CN114345369A - Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate - Google Patents
Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate Download PDFInfo
- Publication number
- CN114345369A CN114345369A CN202210030577.1A CN202210030577A CN114345369A CN 114345369 A CN114345369 A CN 114345369A CN 202210030577 A CN202210030577 A CN 202210030577A CN 114345369 A CN114345369 A CN 114345369A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- active component
- acetate
- palladium
- alkali metal
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 42
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 27
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 25
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 25
- 210000003278 egg shell Anatomy 0.000 claims abstract description 25
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004021 humic acid Substances 0.000 claims abstract description 19
- 238000007740 vapor deposition Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 24
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 20
- 229910052700 potassium Inorganic materials 0.000 claims description 20
- 239000011591 potassium Substances 0.000 claims description 20
- 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 16
- 238000007792 addition Methods 0.000 claims description 16
- -1 alkali metal acetate Chemical class 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 235000011056 potassium acetate Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 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 7
- 239000001307 helium Substances 0.000 claims description 7
- 229910052734 helium Inorganic materials 0.000 claims description 7
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 5
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 229940095100 fulvic acid Drugs 0.000 claims description 5
- 239000002509 fulvic acid Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000002940 palladium Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 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
- 150000003839 salts Chemical class 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 26
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000008188 pellet Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000006137 acetoxylation reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZPLQIPFOCGIIHV-UHFFFAOYSA-N Gimeracil Chemical compound OC1=CC(=O)C(Cl)=CN1 ZPLQIPFOCGIIHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229950009822 gimeracil Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 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 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 active component and an auxiliary agent; the support is an oxide comprising silica; the active component comprises (a) Pd element, (b) compound containing at least one element selected from Cu, Au and Sn element; the active components are distributed in an egg shell shape, and the auxiliary agent is alkali metal acetate. Provides a preparation method of an acetyl oxidation catalyst, which comprises the steps of alkali metal vapor deposition, active component deposition and precipitation, active component reduction and auxiliary agentAdding; the active component is distributed in an eggshell shape by alkali metal vapor deposition, and the active component is added with humic acid to promote palladium in the active component and other metal elements to form palladium-based alloy, so that more exposed palladium active sites are provided, the catalytic activity and selectivity are high, and the catalyst can be industrially applied to C2‑C4Alkene, 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 method, 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 synthesis intermediate, and typical vinyl acetate is vinyl acetate, allyl acetate, methyl allyl alcohol acetate and the like. The allyl acetate is a colorless flammable liquid, is slightly soluble in water, is easily soluble in alcohol and ether, can be dissolved in acetone, is used as an important chemical raw material, is mainly used for producing important organic synthetic raw materials such as allyl alcohol, epoxy chloropropane, glycerol and the like, and is also used for synthesizing resin and adhesives.
In the 80 s of the 20 th century, Japanese Showa electrician first realized the industrial production of allyl acetate, developed acetyl oxidation technology, and prepared allyl acetate by using propylene, oxygen and acetic acid as raw materials and adopting a fixed bed gas phase reaction in the presence of palladium and a cocatalyst. The acetyl oxidation catalyst used is SiO2、Al2O3Or SiO2And Al2O3The formed mixture is a carrier, palladium, copper and potassium acetate are loaded, and the palladium and copper active components are distributed in an eggshell shape.
Patent application publication No. CN 101657259B describes a catalyst for preparing allyl acetate, the preparation process of the catalyst includes four steps, wherein in order to prepare a catalyst with active components in an "eggshell" type distribution, a method of soaking a carrier with an alkaline solution is employed, and although the "eggshell" type catalyst is prepared, soaking the carrier with an alkaline solution easily causes reduction in the strength of the carrier, breakage of pore channels, and loss of the active components during the soaking process.
Patent document application publication No. CN 1131199C describes an oxoacylation catalyst for producing allyl acetate, which is added with metallic tin or a mixture of tin and an additional promoter metal during the production process, and by adding tin, the catalyst life can be maintained without deterioration without adding water to the raw materials. Since water is produced in the acetoxylation reaction and the produced water removes a part of the heat generated in the acetoxylation reaction, the method by which water is not added has no industrial advantage.
Patent application publication No. CN 103120961B describes an allyl acetate catalyst and a preparation method thereof. The catalyst is made of SiO2、Al2O3Or the mixture thereof is used as a carrier, the loaded active component comprises metal palladium, metal copper and alkali metal acetate, and the average grain diameter of palladium copper crystal grains is 5-7 nm; in the preparation process of the catalyst, liquid carbon dioxide is used as an impregnation liquid, the used palladium compound is acetylacetone group as a ligand, and the preparation method adopts expensive raw materials, so that the production cost is too high, and the industrial application economy is not achieved.
Patent application publication No. 106582871B describes a catalyst for allyl acetate production, the carrier of the catalyst comprises a carrier substrate and a surface coating, the substrate is porous silica, the coating is composed of at least one of platinum cluster metal elements and IVA metal elements, the coating adopted in the preparation method is platinum cluster metal which is expensive and not easy to recover and separate, therefore, the catalyst production cost is high, and the catalyst is not beneficial to industrial large-scale application.
Disclosure of Invention
The invention aims to provide a catalyst for acetyl oxidation and a preparation method thereof, wherein the active components of the acetyl oxidation catalyst are distributed in an eggshell shape, the formed palladium-based alloy has more stable property, the active components are not easy to run off, the catalytic activity and the selectivity are higher, and the service life is longer.
The invention also aims to provide a method for preparing an allyl acetate compound, in particular to a method for preparing an allyl acetate compound, and the allyl acetate prepared under the action of the catalyst provided by the invention has the characteristics of high activity and high selectivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an acetyl oxidation catalyst comprising a support, an active component and a promoter;
the carrier comprises SiO2And optionally Al2O3、Fe2O3(ii) a The active component comprises (a) palladium element and (b) at least one of copper, gold and tin; the auxiliary agent is alkali metal acetate.
Preferably, the carrier has one or more of the following characteristics:
A) the average grain diameter is 3-10 mm;
B) specific surface area of 100-600m2The pore volume is 0.3-1.2mL/g, the average pore diameter is 5-20nm, and the bulk density is 300-;
C) SiO in the carrier according to the weight portion285 to 100 portions of Al2O30-10 parts of Fe2O3The content is 0-5 parts.
Preferably, the specific surface area of the carrier is 120-400m2G, more preferably 150-2(ii)/g; the pore volume is 0.4-1.0mL/g, more preferably 0.6-0.9 mL/g; an average pore diameter of 6 to 19nm, more preferably 9 to 18 nm; the bulk density is 350-800g/L, and more preferably 400-700 g/L.
The active component comprises (a) palladium and (b) at least one of copper, gold and tin, preferably, the content of the palladium (a) in the active component is 0.5-15g/L, more preferably 0.6-10 g/L; the content of (b) in the active ingredient is 0.1 to 10g/L, more preferably 0.2 to 6 g/L.
Further, the active component is in an 'egg shell' type distribution; the eggshell-shaped distribution is that the active component is positioned on the surface layer of the carrier; the particle size of the active component is 2-10nm, preferably 3-8 nm; the thickness of the active component is 50-500 μm, preferably 100-350 μm.
The auxiliary agent is alkali metal acetate, preferably, the alkali metal acetate is at least one of sodium acetate, potassium acetate and cesium acetate, and more preferably potassium acetate and cesium acetate; the content of alkali metal acetate is 10-100g/L, more preferably 15-80 g/L.
The preparation method of the catalyst comprises the following steps:
1) alkali metal vapor deposition: putting alkali metal into a gasifier for melting and gasifying, taking inert gas as carrier gas, introducing a certain amount of alkali metal into a reaction tube provided with a carrier for chemical vapor deposition, and obtaining the carrier with the surface loaded with the alkali metal;
2) active component deposition precipitation: preparing a solution containing palladium salt, (b) element metal salt and humic acid, and slowly adding the prepared metal solution into the carrier obtained in the step 1) to obtain an active component with a certain thickness, namely an eggshell-shaped catalyst precursor 1;
3) reduction of active components: reacting the catalyst precursor 1 obtained in the step 2 with a reducing agent for reduction treatment, washing and drying to obtain a catalyst precursor 2;
4) addition of an auxiliary agent: and (3) preparing a certain amount of alkali metal acetate, soaking the alkali metal acetate into the catalyst precursor 2, and drying to obtain a catalyst finished product.
Further, the alkali metal used was vapor-deposited according to step 1. Preferably, the alkali metal comprises at least one of lithium, sodium, potassium, cesium, preferably sodium, potassium; the content of the alkali metal is 1.0 to 4.0 times, preferably 1.5 to 3.0 times of the molar content of the active component palladium. The inert gas used for the vapor deposition is carried out according to step 1. Preferably, the inert gas comprises at least one of nitrogen, argon, helium, preferably argon, helium.
The inventor researches and discovers that the molar quantity of alkali metal and active component palladium used in vapor deposition influences the eggshell distribution of the active component and the thickness of the active component, and the molar ratio of the alkali metal to the active component palladium is too low, so that loss in the preparation process of the active component is caused; the molar ratio of the alkali metal to the active component palladium is too high, so that the eggshell thickness of the active component is too thick, and the activity of the catalyst is too low. The inventor finds that the molar ratio range of specific alkali metal and active component palladium is adjusted, so that the eggshell type distribution and the thickness of the active component of the catalyst can be effectively considered, and the catalyst with high activity and high selectivity can be prepared.
Further, in the step 2, (a) the palladium salt is at least one of sodium chloropalladate, potassium chloropalladate, palladium chloride, palladium acetate, palladium nitrate and palladium sulfate, preferably sodium chloropalladate; (b) the element is at least one of soluble chloride, nitrate and sulfide of copper, gold and tin, preferably (b) the element soluble chloride; the humic acid is at least one of humic acid, gimeracil acid and fulvic acid, and fulvic acid is preferred; the mass ratio of the addition amount of the humic acid to the addition amount of the active component palladium is 0.05:1-2:1, preferably 0.1:1-1: 1.
The inventor researches and discovers that in the process of preparing the catalyst by deposition and precipitation, the addition of humic acid influences the alloying of palladium and other metal elements in the active component, compared with the catalyst prepared without humic acid, the addition of a proper amount of humic acid can obviously promote the active component to form palladium-based alloy, and the addition of humic acid can promote the alloying of the palladium element and other metal elements and can more easily form uniform-phase alloy. The palladium-based alloying of the active component can be promoted by adjusting the concentration (0.005-0.02mol/L) of the salt solution of the active component and the addition amount of humic acid, the exposed palladium active sites are more, and the activity and the selectivity are higher.
Further, the reducing agent in step 3 comprises at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene and isobutene, preferably hydrazine hydrate and hydrogen; the molar ratio of the addition amount of the reducing agent to the addition amount of the active component palladium is 1:1-10: 1.
Further, in the step 4, the alkali metal acetate is at least one of sodium acetate, potassium acetate and cesium acetate, and preferably potassium acetate.
A process for preparing vinyl acetate from acetic acid, oxygen and C in the presence of catalyst2-C4Olefin is used as a raw material to prepare vinyl acetate through acetyl oxidation reaction.
Further, the method for preparing the vinyl acetate comprises the following steps:
mixing acetic acid, oxygen and C2-C4The olefin feed is fed to a reactor packed with the catalyst of the invention in terms of molar ratio, C2-C4Olefin, acetic acid, oxygen 1 (0.1-0.5) and (0.1-0.5), acetyl oxidation reaction is carried out at the temperature of 120 ℃ and 180 ℃ and under the condition of 0.1-1.5MPaG,the volume space velocity is 1000-3000h-1To prepare vinyl acetate;
preferably, said C2-C4The olefin feedstock is propylene.
Furthermore, the method for preparing allyl acetate comprises the steps of carrying out acetyl oxidation reaction on propylene, acetic acid, oxygen, water and water in a molar ratio of (0.1-0.5) to (0.1-1) at the temperature of 120 ℃ and 180 ℃ and under the pressure of 0.1-1.5MPaG, wherein the volume space velocity is 1000--1And allyl acetate is prepared.
The invention has the following beneficial effects:
1) the invention can prepare the acetyl oxidation catalyst with the active components distributed in an eggshell shape and the controllable eggshell thickness by vapor deposition of a certain amount of alkali metal on the surface of the carrier, and the activity and the selectivity of the catalyst are improved.
2) According to the invention, humic acid is added into the active component solution, and the humic acid promotes the alloying of the active component palladium and other metal elements, so that the prepared active component can easily form palladium-based alloy, more palladium active sites are exposed on the palladium-based alloy, and the activity and selectivity of the catalyst are obviously improved.
3) Compared with the prior catalyst preparation technology, the acetyl oxidation catalyst provided by the invention has the advantages of simple steps, low raw material cost, production cost saving, difficult loss of active components and industrial application competitiveness. The pressure referred to in the present invention is gauge pressure.
Description of the drawings: fig. 1 is an optical microscopic view of the distribution of active components of the catalyst obtained in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
Information of main raw materials:
silica gel beads, graves specialty chemicals and materials company;
montmorillonite pellets, kraine chemical ltd;
humic acid, shanghai yan chemical technology ltd;
other raw materials are all commercially available materials unless otherwise specified.
The calculation methods and test methods used in the examples or comparative examples are as follows:
1. the contents of the components in the reaction product were analyzed by gas chromatography using an Agilent GC 8890A chromatograph, and the activity and selectivity of the catalyst were calculated according to the following formulas
2. Method for measuring information of specific surface area and pore structure of catalyst
Pore structure of catalyst by N2The specific surface area is measured by a physical adsorption method, the specific surface area is obtained by a BET method and the pore volume is obtained by a BJH desorption method, and the model of a testing instrument is Micromeritics ASAP 2460.
3. Determination of palladium active site in 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 subjected to CO pulse chemisorption measurement with a Micromeritics AutoChem II 2920, and the palladium active site in the active component was ═ chemisorbed CO molar amount/actual supported molar amount of palladium × 100%.
4. Determination of particle size of 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, as measured by a JEOL 2100plus Transmission Electron Microscope (TEM).
5. Determination of the position and thickness of the active component of the catalyst
The catalyst is divided into two parts by adopting a slicer to obtain a cross section of the catalyst, and the position and the thickness of the active component of the catalyst are measured by adopting a Zeiss Axiolab 5 optical microscope.
[ example 1 ]
1) Preparation of the catalyst
Taking 1L of silica gel beads (average particle diameter of 5mm, specific surface area of 221 m)2Perg, the pore volume is 0.86mL/g, the average pore diameter is 14nm, and the bulk density is 504g/L) is put into a vapor deposition reactor, 2.4g of potassium is put into a gasifier, the potassium is melted and gasified, helium is introduced, the gasified potassium is introduced into the vapor deposition reactor with a carrier, and silica gel pellets with uniformly loaded potassium on the surface are obtained; preparing 2L of sodium chloropalladate and copper chloride aqueous solution containing 3.5g of Pd and 0.5g of Cu, adding 1.8g of fulvic acid, fully and uniformly stirring, then adding the mixture into silica gel pellets, and standing for 2 hours to obtain a catalyst precursor 1; then adding 15g of 80% hydrazine hydrate solution, fully stirring, standing and reducing the catalyst precursor 1 for 6h, fully washing the reduced catalyst precursor 1 with deionized water, and drying at 110 ℃ for 4h to obtain a catalyst precursor 2; and (3) dissolving 40g of potassium acetate in 400g of deionized water, soaking the solution on the precursor 2, and drying the solution at 110 ℃ for 2 hours to obtain a catalyst finished product.
Through analysis, the active site of the active component palladium is 52.1 percent, the average grain diameter of the active component is 3.8nm, the active component is distributed in an egg shell shape, and the average thickness of the egg shell is 136 mu m.
2) Testing of catalyst Performance
Putting 500mL of catalyst into a fixed bed reactor with the inner diameter of 3cm and the height of 150cm, filling inert ceramic balls at the upper end and the lower end of the catalyst, leaking nitrogen, heating a reaction system, introducing reaction raw materials, controlling the reaction temperature to be 145 ℃, the reaction pressure to be 0.8MPaG and the volume space velocity to be 2500h-1The raw materials comprise propylene, acetic acid, oxygen and water in a ratio of 1:0.3:0.25:0.35, after stable reaction for 100 hours, the mixture obtained by the reaction is cooled, separated from gas and liquid, and analyzed by gas chromatography. The activity of the catalyst is 452.1g/L/h and the selectivity of allyl acetate is 96.3 percent. After the continuous evaluation for 4000 hours, the catalyst activity is 334.5g/L/h, the allyl acetate selectivity is 94.5%, and the catalyst activity and selectivity can still meet the industrial application requirements.
[ example 2 ]
1) Preparation of the catalyst
Taking 1L of silica gel beads (average particle diameter of 5mm, specific surface area of 221 m)2(g), the pore volume is 0.86mL/g, the average pore diameter is 14nm, and the bulk density is 504g/L), putting the mixture into a vapor deposition reactor, taking 4.5g of potassium, putting the potassium into a gasifier, melting and gasifying the potassium, introducing helium, introducing the gasified potassium into the vapor deposition reactor with a carrier, and obtaining silica gel pellets with the potassium uniformly loaded on the surface; preparing 4L of sodium chloropalladate, copper chloride and chloroauric acid aqueous solution containing 5.0g of Pd, 0.5g of Cu and 0.5g of 0.5gAu, adding 0.5g of Gimadurac acid, fully and uniformly stirring, then adding the mixture into a silica gel pellet, and standing for 2 hours to obtain a catalyst precursor 1; then adding 29g of 80% hydrazine hydrate solution, fully stirring, standing and reducing the catalyst precursor 1 for 10h, fully washing the reduced catalyst precursor 1 with deionized water, and drying at 110 ℃ for 4h to obtain a catalyst precursor 2; 50g of potassium acetate is dissolved in 400g of deionized water, and is soaked on the precursor 2, and the precursor is dried for 2 hours at 110 ℃ to obtain a catalyst finished product.
Through analysis, the active site of the active component palladium is 58.6 percent, the average particle size of the active component is 3.0nm, the active component is distributed in an eggshell shape, and the average thickness of the eggshell is 179 mu m.
2) Testing of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the catalyst activity is 465.2g/L/h, and the allyl acetate selectivity is 98.0%. After the continuous evaluation for 4000 hours, the catalyst activity is 342.1g/L/h, the allyl acetate selectivity is 96.2%, and the catalyst activity and selectivity can still meet the industrial application requirements.
[ example 3 ]
1) Preparation of the catalyst
Taking 1L of montmorillonite small ball (average particle diameter 5mm, specific surface area 136 m)2(ii)/g, pore volume of 0.45mL/g, average pore diameter of 12nm, bulk density of 586g/L, 5.2% Al2O3And 1.4% Fe2O3) Putting into a vapor deposition reactor, putting 3.2g of sodium into a gasifier, melting and gasifying the sodium, introducing helium, introducing the gasified sodium into a vapor deposition device filled with a carrierDepositing in a reactor to obtain silica gel balls with potassium uniformly loaded on the surface; preparing 6.0L of sodium chloropalladate, copper chloride and stannous chloride aqueous solution containing 4.0g of Pd, 0.33g of Cu and 0.5g of 0.5gSn, adding 4.0g of fulvic acid, fully and uniformly stirring, adding into a silica gel pellet, and standing for 2 hours to obtain a catalyst precursor 1; then adding 10g of 80% hydrazine hydrate solution, fully stirring, standing and reducing the catalyst precursor 1 for 4h, fully washing the reduced catalyst precursor 1 with deionized water, and drying at 110 ℃ for 4h to obtain a catalyst precursor 2; 70g of potassium acetate is dissolved in 400g of deionized water, and is soaked on the precursor 2, and the precursor is dried for 2 hours at 110 ℃ to obtain a catalyst finished product.
Through analysis, the active site of the active component palladium is 47.2 percent, the average particle size of the active component is 4.6nm, the active component is distributed in an egg shell shape, and the average thickness of the egg shell is 263 mu m.
2) Testing of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. The catalyst activity was analyzed to be 407.6g/L/h, and the allyl acetate selectivity was 94.5%. After the continuous evaluation for 4000 hours, the catalyst activity is 329.6g/L/h, the allyl acetate selectivity is 92.9%, and the catalyst activity and selectivity can still meet the industrial application requirements.
Comparative example 1
In the preparation process of the catalyst, alkali metal vapor deposition is not adopted on the surface of the carrier, 2L of sodium chloropalladate containing 3.5g of Pd and 0.5g of Cu and aqueous solution of copper chloride are added into 1L of silica gel beads, 3.45g of potassium hydroxide is dissolved in 60mL of deionized water and is dripped into the active component salt solution, the solution is kept stand for 2 hours, and the other preparation conditions are the same as those in example 1. Through analysis, the active site of the active component palladium is 33.9 percent, the average grain diameter of the active component is 7.2nm, the active component is uniformly distributed, and the active component is lost. The catalyst evaluation conditions were the same as in example 1, and the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. Through analysis, the catalyst activity is 288.6g/L/h, the allyl acetate selectivity is 80.3%, and the initial performance of the catalyst does not meet the requirement of industrial use.
Comparative example 2
Humic acid is not added to active components in the preparation process of the catalyst. Taking 1L of silica gel pellets, putting the silica gel pellets into a vapor deposition reactor, taking 2.4g of potassium, putting the potassium into a gasifier, melting and gasifying the potassium, introducing helium, introducing the gasified potassium into the vapor deposition reactor with a carrier, and obtaining the silica gel pellets with potassium uniformly loaded on the surface; 2L of an aqueous solution of sodium chloropalladate and copper chloride containing 3.5g of Pd and 0.5g of Cu were prepared and then added to the silica gel pellets, and the other preparation conditions were the same as in example 1. Through analysis, the active site of the active component palladium is 35.6 percent, the average grain diameter of the active component is 8.3nm, the active component is distributed in an egg shell shape, and the average thickness of the egg shell is 147 mu m. The catalyst evaluation conditions were the same as in example 1, and the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. The activity of the catalyst is 322.3g/L/h and the selectivity of allyl acetate is 87.8 percent. After the continuous evaluation for 1000 hours, the catalyst activity is 300.2g/L/h, the allyl acetate selectivity is 86.8 percent, and the catalyst activity and the selectivity can not meet the industrial application requirements.
Comparative example 3A catalyst was prepared according to the preferred protocol in CN 101657259B and evaluated for performance
Taking 1L of silica gel pellets, preparing 445mL of aqueous solution of sodium chloropalladate, copper sulfate and chloroauric acid containing 6.0g of Pd, 0.8g of Cu and 0.6g of 0.6gAu, dipping the silica gel pellets until the solution is completely absorbed, dissolving 35.6g of sodium silicate nonahydrate in 890mL of deionized water, putting the dipped silica gel pellets in the deionized water, and standing for 20 hours; then adding 33.3g of 80% hydrazine hydrate aqueous solution, standing for 4h, fully washing, and drying at 110 ℃ for 4h to obtain a catalyst precursor; and (3) dissolving 60g of potassium acetate in 400g of deionized water, soaking the solution on the catalyst precursor, and drying the solution at the temperature of 110 ℃ for 4 hours to obtain a catalyst finished product.
Through analysis, the active site of the active component palladium is 38.7 percent, the average grain diameter of the active component is 6.3nm, the active component is distributed in an egg shell shape, and the average thickness of the egg shell is 397 mu m. The catalyst evaluation conditions were the same as in example 1, and the mixture obtained by the reaction was cooled, separated into gas and liquid, and analyzed by gas chromatography. The catalyst activity was analyzed to be 387.1 g/L/h, and the allyl acetate selectivity was 83.8%. After continuous evaluation for 2000h, the catalyst activity is 302.6g/L/h, the allyl acetate selectivity is 82.1%, and the catalyst activity and selectivity are obviously reduced.
From the above test results it can be seen that:
(1) as can be seen from example 1 and comparative example 1, example 1 can prepare a catalyst having an active component in an "eggshell" type distribution by vapor depositing a layer of alkali metal on the surface of a support, comparative example 1 has a uniform type distribution of an active component not prepared by vapor depositing an alkali metal, and the activity and selectivity of the catalyst in comparative example 1 are significantly lower than those of the catalyst in example 1;
(2) as can be seen from example 1 and comparative example 2, the catalyst prepared without adding humic acid to the active component solution does not easily form a palladium-based alloy, the exposed palladium active sites are significantly reduced, and the activity and selectivity of the catalyst in comparative example 2 are significantly lower than those of the catalyst in example 1;
(3) as can be seen from comparison of example 1 with comparative example 3, the solution of the present invention shows higher catalyst activity and selectivity compared to the solution of preparing an "eggshell" type catalyst by impregnation of the active component and migration.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. An acetyl oxidation catalyst, characterized in that the catalyst comprises a carrier, an active component and an auxiliary agent; the carrier comprises SiO2And optionally Al2O3、Fe2O3(ii) a The active component comprises (a) palladium element and (b) at least one of copper, gold and tin; the auxiliary agent is alkali metal acetate.
2. The catalyst of claim 1, wherein the support has one or more of the following characteristics:
A) the average grain diameter is 3-10 mm;
B) specific surface area of 100-600m2The pore volume is 0.3-1.2mL/g, the average pore diameter is 5-20nm, and the bulk density is 300-;
C) SiO in the carrier according to the weight portion285 to 100 portions of Al2O30-10 parts of Fe2O3The content is 0-5 parts.
3. The catalyst according to claim 1 or 2, wherein the content of (a) Pd in the active component is 0.5 to 15g/L, and the content of (b) element in the active component is 0.1 to 10 g/L; the active components of the catalyst are distributed in an egg shell shape; the particle size of the active component is 2-10nm, and the thickness of the active component is 50-500 μm.
4. The catalyst of any one of claims 1-3, wherein the alkali metal acetate is at least one of sodium acetate, potassium acetate, and cesium acetate, and wherein the alkali metal acetate is present in an amount of 10-100 g/L.
5. The method for preparing a catalyst according to any one of claims 1 to 4, comprising the steps of:
1) alkali metal vapor deposition: putting alkali metal into a gasifier for melting and gasifying, taking inert gas as carrier gas, introducing a certain amount of alkali metal into a reaction tube provided with a carrier for chemical vapor deposition, and obtaining the carrier with the surface loaded with the alkali metal;
2) active component deposition precipitation: preparing a solution containing palladium salt, (b) element metal salt and humic acid, and slowly adding the prepared metal solution into the carrier obtained in the step 1) to obtain an active component with a certain thickness, namely an eggshell-shaped catalyst precursor 1;
3) reduction of active components: reacting the catalyst precursor 1 obtained in the step 2) with a reducing agent for reduction treatment, washing and drying to obtain a catalyst precursor 2;
4) addition of an auxiliary agent: and (3) preparing a certain amount of alkali metal acetate, soaking the alkali metal acetate into the catalyst precursor 2, and drying to obtain a catalyst finished product.
6. The method for preparing the catalyst according to claim 5, wherein the alkali metal in step 1) includes at least one of lithium, sodium, potassium, cesium; the content of the alkali metal is 1.0 to 4.0 times of the molar content of the active component palladium; the inert gas comprises at least one of nitrogen, argon and helium.
7. The method for preparing a catalyst according to claim 5 or 6, wherein the palladium salt in step 2) is at least one of sodium chloropalladate, potassium chloropalladate, palladium chloride, palladium acetate, palladium nitrate and palladium sulfate, preferably sodium chloropalladate; and/or, the (b) element metal salt is at least one of soluble chloride, nitrate and sulfide of copper, gold and tin; and/or the humic acid is at least one of humic acid, gemmamelphalan acid and fulvic acid; the mass ratio of the addition amount of the humic acid to the addition amount of the active component palladium is 0.05:1-2: 1.
8. The method for preparing a catalyst according to any one of claims 5 to 7, wherein the reducing agent in step 3) comprises at least one of hydrazine hydrate, sodium borohydride, formaldehyde, glucose, hydrogen, ethylene, propylene, isobutylene; the molar ratio of the addition amount of the reducing agent to the addition amount of the active component palladium is 1:1-10: 1; and/or, the alkali metal acetate in the step 4) is at least one of sodium acetate, potassium acetate and cesium acetate, and preferably potassium acetate.
9. A process for the preparation of an alkenyl acetate, characterized in that acetic acid, oxygen, C are used in the presence of a catalyst according to any one of claims 1 to 4 or a catalyst prepared by a process according to any one of claims 5 to 82-C4Olefin is used as a raw material to prepare vinyl acetate through acetyl oxidation reaction.
10. The method of claim 9 for preparing an alkene acetateThe ester method is characterized in that the reaction temperature is 120-180 ℃, the reaction pressure is 0.1-1.5MPaG, and the raw materials are calculated by molar ratio C2-C4Olefin, acetic acid and oxygen 1 (0.1-0.5) to 0.1-0.5), and the volume space velocity of the raw materials is 1000-3000h-1Preferably, the olefin is propylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739177A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5011980A (en) * | 1988-09-29 | 1991-04-30 | Showa Denko K.K. | Process for preparation of allyl acetate |
| CN1281384A (en) * | 1997-12-11 | 2001-01-24 | 人造丝化学欧洲有限公司 | Catalyst based on palladium, gold, alkali, and lanthanoid, and method for producing vinyl acetate |
| CN1306459A (en) * | 1998-06-23 | 2001-08-01 | 阿温提斯研究技术两合公司 | Method for producing shell catalysts by CVD process |
| CN101722045A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Carrier catalyst |
| CN101722044A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Load catalyst used for preparing vinyl acetate monomer |
| CN101745391A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | A kind of catalyst of removing traces of oxygen in catalytic cracking dry gas |
| US20100209628A1 (en) * | 2007-04-20 | 2010-08-19 | Regents Of The University Of Minnesota | Growth of coatings of nanoparticles by photoinduced chemical vapor deposition |
| CN102247856A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Eggshell nickel-based bifunctional hydrogenation catalyst and preparation method and application thereof |
| CN106582855A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
| CN109133037A (en) * | 2017-06-28 | 2019-01-04 | 比亚迪股份有限公司 | Carbon nanotube and its preparation method and application |
| JP2021030127A (en) * | 2019-08-21 | 2021-03-01 | 昭和電工株式会社 | Manufacturing method of catalyst for producing allyl acetate |
-
2022
- 2022-01-12 CN CN202210030577.1A patent/CN114345369B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5011980A (en) * | 1988-09-29 | 1991-04-30 | Showa Denko K.K. | Process for preparation of allyl acetate |
| CN1281384A (en) * | 1997-12-11 | 2001-01-24 | 人造丝化学欧洲有限公司 | Catalyst based on palladium, gold, alkali, and lanthanoid, and method for producing vinyl acetate |
| CN1306459A (en) * | 1998-06-23 | 2001-08-01 | 阿温提斯研究技术两合公司 | Method for producing shell catalysts by CVD process |
| US20010048970A1 (en) * | 1998-06-23 | 2001-12-06 | Alfred Hagemeyer | Process for producing coated catalysts by CVD |
| US20100209628A1 (en) * | 2007-04-20 | 2010-08-19 | Regents Of The University Of Minnesota | Growth of coatings of nanoparticles by photoinduced chemical vapor deposition |
| CN101722045A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Carrier catalyst |
| CN101722044A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Load catalyst used for preparing vinyl acetate monomer |
| CN101745391A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | A kind of catalyst of removing traces of oxygen in catalytic cracking dry gas |
| CN102247856A (en) * | 2010-05-21 | 2011-11-23 | 中国石油化工股份有限公司 | Eggshell nickel-based bifunctional hydrogenation catalyst and preparation method and application thereof |
| CN106582855A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing allyl acetate |
| CN109133037A (en) * | 2017-06-28 | 2019-01-04 | 比亚迪股份有限公司 | Carbon nanotube and its preparation method and application |
| JP2021030127A (en) * | 2019-08-21 | 2021-03-01 | 昭和電工株式会社 | Manufacturing method of catalyst for producing allyl acetate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739177A (en) * | 2022-12-08 | 2023-03-07 | 万华化学集团股份有限公司 | Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
| CN115739177B (en) * | 2022-12-08 | 2024-02-27 | 万华化学集团股份有限公司 | Acetyloxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
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