EP2155380A2 - Catalyseur sous enveloppe servant à la production de vam, procédé de production et d'utilisation dudit catalyseur - Google Patents
Catalyseur sous enveloppe servant à la production de vam, procédé de production et d'utilisation dudit catalyseurInfo
- Publication number
- EP2155380A2 EP2155380A2 EP08758900A EP08758900A EP2155380A2 EP 2155380 A2 EP2155380 A2 EP 2155380A2 EP 08758900 A EP08758900 A EP 08758900A EP 08758900 A EP08758900 A EP 08758900A EP 2155380 A2 EP2155380 A2 EP 2155380A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- catalyst support
- mass
- support
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 310
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 37
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000000440 bentonite Substances 0.000 claims abstract description 22
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 22
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims description 80
- 239000002243 precursor Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 43
- 229910000510 noble metal Inorganic materials 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 18
- 101150003085 Pdcl gene Proteins 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- -1 alkali metal acetate Chemical class 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 239000012696 Pd precursors Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000012876 carrier material Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000002826 nitrites Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 98
- 239000010931 gold Substances 0.000 description 85
- 239000000243 solution Substances 0.000 description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 66
- 235000012216 bentonite Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000000465 moulding Methods 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 16
- 235000011054 acetic acid Nutrition 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000010970 precious metal Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000003112 potassium compounds Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 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
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000004760 silicates Chemical group 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
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- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000008298 dragée Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003298 rubidium compounds Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229940080262 sodium tetrachloroaurate Drugs 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/16—Reducing
-
- 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
Definitions
- VAM shell catalyst process for its preparation and its use
- the present invention relates to a coated catalyst for the production of vinyl acetate monomer (VAM) comprising a loaded with Pd and Au, porous, formed as a shaped catalyst support on the basis of a natural phyllosilicates, in particular based on an acid-treated calcined bentonite.
- VAM vinyl acetate monomer
- VAM is an important monomer building block in the synthesis of plastic polymers.
- the main application areas of VAM are i.a. the preparation of polyvinyl acetate, polyvinyl alcohol and polyvinyl acetal and the co- and terpolymerization with other monomers such as ethylene, vinyl chloride, acrylate, maleate, fumarate and vinyl laurate.
- VAM is predominantly produced in the gas phase from acetic acid and ethylene by reaction with oxygen, wherein the catalysts used for this synthesis preferably contain Pd and Au as active metals and a
- Alkali metal component as a promoter, preferably potassium in the form of the acetate.
- the active metals Pd and Au are presumably not in the form of metal particles of the respective pure metal, but rather in the form of Pd / Au alloy particles of possibly different composition, although the presence of unalloyed particles is not excluded can.
- Cd or Ba may also be used as second active metal component.
- VAM is predominantly using so-called
- shell catalysts With the help of shell catalysts, a more selective reaction is possible in many cases than with
- the shell catalysts known in the prior art for the production of VAM can be, for example, catalyst supports based on silica, alumina, aluminosilicate,
- Titanium oxide or zirconium oxide (cf., for this purpose, EP 839 793 A1,
- Catalyst carriers are not long-term stable to acetic acid and relatively expensive.
- VAM shell catalysts are usually prepared in a so-called chemical way in which the catalyst support with solutions of corresponding metal precursor compounds, for example by immersing the carrier in the solutions or by Incipient-Wetness method (pore filling method), in which the carrier with a is loaded with solution volume corresponding to its pore volume.
- the Pd / Au shell of the catalyst is produced, for example, by first impregnating the catalyst support molding in a first step with a Na 2 PdCl 4 solution and then in a second step the Pd component with NaOH solution on the catalyst support in the form a Pd hydroxide compound is fixed. In a subsequent, separate third step, the catalyst support is then impregnated with a NaAuCl ⁇ solution and then the Au component also fixed by means of NaOH. After fixing the noble metal components in an outer shell of the catalyst support, the loaded catalyst support is then washed largely free of chloride and Na ions, then dried and finally reduced at 150 ° C. with ethylene.
- the generated Pd / Au shell usually has a thickness of about 100 to 500 microns.
- the catalyst carrier loaded with the noble metals is loaded with potassium acetate after the fixation or reduction step, wherein the loading with potassium acetate takes place not only in the outer, shell loaded with precious metals, but the catalyst support is completely impregnated with the promoter.
- the catalyst carrier used is predominantly a spherical carrier with the designation "KA-160” from SÜD-Chemie AG based on natural acid-treated bentonites as natural layered silicate, which has a BET surface area of about 160 m 2 / g.
- VAM shell catalysts based on Pd and Au as active metals and KA-160 supports as catalyst support are about 90 mol .-% based on the supplied ethylene, wherein the remaining 10 mol .-% of the reaction products are essentially CO 2 , which is formed by total oxidation of the organic starting materials / products.
- VAM selectivity is desirable to reduce the cost of raw material losses and to make the work-up of the reaction product VAM simpler and thus more cost-effective.
- the object of the present invention is therefore to provide a shell catalyst for the production of VAM, which is characterized by a relatively high VAM selectivity and high activity.
- This object is achieved on the basis of a shell catalyst of the generic type in that the catalyst support has a surface area of less than 130 m 2 / g.
- the invention thus relates to a shell catalyst comprising a natural layered silicate, in particular an acid-treated calcined bentonite catalyst support molding having an outer shell, are contained in the metallic Pd and Au, wherein the catalyst support molded body has a BET surface area of less than 130 m 2 / g.
- Shelled catalysts with a support in whose outer shell the active species has penetrated are also referred to in the art as "egg-shell" shell catalysts.
- the coated catalyst according to the invention is characterized by a VAM selectivity increased by at least 1 mol% compared to the corresponding catalysts known in the prior art for the preparation of VAM.
- the increase in selectivity is essentially due to a decrease in the unwanted total oxidation of acetic acid, ethene and VAM to CO 2 .
- the catalyst according to the invention has an activity which is at least equal to that of the corresponding catalysts known in the prior art for the preparation of VAM.
- the activity of the catalyst according to the invention can be increased significantly by increasing the thickness of the Pd / Au shell, without having to accept significant losses in the VAM selectivity.
- an increase in the shell thickness is accompanied by a markedly reduced VAM selectivity.
- the catalyst according to the invention has excellent mechanical stability and exhibits high chemical resistance compared with the educts and products to be used and high thermal stability compared with the temperatures prevailing in VAM synthesis. If one leaves the reaction conditions in the technical use of the catalyst of the invention unchanged compared to a corresponding shell catalyst of the prior art, then more VAM per reactor volume and time can be produced, which is equivalent to an increase in capacity and additional investment. In addition, the work-up of the obtained Rohvinylacetats is facilitated because the VAM content in the product gas is higher, resulting in energy savings in the VAM workup. Suitable work-up procedures are disclosed, for example, in US Pat. No. 5,066,365 A and DE 29 45 913 A1.
- the reaction temperature can be lowered, whereby a further increase in the VAM selectivity can be obtained with the aforementioned advantageous effects.
- This also reduces the proportion of CO 2 produced as a by-product and therefore to be rejected and the entrainment loss associated with entrained ethylene.
- such a process management of a corresponding system due to lower temperatures leads to an extension of the catalyst life.
- a natural layered silicate as used herein means that the catalyst support molding comprises a natural layered silicate, wherein the natural layered silicate may be present in the catalyst support in both untreated and treated form Phyllosilicate before use as Carrier material may include, for example, treating with acids and / or calcining.
- natural sheet silicate for which the term “phyllosilicate” is also used in the literature, in the context of the present invention is understood to mean silicate mineral originating from natural sources, in which SiO 4 tetrahedron, which is the basic structural unit of all silicates form, in layers of the general formula [Si 2 O] 2 are interlinked.
- Phyllosilicates preferred in the context of the present invention are clay minerals, in particular kaolinite,
- a particularly preferred natural layered silicate in the context of the present invention is a bentonite.
- Bentonites are not natural layer silicates in the actual sense, but rather a mixture of predominantly clay minerals, in which phyllosilicates are contained.
- the natural sheet silicate is a bentonite, it is to be understood that the natural sheet silicate is present in the catalyst support in the form or as part of a bentonite.
- the surface of the catalyst support has a size of less than 125 m 2 / g, preferably one of less than 120 m 2 / g, preferably one of less than 100 m 2 / g, more preferably one of less than 80 m 2 / g and particularly preferably less than 65 m 2 / g.
- the term "surface area" of the catalyst support is understood to mean the BET surface area of the support, which is determined by adsorption of nitrogen in accordance with DIN 66132.
- the catalyst support has a surface area of between 130 and 40 m 2 / g, preferably one of between 128 and 50 m 2 / g, preferably one of between 126 and 50 m 2 / g, more preferably one of between 125 and 50 m 2 / g, more preferably one of between 120 and 50 m 2 / g and most preferably one of between 100 and 60 m 2 / g.
- a acid-treated (uncalcined) bentonite as a layered silicate and water-containing molding mixture under compression a shaped body by means of those skilled in the art devices, such as extruders or tablet presses molded, and then the uncured molded body is calcined to form a stable shaped body.
- the size of the specific surface of the catalyst support depends in particular on the quality of the (bent) bentonite used, the acid treatment process of the bentonite used, ie, for example, the nature and relative to bentonite and the concentration of the inorganic acid used, the acid treatment time and -temperature, from
- a corresponding catalyst support with a surface area of about 100 m 2 / g is offered by SÜD-Chemie AG under the name "KA-0".
- Acid-treated bentonites can be obtained by treating bentonites with strong acids, such as sulfuric acid, phosphoric acid or hydrochloric acid.
- strong acids such as sulfuric acid, phosphoric acid or hydrochloric acid.
- Bentonites which are particularly preferred in the context of the present invention are natural aluminum-containing sheet silicates which contain montmorillonite (as smectite) as the main mineral. After the acid treatment, the bentonite is usually washed with water, dried and ground to a powder.
- the acidity of the catalyst support can advantageously influence the activity of the catalyst according to the invention in the gas-phase synthesis of VAM from acetic acid and ethene.
- the catalyst support has an acidity of between 1 and 150 ⁇ val / g, preferably one of between 5 and 130 ⁇ val / g, preferably one of between 10 and 100 ⁇ val / g and most preferably one of between 10 and 60 ⁇ val / g.
- the acidity of the catalyst support is determined as follows: 1 g of the finely ground catalyst support is mixed with 100 ml of water (with a pH blank value) and extracted with stirring for 15 minutes.
- the titration curve (ml 0.01 NaOH versus pH) is then plotted and the point of intersection of the titration curve at pH 7 is determined.
- the molar equivalents are calculated in 10 ⁇ 6 equiv / g carriers, which result from the NaOH consumption for the point of intersection at pH 7.
- the catalyst support has an average pore diameter of 8 to 50 nm, preferably one of 10 to 35 nm and preferably one of 11 to 30 nm.
- the catalyst according to the invention is usually prepared by subjecting a multiplicity of catalyst support shaped bodies to a "batch" process in whose individual process steps the shaped bodies are imparted, for example by stirring and mixing tools, to relatively high mechanical loads.
- the catalyst according to the invention can be mechanically stressed during the filling of a reactor, which can lead to an undesirable development of dust and damage to the catalyst support, in particular its located in an outer region, catalytically active shell.
- the catalyst has a hardness greater than or equal to 20 N, preferably greater than or equal to 25 N, more preferably greater than or equal to 35 N, and most preferably one of greater than or equal to 40 N.
- the hardness is determined by means of a tablet hardness tester 8M from Dr. Ing. Schleuniger Pharmatron AG to 99 pieces of coated catalysts as an average determined after drying the catalyst at 130 ° C for 2h, the device settings are as follows:
- the hardness of the catalyst or catalyst support can be influenced, for example, by varying certain parameters of the process for its preparation, for example by selecting the phyllosilicate, the calcination time and / or the calcination temperature of an uncured molding formed from a corresponding support mixture, or by certain additives such as for example, methyl cellulose or magnesium stearate.
- the catalyst according to the invention comprises a catalyst support based on a natural sheet silicate, in particular based on an acid-treated calcined bentonite.
- the term "on the basis" means in the context of the present invention that the catalyst comprises a natural layered silicate.
- the proportion of the catalyst support to phyllosilicate, in particular to acid-treated calcined bentonite is greater than or equal to 50% by mass, preferably greater than or equal to 60% by mass, preferably greater than or equal to 70% by mass preferably greater than or equal to 80% by mass, more preferably greater than or equal to 90% by mass and most preferably greater than or equal to 95% by mass, based on the mass of the catalyst support.
- the VAM selectivity of the catalyst according to the invention is dependent on the integral pore volume of the catalyst support. It is preferred if the catalyst support has an integral pore volume to BJH of between 0.25 and 0.7 ml / g, preferably one of between 0.3 and 0.6 ml / g and preferably one of 0.35 to 0, 5 ml / g.
- the integral pore volume of the catalyst support is determined by the method of BJH by means of nitrogen adsorption.
- the surface of the catalyst support and its integral pore volume are determined by the BET method or by the BJH method.
- the sample can be used, for example, with a fully automatic nitrogen porosimeter from Micromeritics, type ASAP 2010 be measured, by means of which an adsorption and desorption isotherm is recorded.
- the pore volume is determined from the measurement data using the BJH method (E.P. Barret, L.J. Joiner, P.P. Haienda, J. Am. Chem. Soc. 73 (1951, 373)). This procedure also takes into account effects of capillary condensation. Pore volumes of certain pore size ranges are determined by summing up incremental pore volumes, which are obtained from the evaluation of the adsorption isotherm according to BJH.
- the integral pore volume according to the BJH method refers to pores with a diameter of 1.7 to 300 nm.
- the water absorbency of the catalyst support is 40 to 75%, preferably 50 to 70% calculated as weight increase by water absorption.
- the absorbency is determined by soaking 10 g of the carrier sample with deionized water for 30 minutes until no more gas bubbles escape from the carrier sample. Then, the excess water is decanted and the soaked sample is blotted with a cotton cloth to free the sample from adherent moisture. Then the water-loaded carrier is weighed and the absorbency calculated according to:
- the integral pore volume of the Catalyst carrier according to BJH are formed by mesopores and macropores, preferably at least 85% and preferably at least 90%.
- micropores, mesopores and macropores are understood to mean pores having a diameter of less than 2 nm, a diameter of 2 to 50 nm and a diameter of greater than 50 nm.
- the catalyst support of the catalyst according to the invention may have a bulk density of more than 0.3 g / ml, preferably greater than 0.35 g / ml and more preferably a bulk density of between 0.35 and 0.6 g / ml.
- the natural phyllosilicate present in the carrier has an SiO 2 content of at least 65% by mass, preferably at least 80% by mass and preferably from 95 to 99.5% Mass .-% based on the mass of the layered silicate.
- the phyllosilicate therefore contains less than 10% by weight of Al 2 O 3 , preferably 0.1 to 3% by mass and preferably 0.3 to 1.0% by mass, based on the mass of the phyllosilicate.
- the catalyst support of the catalyst according to the invention is formed as a shaped body. In this case, the catalyst support can basically take the form of any geometric body on which a corresponding noble metal shell can be applied.
- the catalyst support as a ball, cylinder (also with rounded faces), perforated cylinder (also with rounded faces), trilobus, "capped tablet”, tetralobus, ring, donut, star, cartwheel, “inverse” cartwheel, or as a strand, preferably as Rippstrang or star train, is formed, preferably as a ball.
- Catalyst support of the catalyst according to the invention is preferably 2 to 9 mm, depending on the geometry of the reactor tube in which the catalyst is to be used. If the catalyst support is designed as a sphere, then the catalyst support preferably has a diameter of greater than 2 mm, preferably a diameter of greater than 3 mm and preferably a diameter of 4 mm to 9 mm.
- the catalyst support is doped with at least one oxide of a metal selected from the group consisting of Zr, Hf, Ti, Nb, Ta, W, Mg, Re, Y and Fe, preferably with ZrO 2 , HfO 2 or Fe 2 Os. It may be preferred if the proportion of the catalyst support to doping oxide is between 0.01 and 20 mass%, preferably 1.0 to 10 mass% and preferably 3 to 8 mass%, based on the mass of the catalyst support , The amount of doping oxide depends primarily on the nature of the doping oxide to be used.
- the shell of the catalyst has a thickness of less than 300 microns, preferably one of less than 200 microns, preferably one of less than 150 microns, more preferably one of less than 100 microns, and more preferably one smaller than 80 ⁇ m.
- the thickness of the shell can be optically measured by means of a microscope. Indeed, the area where the precious metals are deposited appears black, while the non-precious areas appear white. The borderline between precious metal-containing and -free areas is usually very sharp and visually clearly visible. If the abovementioned boundary line is not sharp and can not be clearly identified, the thickness of the shell corresponds to the thickness of a shell, measured from the outer surface of the catalyst support, in which 95% of the precious metal deposited on the support is contained.
- the Pd / Au shell (as a function of the BET surface area of the support) can be formed with a relatively large thickness causing a high activity of the catalyst, without any appreciable reduction of the catalyst To effect VAM selectivity of the catalyst of the invention.
- the thickness of the noble metal shell can increase in thickness approximately inversely proportional to the BET surface area of the catalyst support.
- the shell of the catalyst therefore has a thickness of between 200 and 2000 microns, preferably one of between 250 and 1800 microns, preferably one of between 300 and 1500 microns, and more preferably one of between 400 and 1200 microns.
- the proportion of the catalyst in Pd is 0.6 to 2.5 mass%, preferably 0.7 to 2.3 mass% and preferably 0.8 to 2 mass. % based on the mass of the noble metal-loaded catalyst support.
- the catalyst according to the invention may have a Pd content of from 1 to 20 g / l, preferably from 2 to 15 g / l and preferably from 3 to 10 g / l.
- Au / Pd atomic ratio of the catalyst preferably between 0 and 1.2, preferably between 0.1 and 1, preferably between 0.3 and 0.9 and particularly preferably between 0.4 and 0.8.
- the Au content of the catalyst of the present invention is from 1 to 20 g / L, preferably from 1.5 to 15 g / L, and preferably from 2 to 10 g / L.
- the noble metal concentration should vary only relatively little over the shell thickness. That is, the profile of the noble metal concentration of the catalyst is over a range of 90% of the shell thickness, with the range to the outer and inner
- Each shell edge is separated by 5% of the shell thickness, from the average noble metal concentration of this range a maximum of +/- 20% off, preferably by a maximum of +/- 15% and preferably by a maximum of +/- 10%.
- its content of chloride is less than 250 ppm, preferably less than 150 ppm.
- the catalyst according to the invention may be used in addition to or as an alternative to the abovementioned doping oxides as further
- Promoter at least one alkali metal compound, preferably a potassium, a sodium, a cesium or a rubidium compound, preferably a potassium compound.
- Suitable and particularly preferred potassium compounds include potassium acetate KOAc, potassium carbonate K 2 CO 3 , potassium formate KFA, potassium hydrogen carbonate KHCO 3 and potassium hydroxide KOH, and all potassium compounds which convert to K-acetate KOAc under the respective reaction conditions of VAM synthesis.
- the potassium compound can be applied both before and after the reduction of the metal components to the metals Pd and Au on the catalyst support.
- the catalyst comprises an alkali metal acetate, preferably potassium acetate. It is particularly preferred for ensuring a sufficient promoter activity when the content of the catalyst of alkali metal acetate is 0.1 to 0.7 mol / 1, preferably 0.3 to 0.5 mol / 1.
- the alkali metal / Pd atomic ratio is between 1 and 12, preferably between 2 and 10 and more preferably between 4 and 9.
- the alkali metal / Pd atomic ratio is preferably the same smaller, the smaller the surface of the catalyst support.
- the present invention furthermore relates to a first process for preparing a coated catalyst, in particular the coated catalyst according to the invention, comprising the steps:
- Catalyst support has a surface area of less than 130 m 2 / g;
- any Pd or Au compound which can be used to achieve a high degree of dispersion of the metals can be used as the Pd and Au precursor compounds.
- degree of dispersion is understood to mean the ratio of the number of all surface metal atoms of all metal / alloy particles of a supported metal catalyst to the total number of all metal atoms of the metal / alloy particles corresponds to relatively high numerical value, since in this case as many metal atoms are freely accessible for a catalytic reaction. That is, with a relatively high degree of dispersion of a supported metal catalyst, a certain catalytic activity thereof can be achieved with a relatively small amount of metal used. According to a further preferred embodiment of the catalyst according to the invention, the degree of dispersion of the paladium is 1 to 30%.
- the Pd and Au precursor compounds may be selected from the halides, in particular chlorides, oxides, nitrates, nitrites, formates, propionates, oxalates, acetates, hydroxides, bicarbonates, amine complexes or organic complexes, for example triphenylphosphine complexes or acetylacetonate complexes, these metals.
- halides in particular chlorides, oxides, nitrates, nitrites, formates, propionates, oxalates, acetates, hydroxides, bicarbonates, amine complexes or organic complexes, for example triphenylphosphine complexes or acetylacetonate complexes, these metals.
- Pd precursor compounds are water-soluble Pd salts.
- the Pd precursor compound is selected from the group consisting of Pd (NH 3 J 4 (OH) 2 , Pd (NH 3 J 4 (OAc) 2 , H 2 PdCl 4 , Pd (NH 3 ) 4 (HCO 3 ) 2 , Pd (NH 3 ) 4 (HPO 4 ), Pd (NH 3 J 4 Cl 2 , Pd (NH 3 ) 4 -xalate, Pd-oxalate, Pd (NO 3 J 2 , Pd ( NH 3 ) 4 (NO 3 ) 2 , K 2 Pd (OAc) 2 (OH) 2 , Na 2 Pd (OAc) 2 (OH) 2 , Pd (NH 3 J 2 (NO 2 ) 2 , K 2 Pd (NO 2 J 4 , Na 2 Pd (NO 2 J 4 , Pd (OAc) 2 , K 2 PdCl 4 ,
- Pd nitrite precursor compounds may also be preferred.
- Preferred Pd nitrite precursor compounds are, for example, those obtained by dissolving Pd (OAc) 2 in a NaNO 2 solution.
- the Au precursor compound is selected from the group consisting of KAuO 2 , HAuCl 4 , KAu (NO 2 ) 4, NaAu (NO 2 J 4 , AuCl 3 , NaAuCl 4 , KAuCl 4 , KAu ( OAc) 3 (OH), HAu (NO 3 J 4 , NaAuO 2 , NMe 4 AuO 2 , RbAuO 2 , CsAuO 2 , NaAu (OAc) 3 (OH), RbAu (OAc) 3 OH, CsAu (OAc) 3 OH , NMe 4 Au (OAc) 3 0H and Au (OAc) 3. It may be advisable to use the Au (OAc) 3 or KAuO 2 by precipitating the oxide / hydroxide from a solution of gold acid, washing and isolating the precipitate,
- Suitable solvents for the precursor compounds are all pure solvents or solvent mixtures in which the selected precursor compounds are soluble and, after application to the catalyst support, can easily be removed therefrom by drying.
- Preferred solvent examples of the metal acetates as precursor compounds are above all unsubstituted carboxylic acids, in particular acetic acid, or acetone, and for the metal chlorides especially water or dilute hydrochloric acid.
- solvents are preferably those solvents which are inert and are miscible with acetic acid or water.
- Preferred solvents which are suitable as an additive to acetic acid are ketones, for example acetone or acetylacetone, furthermore ethers, for example tetrahydrofuran or dioxane,
- Preferred solvents or additives which are suitable as an additive to water are ketones, for example acetone, or alcohols, for example ethanol or isopropanol or methoxyethanol, alkalis, such as aqueous KOH or NaOH, or organic acids, such as acetic acid, formic acid, citric acid, tartaric acid , Malic acid, glyoxylic acid, glycolic acid, oxalic acid, pyruvic acid, oxamic acid, lactic acid or amino acids such as glycine.
- ketones for example acetone
- alcohols for example ethanol or isopropanol or methoxyethanol
- alkalis such as aqueous KOH or NaOH
- organic acids such as acetic acid, formic acid, citric acid, tartaric acid , Malic acid, glyoxylic acid, glycolic acid, oxalic acid, pyruvic acid, oxamic acid, lactic acid or amino acids such as glycine.
- chloride compounds are used as precursor compounds, it must be ensured that the chloride ions are reduced to a tolerable residual amount before use of the catalyst prepared by the process according to the invention, since chloride is a catalyst poison.
- the catalyst support is usually washed extensively with water after fixing the Pd and Au components of the Pd or Au precursor compound on the catalyst support. This is generally done either immediately after fixation by hydroxide precipitation of the Pd and Au components by means of caustic or after reduction of the precious metal components to the respective metal / alloy.
- chloride-free Pd and Au precursor compounds are used and chloride-free Solvent to keep the content of the catalyst of chloride as low as possible and to avoid a complex chloride-free washing.
- the corresponding acetate, hydroxide, nitrite compounds or bicarbonate compounds are preferably used as precursor compounds, since these only contaminate the catalyst support with chloride to a very small extent.
- the deposition of the Pd and Au precursor compounds onto the catalyst support in the region of an outer shell of the catalyst support can be achieved by processes known per se.
- the precursor solutions may be applied by impregnation by immersing the support in the precursor solutions or soaking in accordance with the incipient wetness method.
- a base for example sodium hydroxide solution or potassium hydroxide solution, is applied to the catalyst support, whereby the noble metal components in the form of hydroxides are precipitated onto the support.
- the Pd and the Au precursor compound is applied to the catalyst support by the catalyst support with the solution of the Pd precursor compound and with the solution of the Au precursor compound or with a solution impregnated with both the Pd and Au precursor compounds.
- the active metals Pd and Au are applied starting from chloride compounds in the region of a shell of the support on the same by means of impregnation.
- this technique has reached its limits, which is minimal Shell thickness and maximum Au loading.
- the smallest shell thicknesses of the corresponding known VAM catalysts are at best about 100 microns and it is not foreseeable that even thinner shells can be obtained by impregnation.
- higher Au loadings within the desired shell by impregnation are difficult to realize because the Au precursor compounds tend to diffuse from the shell to inner zones of the catalyst support body, resulting in wide Au shells that are scarcely in regions mixed with Pd.
- the active metals or their precursor compounds can also be applied to the carrier by means of so-called physical methods.
- the support according to the invention can preferably be sprayed, for example, with a solution of the precursor compounds, the catalyst support being moved in a coating drum into which warm air is blown in so that the solvent evaporates rapidly.
- the solution of the Pd precursor compound and the solution of Au precursor compound is applied to the catalyst support by the solutions are sprayed onto a fluidized bed or a fluidized bed of the catalyst support, preferably by means of a Aerosols of solutions.
- the shaped bodies preferably run around elliptically or toroidally.
- Fluid bed system can be performed. Particularly preferred is a fluidized bed system in which there is a so-called controlled Heilgleit Mrs.
- the catalyst support moldings are well mixed by the controlled Luftgleit für while rotating about its own axis, whereby they are dried evenly from the process air.
- the catalyst carrier shaped bodies pass the spraying process (application of the precursor compounds) in almost constant frequency.
- a substantially uniform shell thickness of a treated batch of moldings is achieved.
- the noble metal concentration varies only relatively small over a relatively large range of the shell thickness, ie, that the noble metal concentration over a large range of shell thickness is approximately a distorted rectangular function with high metal enrichment outside and slightly lower
- Metal enrichment inside describes, whereby a largely uniform activity of the resulting catalyst is ensured across the thickness of the Pd / Au shell away.
- Fluidized bed plants for carrying out the process according to the invention according to preferred embodiments are known in the art and are e.g. from the companies Heinrich Brucks GmbH (Alfeld, Germany), ERWEK GmbH (Heusenstamm, Germany), Stechel (Germany), DRIAM
- the catalyst support is heated during the application of the solutions, for example by means of heated process air.
- the degree of heating of the catalyst supports can be used to determine the drying rate of the applied solutions of the noble metal precursor compounds.
- the rate of desiccation is relatively low, so that, given a corresponding quantitative application, the formation of larger shell thicknesses may occur due to the high diffusion of the precursor compounds due to the presence of solvent.
- the rate of desiccation is relatively high, so that solution of the precursor compounds coming into contact with the shaped article dries almost instantaneously, so solution applied to the catalyst support can not penetrate deeply into it.
- relatively high temperatures the rate of desiccation is relatively high, so that solution of the precursor compounds coming into contact with the shaped article dries almost instantaneously, so solution applied to the catalyst support can not penetrate deeply into it.
- Pd (NH 3 ) 2 (NO 2 ) 2 and KAuO 2 used. These precursor compounds are basic in solution, while the classic chloride, nitrate, and acetate precursors all react acidically in solution.
- aqueous Na 2 PdCl 4 and NaAuCl 3 solutions preference is usually given to using aqueous Na 2 PdCl 4 and NaAuCl 3 solutions. These metal salt solutions are normally applied to the support at room temperature and then the metal components are fixed with NaOH as insoluble Pd or Au hydroxides. Thereafter, the loaded carrier is usually washed free of chloride with water.
- the Au fixation is with Disadvantages such as long exposure times of the base to induce the precipitation of the stable Au-Tetrachlorokomplexes, incomplete precipitation and associated poor Au retention.
- the method comprises the steps:
- This embodiment of the method according to the invention uses two mutually different precursor solutions, one of which, for example, contains one Pd and the other an Au precursor compound.
- one of the solutions has a basic and the other an acidic pH, as a rule.
- the application of the solutions to the catalyst support is usually carried out by first impregnating the support with the first and then, in a subsequent step, with the second solution as described above by impregnation.
- the second solution When applying the second solution, the two solutions are then combined on the support, whereby the pH of the solutions changes and the Pd or Au component of the respective precursor compound is precipitated on the support, without the need for a as in Conventional auxiliary base such as NaOH or KOH must be applied to the carrier.
- the mentioned embodiment of the method according to the invention is thus based on an impregnation of the catalyst support with the first solution of a Pd and / or Au catalyst.
- Precursor compound and the second solution of a Pd and / or Au precursor compound wherein the two solutions are incompatible with each other, that is, that the first solution causes precipitation of the noble metal component (s) of the precursor compound (s) of the second solution and vice versa, so that in the
- Suitable aqueous solutions of Pd precursor compounds for impregnation with incompatible solutions are listed by way of example in Table 1.
- Suitable aqueous solutions of Au precursor compounds for impregnation with incompatible solutions are listed by way of example in Table 2.
- Suitable combinations of incompatible solutions for base-free precipitation of the noble metal components are, for example, a PdCl 2 and a KAu ⁇ 2 solution; a Pd (NO 3 J 2 and a KAuO 2 solution; a Pd (NH 3 J 4 (OH) 2 and an AuCl 3 or HAuCl 4 solution.
- Pd can also be precipitated with incompatible Pd solutions and analogously Au with incompatible Au solutions, for example by contacting a PdCl 2 solution with a Pd (NH 3 ) 4 (OH) 2 solution or a HAuCl 4 - with a KAuO 2 solution.
- PdCl 2 solution with a Pd (NH 3 ) 4 (OH) 2 solution or a HAuCl 4 - with a KAuO 2 solution.
- a mixed solution is a solution containing PdCl 2 and AuCl 3 , whose noble metal components can be precipitated with a KAu ⁇ 2 solution, or a solution containing Pd (NHa) 4 (OH) 2 and KAuO 2 , their noble metal components can be precipitated with a solution containing PdCl 2 and HAuCl 4 .
- Another example of a mixed solution is the pair HAuCl 4 and KAuO 2 .
- the impregnation with the incompatible solutions is preferably carried out by impregnation or by spray impregnation, wherein the incompatible solutions, for example, simultaneously sprayed by one (two-fluid nozzle) or multiple double nozzle (s) or simultaneously by means of two nozzles or nozzle groups or seguentiell by means of one or more nozzle (s) become.
- Impregnation with the incompatible solutions may result in thinner shells due to the rapid immobilization (fixation) of the metallic components of the precursor compounds in the shell, and the concomitant shortened Pd and Au diffusion, than the conventional use of mutually compatible solutions.
- fixation the metallic components of the precursor compounds in the shell
- the concomitant shortened Pd and Au diffusion than the conventional use of mutually compatible solutions.
- high noble metal contents in thin shells improved metal retention, faster and more complete precipitation of the noble metals, the reduction of the interfering Na residual content of the carrier, the simultaneous fixation of Pd and Au in just one fixing step and the omission of NaOH. Costs and the NaOH handling and avoidance of mechanical weakening of the carrier can be achieved by contact with excess NaOH.
- the catalyst support is subjected to a fixing step for fixing the noble metal component (s) of the precursor compound. on the catalyst support.
- the fixation step may involve treatment of the carrier with caustic or acid, depending on whether the precursor compound is acidic or basic, or a
- Calcination of the carrier for transferring the noble metal component / s in a hydroxide compound / s or in an oxide include.
- the fixing step can also be omitted and the noble metal components are reduced directly, for example by treatment with a reducing gas phase, for example ethylene, etc. at elevated temperatures of 20 0 C to 200 0 C.
- a reducing gas phase for example ethylene, etc.
- the Pd and / or Au precursor compounds are converted into the oxides and thereby fixed.
- a support material based on a layered silicate as a powder and to impregnate it with the precursor compounds of the active metals.
- the pretreated powder can then be applied in the form of a "washcoat" to a suitable carrier structure, for example a ball of steatite or a KA-160 carrier, preferably by means of a coating drum, and then further processed by calcination and reduction to give the catalyst.
- the invention relates to a second process for the preparation of a shell catalyst, in particular a shell catalyst according to the invention, comprising the steps:
- the said method can also be carried out by first applying the non-noble-loaded, powdery carrier material to a carrier structure and only then applying the noble metals.
- the support for calcining the noble metal components into the corresponding oxides can be calcined.
- the calcination is preferably carried out at temperatures of less than 700 0 C. Particularly preferably between 300-450 0 C with access of air.
- the calcination time depends on the calcination temperature and is preferably chosen in the range of 0.5-6 hours. At a calcination temperature of about 400 ° C., the calcination time is preferably 1-2 hours. At a calcination temperature of 300 ° C., the calcination time is preferably up to 6 hours.
- a preferred embodiment comprises calcining the Pd-laden carrier (with or without prior precipitation fixation) at about 400 0 C to PdO formation followed by Au application and reduction in the (intermediate) to form a Au-sintering avoided can be.
- the noble metal components are reduced before the use of the catalyst, wherein the reduction in situ, ie in the process reactor, or ex situ, ie in a special reduction reactor, can be performed.
- the reduction in situ is preferably carried out with ethylene (5% by volume) in nitrogen at a temperature of about 150 ° C. over a period of, for example, 5 hours.
- the reduction ex situ For example, with 5% by volume of hydrogen in nitrogen, for example by means of forming gas, at temperatures in the range of preferably 150-500 ° C over a period of 5 hours.
- Gaseous or volatilizable reducing agents such as CO, NH 3 , formaldehyde, methanol and hydrocarbons may also be employed, which gaseous reducing agents may also be diluted with inert gas such as carbon dioxide, nitrogen or argon.
- inert gas such as carbon dioxide, nitrogen or argon.
- an inert gas is diluted
- Reducing agent used Preference is given to mixtures of hydrogen with nitrogen or argon, preferably with a hydrogen content of between 1% by volume and 15% by volume.
- the reduction of the noble metals can also be carried out in the liquid phase, preferably by means of the reducing agents hydrazine, K-formate, Na-formate, ammonium formate, formic acid, K-hypophosphite, hypophosphorous acid, H 2 O 2 or Na hypophosphite.
- the amount of reducing agent is preferably selected so that at least the equivalent necessary for complete reduction of the noble metal components is passed over the catalyst during the treatment period. Preferably, however, an excess of reducing agent is passed over the catalyst to ensure rapid and complete reduction.
- it is depressurized, ie at an absolute pressure of about 1 bar, reduced.
- a rotary kiln or a fluidized bed reactor or a fluidized bed reactor used to ensure a uniform reduction of the catalyst.
- the invention furthermore relates to the use of the catalyst according to the invention as oxidation catalyst, as hydrogenation / dehydrogenation catalyst, as catalyst in hydrodesulfurization, as hydrodenitrification catalyst, as hydrodeoxigenation catalyst or as catalyst in the synthesis of alkenylalkanoates, in particular in the synthesis of vinyl acetate monomer, especially in the gas phase oxidation of ethylene and acetic acid to vinyl acetate monomer.
- the catalyst according to the invention is preferably used for the production of VAM. This is generally done by passing acetic acid, ethylene and oxygen or
- Example 1 225 g of spherical, formed from an acid-treated calcined bentonite as a natural sheet silicate catalyst support molding from SÜD-Chemie AG (Munich, Germany) with the trade name "KA-0" and the characteristics listed in Table 3:
- Precious metal mixed solution was sprayed onto the fluidized bed of the moldings a 0.05 molar NaOH solution at a temperature of 80 ° C over a period of 30 min.
- the NaOH precipitates predominantly within the shell and fixes the Pd and Au metal components without exposing the support to excessively high NaOH concentrations.
- the supports were washed extensively with water in the fluidized bed apparatus to substantially free the support from alkali metal and chloride introduced into the support via the noble metal compounds and NaOH.
- the moldings were dried by moving in hot process air (100 ° C.) in the fluidized bed apparatus.
- the resulting coated catalyst contained about 1.2 mass% Pd and had an Au / Pd atomic ratio of about 0.5, a shell thickness of about 160 microns and a hardness of 38 N.
- the noble metal concentration of the Pd / Au coated catalyst thus produced deviated over a range of 90% of the shell thickness, with the outer and inner shell boundary areas each spaced 5% of the shell thickness, from the average noble metal concentration of this region by a maximum of +/- 10 % off.
- the determination of the noble metal distribution was carried out on a scanning electron microscope LEO 430VP, equipped with an energy-dispersive spectrometer from Bruker AXS.
- a catalyst ball was cut through, glued onto an aluminum sample holder and then vapor-deposited with carbon.
- a nitrogen-free silicon drift chamber detector (XFlash® 410) was used with an energy resolution of 125 eV for the manganese K a i Pha ⁇ line.
- catalyst support shaped bodies "KA-0" as defined in Example 1 are mixed with 43.8 ml of an aqueous solution according to the incipient wetness method, in which a support having a solution volume corresponding to its pore volume is impregnated containing 1.568 g of Na 2 PdCl 4 and 0.367 g of HAuCl ⁇ impregnated After the impregnation 89.17 g of a 0.35 molar NaOH solution to the
- Catalyst support molded body and allowed to stand overnight at RT for 22 hours. After decanting the fixing solution, the catalyst precursor thus prepared is reduced with 73.68 g of a 10% NaH 2 PO 2 solution (Fluka) for 2 hours. After draining the reduction solution, the catalysts are washed with dist. Water for 8 hours at RT while constantly changing the water (flow 140 rpm) to Washed removal of Cl residues. The final value of the conductivity of the washing solution is 1.2 ⁇ S.
- the catalyst is then dried in the fluidized bed at 90 ° C. for 50 minutes.
- the dried spheres are mixed with a mixture of 27.29 g 2 molar KOAc solution and 18.55 g
- the theoretical metal loading is 0.8 wt% Pd and 0.3 wt% Au;
- the values experimentally determined by elemental analysis by ICP (Inductively Couples Plasma) were 0.77 wt% Pd and 0.27 wt% Au.
- the shell thickness was 312 microns.
- a catalyst was prepared analogously to Example 2, with the catalyst support molding being a support from St) D-
- the theoretical metal loading is 0.8 wt% Pd and 0.3 wt% Au; the values experimentally determined by elemental analysis by ICP were 0.78 wt% Pd and 0.27 wt% Au.
- the shell thickness was 280 ⁇ m.
- the space-time yield is given as g VAM / 1 catalyst / h.
- the oxygen conversion is calculated according to (mole O 2 in-mole O 2 out) / mole O 2 in.
- the inventive catalyst according to Example 2 shows a selectivity S (C 2 H 4 ) of 92.3% and a space-time yield (determined by gas chromatography) of 615 g VAM / 1 catalyst / h at an oxygen conversion of 36.5%.
- the catalyst according to Comparative Example 1 showed a selectivity S (C 2 H 4 ) of 91.0% and a space-time yield (determined by gas chromatography) of 576 g VAM / 1 catalyst / h at an oxygen conversion of 36.1%.
- the inventive catalyst according to Example 2 shows both a higher selectivity and activity in the VAM synthesis compared to a catalyst of the prior art according to Comparative Example 1.
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Abstract
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DE102007025444A DE102007025444A1 (de) | 2007-05-31 | 2007-05-31 | VAM-Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung |
PCT/EP2008/004329 WO2008145389A2 (fr) | 2007-05-31 | 2008-05-30 | Catalyseur sous enveloppe servant à la production de vam, procédé de production et d'utilisation dudit catalyseur |
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US (1) | US20100197956A1 (fr) |
EP (1) | EP2155380A2 (fr) |
JP (1) | JP5476293B2 (fr) |
KR (1) | KR20100031702A (fr) |
CN (1) | CN101730584A (fr) |
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2007
- 2007-05-31 DE DE102007025444A patent/DE102007025444A1/de not_active Withdrawn
-
2008
- 2008-05-30 JP JP2010509741A patent/JP5476293B2/ja not_active Expired - Fee Related
- 2008-05-30 CN CN200880018044A patent/CN101730584A/zh active Pending
- 2008-05-30 WO PCT/EP2008/004329 patent/WO2008145389A2/fr active Application Filing
- 2008-05-30 KR KR1020097027579A patent/KR20100031702A/ko not_active Application Discontinuation
- 2008-05-30 US US12/602,315 patent/US20100197956A1/en not_active Abandoned
- 2008-05-30 EP EP08758900A patent/EP2155380A2/fr not_active Withdrawn
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JP2010527778A (ja) | 2010-08-19 |
WO2008145389A3 (fr) | 2009-04-09 |
CN101730584A (zh) | 2010-06-09 |
DE102007025444A1 (de) | 2008-12-11 |
WO2008145389A2 (fr) | 2008-12-04 |
US20100197956A1 (en) | 2010-08-05 |
JP5476293B2 (ja) | 2014-04-23 |
KR20100031702A (ko) | 2010-03-24 |
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