pore volume of 0.92mL/g, average pore diameter of 12.4nm, bulk density of 476g/L, and roasting in a muffle furnace at 350 deg.C for 8h under air atmosphere;
365mL of aqueous solution containing 3.2g of indirubin is prepared, fully and uniformly stirred, uniformly sprayed on silica gel pellets, stood for 8h and then thoroughly dried in a 110 ℃ oven;
preparing 420mL of aqueous solution containing 4.5g Pd and 0.8g Cu of sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 19g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A; then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, then fully washing with deionized water until no chloride ions are detected, putting into a baking oven for baking to obtain a catalyst precursor B, dipping 400mL of solution containing 60g of potassium malate into the catalyst precursor B, and fully drying to obtain a catalyst finished product. The active component has an average particle size of 3.6nm as analyzed.
2) Catalyst Performance test
The catalyst evaluation conditions were the same as in example 1, and after the reaction was stabilized for 100 hours, the mixture obtained by the reaction was cooled, gas-liquid separated, and then analyzed by gas chromatography. The activity of the catalyst was 418g/L/h and the allyl acetate selectivity was 96.6% by analysis. After continuous evaluation for 3000 hours, no potassium ions are detected in the reaction liquid, the catalyst activity is 341g/L/h, the allyl acetate selectivity is 96.0%, and the catalyst activity and selectivity can still meet the industrial use requirements.
Comparative example 1
1) Preparation of the catalyst
The surface of the carrier does not adopt an additive indigoid compound or a derivative thereof in the preparation process of the catalyst.
1L of silica gel beads (average particle size 5mm, specific surface area 221 m) 2 Per g, wherein the pore volume is 0.86mL/g, the average pore diameter is 14nm, the bulk density is 504g/L, and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ under the air atmosphere;
preparing 420mL of aqueous solution containing 4.8g Pd and 1.0g Cu of sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 53.5g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A; then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, then fully washing with deionized water until no chloride ions are detected, putting into a baking oven for baking to obtain a catalyst precursor B, dipping 400mL of solution containing 55g of potassium citrate into the catalyst precursor B, and fully drying to obtain a catalyst finished product. The active component has an average particle size of 5.2nm as analyzed.
The catalyst evaluation conditions were the same as in example 1, and after the reaction was stabilized for 100 hours, the mixture obtained by the reaction was cooled, gas-liquid separated, and then analyzed by gas chromatography. The activity of the catalyst was 382g/L/h, and the selectivity of allyl acetate was 94.2%. After continuous evaluation for 3000 hours, the content of potassium ions in the reaction solution is 6.2ppm, potassium loss exists, the catalyst activity is 283g/L/h, the allyl acetate selectivity is 90.4%, and the catalyst activity and selectivity can not meet the industrial use requirement.
Comparative example 2
1) Preparation of the catalyst
In the preparation process of the catalyst, the surface of the carrier does not adopt a polybasic potassium carboxylate auxiliary agent, and adopts a conventional potassium acetate auxiliary agent.
1L of silica gel beads (average particle size 5mm, specific surface area 221 m) 2 Per g, wherein the pore volume is 0.86mL/g, the average pore diameter is 14nm, the bulk density is 504g/L, and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ under the air atmosphere;
296mL of aqueous solution containing 2.1g of indigo is prepared, fully and uniformly stirred, uniformly sprayed on silica gel pellets, and kept stand for 4 hours, and then thoroughly dried in a baking oven at 150 ℃;
preparing 420mL of aqueous solution containing 4.8g Pd and 1.0g Cu of sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 53.5g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A; then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, then fully washing with deionized water until no chloride ions are detected, putting into a baking oven for baking to obtain a catalyst precursor B, dipping 400mL of solution containing 55g of potassium acetate into the catalyst precursor B, and fully drying to obtain a catalyst finished product. The active component has an average particle size of 3.5nm as analyzed.
The catalyst evaluation conditions were the same as in example 1, and after the reaction was stabilized for 100 hours, the mixture obtained by the reaction was cooled, gas-liquid separated, and then analyzed by gas chromatography. The activity of the catalyst was found to be 412g/L/h and the allyl acetate selectivity was found to be 95.0%. After continuous evaluation for 3000 hours, the content of potassium ions in the reaction solution is 10.5ppm, potassium loss exists, the catalyst activity is 262g/L/h, the allyl acetate selectivity is 88.6%, and the catalyst activity and selectivity can not meet the industrial use requirement.
[ comparative example 3 ]
1) Preparation of the catalyst
The surface of the carrier does not adopt an additive indigoid compound or a derivative thereof and a polycarboxylic acid potassium auxiliary agent in the preparation process of the catalyst.
1L of silica gel beads (average particle size 5mm, specific surface area 221 m) 2 Per g, wherein the pore volume is 0.86mL/g, the average pore diameter is 14nm, the bulk density is 504g/L, and the mixture is put into a muffle furnace to be roasted for 4 hours at 500 ℃ under the air atmosphere; preparing 420mL of aqueous solution containing 4.8g Pd and 1.0g Cu of sodium chloropalladate and copper chloride, fully and uniformly stirring, adding the aqueous solution into the silica gel pellets, preparing 1.2L of solution containing 53.5g sodium silicate nonahydrate, and putting the silica gel pellets into the sodium silicate solution to obtain a catalyst precursor A; then adding 40g of hydrazine hydrate solution with the concentration of 80% into the precursor A, fully stirring, reducing the catalyst precursor A for 8 hours, then fully washing with deionized water until no chloride ions are detected, putting into a baking oven for baking to obtain a catalyst precursor B, dipping 400mL of solution containing 55g of potassium acetate into the catalyst precursor B, and fully drying to obtain a catalyst finished product. The active component has an average particle size of 6.1nm as analyzed.
The catalyst evaluation conditions were the same as in example 1, and after the reaction was stabilized for 100 hours, the mixture obtained by the reaction was cooled, gas-liquid separated, and then analyzed by gas chromatography. The catalyst activity was found to be 352g/L/h and the allyl acetate selectivity was found to be 94.3%. After continuous evaluation for 3000 hours, the content of potassium ions in the reaction solution is 15.4ppm, potassium loss exists, the catalyst activity is 227g/L/h, the allyl acetate selectivity is 84.1%, and the catalyst activity and selectivity can not meet the industrial use requirement.
From the above test results, it can be seen that:
(1) As can be seen from example 1 and comparative example 1, the catalyst of example 1 was prepared using the additive indigo, the catalyst of comparative example 1 was prepared without using the indigo compound or its derivative, the catalyst of comparative example 1 was significantly larger in active size and had significantly lower potassium loss, initial and long-term activities and selectivities than those of example 1;
(2) As can be seen from examples 1 and 2, comparative example 2 does not use a potassium polycarboxylic acid auxiliary agent, and has obvious auxiliary agent potassium loss during long-term use, and the catalyst in comparative example 2 has obviously lower long-period activity and selectivity than that in example 1;
(3) As can be seen from the comparison of example 1 with comparative example 3, without the addition of the indigoid compound or derivative thereof and the potassium polycarboxylic acid, the initial and long-term activity and selectivity of the catalyst of comparative example 3 are significantly lower than those of example 1, and the inventive scheme exhibits higher and longer-lasting catalyst activity and selectivity.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. An acetyl oxidation catalyst, characterized in that the catalyst comprises a carrier, an additive, an active component and an auxiliary agent;
the additive is at least one selected from indigo, isoindigo, indigo red, indirubin, methyl indigo red, hydroxyl indigo red, allyl indigo red, benzyl indigo red, thioindigo blue and thioindigo red;
the active component comprises at least one of (a) Pd element and (b) Cu, au and Sn element;
the auxiliary agent is at least one of potassium tartrate, potassium malate, potassium oxalate and potassium citrate;
the main chemical component of the carrier is SiO 2 、Al 2 O 3 、Fe 2 O 3 Or a mixture thereof.
2. The catalyst of claim 1, wherein the support has a specific surface area of from 100 to 600m 2 Per g, pore volume of 0.3-1.2mL/g, average pore diameter of 5-20nm, and bulk density of 300-900g/L.
3. The catalyst of claim 1 wherein the additive is present in an amount of 0.05 to 10g/L.
4. The catalyst of claim 1, wherein the Pd is present in an amount of 0.5 to 15g/L and the element (b) is present in an amount of 0.1 to 10g/L.
5. The catalyst of claim 1 wherein the promoter is present in an amount of 5 to 80g/L.
6. The method for preparing a catalyst according to any one of claims 1 to 5, comprising the steps of:
1) Roasting a carrier: roasting the carrier at a certain temperature by taking oxygen-containing gas as carrier gas to obtain a treated carrier;
2) Additive loading: slowly adding the solution of the additive into the carrier obtained in the step 1), aging for a period of time, and drying at a certain temperature to obtain a catalyst precursor 1;
3) Active component loading and fixing: slowly adding a salt solution containing active component elements into the precursor 1 obtained in the step 2), and then placing the catalyst precursor 1 impregnated with the active components into alkali liquor for fixing the active components to obtain a catalyst precursor 2;
4) Reduction of active components: carrying out reduction treatment on the catalyst precursor 2 obtained in the step 3) and a reducing agent, washing and drying to obtain a catalyst precursor 3;
5) Addition of auxiliary agent: and (3) dipping the auxiliary agent into the catalyst precursor 3, and drying to obtain a catalyst finished product.
7. The method according to claim 6, wherein in step 1), the oxygen-containing carrier gas is at least one of air, oxygen, a mixture of oxygen and nitrogen; the roasting temperature is 300-900 ℃; and/or:
the drying temperature in the step 2) is 100-300 ℃.
8. The method according to claim 6, wherein the alkali liquor in the step 3) is at least one of sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydroxide, and aqueous potassium hydroxide; and/or:
the reducing agent in the step 4) comprises at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene and isobutene.
9. A process for the preparation of vinyl acetate, characterized in that acetic acid, oxygen, C in the presence of a catalyst according to any one of claims 1 to 5 or a catalyst prepared according to any one of claims 6 to 8 2 -C 4 Alkene is reacted to prepare the vinyl acetate.
10. The process for producing vinyl acetate according to claim 9, wherein the reaction temperature is 120 to 180℃and the reaction pressure is 0.1 to 1.5MPaG,
c in molar ratio 2 -C 4 Olefin, acetic acid and oxygen=1 (0.1-0.5), and the volume space velocity of the raw material is 1000-3000h -1 。
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| CN102218345A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinylacetate and preparation method thereof |
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| WO2017002576A1 (en) * | 2015-06-29 | 2017-01-05 | 昭和電工株式会社 | Method for producing allyl acetate |
| CN114054044A (en) * | 2021-12-06 | 2022-02-18 | 万华化学集团股份有限公司 | Catalyst and preparation method and application thereof |
| CN114345369A (en) * | 2022-01-12 | 2022-04-15 | 万华化学集团股份有限公司 | Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
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| CN102218345A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinylacetate and preparation method thereof |
| CN104437670A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Preparation method of propenyl ethanoate catalyst and synthesis method of propenyl ethanoate |
| WO2017002576A1 (en) * | 2015-06-29 | 2017-01-05 | 昭和電工株式会社 | Method for producing allyl acetate |
| CN114054044A (en) * | 2021-12-06 | 2022-02-18 | 万华化学集团股份有限公司 | Catalyst and preparation method and application thereof |
| CN114345369A (en) * | 2022-01-12 | 2022-04-15 | 万华化学集团股份有限公司 | Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
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