EP2997005A1 - Method for producing vinylidene carboxylic acid (esters) by reacting formaldehyde with alkyl carboxylic acid (esters) - Google Patents
Method for producing vinylidene carboxylic acid (esters) by reacting formaldehyde with alkyl carboxylic acid (esters)Info
- Publication number
- EP2997005A1 EP2997005A1 EP14724697.9A EP14724697A EP2997005A1 EP 2997005 A1 EP2997005 A1 EP 2997005A1 EP 14724697 A EP14724697 A EP 14724697A EP 2997005 A1 EP2997005 A1 EP 2997005A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- formula
- formaldehyde
- vanadium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- -1 vinylidene carboxylic acid Chemical class 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 194
- 150000002148 esters Chemical class 0.000 title abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 79
- 239000012495 reaction gas Substances 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 17
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 9
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 40
- 239000012018 catalyst precursor Substances 0.000 claims description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003682 vanadium compounds Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 230000006315 carbonylation Effects 0.000 claims description 2
- 238000005810 carbonylation reaction Methods 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 90
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000010438 heat treatment Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000000470 constituent Substances 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000001354 calcination Methods 0.000 description 11
- 238000007669 thermal treatment Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000003701 inert diluent Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052756 noble gas Inorganic materials 0.000 description 5
- 150000002835 noble gases Chemical class 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
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- 229910052701 rubidium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 239000004110 Zinc silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000009997 thermal pre-treatment Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Definitions
- the present invention relates to a process for the preparation of vinylidene carboxylic acids and their esters by reacting formaldehyde with alkylcarboxylic acids and their esters.
- the present invention relates to a process for the preparation of acrylic acid by reacting formaldehyde with acetic acid.
- An advantage of this procedure is that it has a comparatively high target product selectivity relative to reacted propene.
- the recycling of unreacted propene allows high acrylic acid yields from the propene used.
- methanol can be produced from synthesis gas (gas mixtures of carbon monoxide and molecular hydrogen) from all carbon-containing fossil raw materials and all carbon-containing renewable raw materials.
- US Pat. No. 4,165,438 discloses a process for preparing acrylic acid and its esters, where the reactants are formaldehyde and a lower alkylcarboxylic acid or its lower alkyl ester in the gas phase at about 300.degree. C. to 500.degree. genwart a catalyst be implemented.
- the catalyst consists mainly of vanadium orthophosphate having an intrinsic surface area of about 10 to about 50 m 2 / g and a P / V atomic ratio of 1: 1 to 1.5: 1.
- the oxidation number of vanadium is given as approx. 3.9 to 4.6.
- the catalyst is said to be activated by heating in an oxygen-containing gas, such as air, deactivated by use and reactivated by reheating.
- EP 0 124 380 A1 discloses a process for the preparation of unsaturated carboxylic acids and esters, wherein a gaseous mixture of a saturated monocarboxylic acid or its ester with formaldehyde or a formaldehyde derivative in the presence of oxygen in a reaction zone over a catalyst in the form of a Mul - timetalloxids leads.
- the oxidation number of the catalyst vanadium is 4.21 to 4.23.
- the object of the present invention was to provide a process for the preparation of vinylidenecarboxylic acids and their esters, which does not have the disadvantages of the processes of the prior art.
- the object was to provide a process which ensures a high conversion of the formaldehyde used over a long period of time and a high selectivity of the conversion of formaldehyde to vinylidenecarboxylic acid or its esters.
- the object is achieved by a process for the preparation of a compound of the formula (I),
- R 1 and R 2 independently of one another, are H or (C 1 -C 4) -alkyl, where a reaction gas, the gaseous formaldehyde, molecular oxygen and a gaseous compound of the formula (II)
- a solid catalyst which brings into contact with a solid catalyst whose active composition is a vanadium-phosphorus oxide having an average oxidation state of vanadium of +4.40 to +5.0, preferably +4.48 to +5.0, more preferably more than + 4.60 to +5.0, more preferably more than +4.65 to +4.99, most preferably more than +4.69 to +4.99,
- an alkylcarboxylic acid which is able to undergo a condensation reaction with formaldehyde can be converted into a vinylidenecarboxylic acid.
- an alkylcarboxylic acid ester capable of undergoing a condensation reaction with formaldehyde can be converted to a vinylidenecarboxylic acid ester.
- reaction between research maldehyde and alkylcarboxylic acid or Alkylcarbonklareester one equivalent of water is released (condensation reaction, see Scheme 1).
- acetic acid is used as compound of the formula (II)
- acrylic acid is obtained as the compound of the formula (I).
- methyl acetate is used as the compound of the formula (II)
- methyl acrylate is obtained as the compound of the formula (I).
- propanoic acid is used as the compound of the formula (II)
- methacrylic acid is obtained as the compound of the formula (I).
- methyl propionate is used as the compound of the formula (II)
- methyl methacrylate is obtained as the compound of the formula (I).
- acetic acid is particularly preferred as the compound of the formula (II).
- a process is particularly preferred in which the compound of the formula (I) is acrylic acid and the compound of the formula (II) is acetic acid.
- R 1 and R 2 are preferably H or CH 3.
- the compound of the formula (I) is particularly preferably acrylic acid and the compound of the formula (II) particularly preferably acetic acid.
- the reaction gas further comprises an inert diluent gas, preferably an inert diluent gas other than water vapor.
- An inert diluent gas is understood as meaning a gas which is inert under the conditions prevailing in the process according to the invention.
- An inert reaction gas constituent per se, in the process according to the invention remains more than 95 mol%, preferably more than 97 mol%, more than 98 mol%, or more than 99 mol% chemically unchanged.
- inert diluent gases are N2, CO2, H2O and noble gases such as Ar and mixtures of the aforementioned gases.
- the inert diluent gas used in the process according to the invention is preferably molecular nitrogen.
- Water vapor plays a special role as an inert diluent gas, since it is obtained both as a by-product (Scheme 1) and in some of the formaldehyde sources mentioned below, and optionally as an impurity in formaldehyde and / or the Compound of formula (II) is contained and the desired condensation reaction usually impaired.
- the water vapor content in the reaction gas to 0 to 50 vol .-%, preferably 0 to 30 vol .-%, particularly preferably 0 to 20 vol .-% measured.
- An increased water vapor content reduces the conversion under given reaction conditions. This effect can be at least partially compensated by raising the reaction temperature.
- the proportion of the inert diluent gas in the reaction gas is preferably from 50 to 95% by volume, preferably from 60 to 90% by volume, particularly preferably from 70 to 90% by volume.
- reaction gas may contain at least one reactant gas constituent predominantly solid under normal conditions (20 ° C., 1013 mbar) as a so-called "solid reaction gas constituent" (eg some of the formaldehyde sources described below, such as trioxane.)
- the reaction gas may further comprise at least one reactant gas constituent. which under normal conditions is predominantly liquid, as a so-called “liquid reaction gas component” (eg acetic acid).
- the reaction gas may also contain a reactant gas constituent that is predominantly gaseous under normal conditions, as a so-called "gaseous reactant gas constituent" (eg, formaldehyde) .
- gaseous reactant gas constituent eg, formaldehyde
- the generation of the reactant gas may include transferring non-gaseous reactant gas constituents to the gaseous phase and combining all reactant gas constituents At least one of the gaseous reaction gas constituents and / or a solid reaction gas constituent may also initially be at least partially taken up in at least one liquid reaction gas constituent and then transferred into the gas phase together with the liquid reaction gas constituent ,
- the conversion into the gas phase takes place by evaporation, preferably by supplying heat and / or reducing the pressure.
- the non-gaseous constituents of the reaction gas can be introduced into gaseous reactant constituents in order to promote the evaporation of the non-gaseous constituents of the reaction gas. Preference is given to a solution containing at least one liquid reaction gas component and if necessary.
- Other reaction gas components may contain, in a storage vessel before and promotes the submitted solution z. B. by means of a pump with the desired volume flow in a gaseous stream of preheated reaction gas components.
- the combination of the presented solution with the gaseous stream of preheated reaction gas constituents can e.g. B. done in an evaporator coil.
- formaldehyde can also be supplied in the form of at least one of the formaldehyde sources mentioned below. Depending on the choice of formaldehyde source, it may be liquid, solid and / or gaseous under standard conditions. Depending on the choice of formaldehyde source, the formaldehyde can be released from the source of formaldehyde before and / or after the transfer to the gas phase. In the reaction gas, the formaldehyde from the formaldehyde source may also be only partially released.
- the reaction gas is generally brought at a reaction temperature of 250 to 400 ° C, preferably at 260 to 390 ° C, more preferably at 270 to 380 ° C, more preferably at 290 to 370 ° C, further particularly preferably at 290 to 340 ° C, and most preferably at 300 to 325 ° C in contact with the catalyst.
- the reaction temperature is the average over the volume of the catalyst temperature of the reaction gas located in the catalyst bed.
- the reaction temperature is calculated from the temperature profile of the catalyst bed. In isothermal reaction, the reaction temperature agrees with the temperature, which is set at the reactor outer wall. To set the temperature, a heater can be used.
- the reaction gas of the reaction zone is preferably already introduced at a temperature in the range from 160 to 400.degree.
- the reaction gas may be brought into contact with solid inert material before being brought into contact with the catalyst. In contact with the solid inert material, the temperature of the reaction gas can be adjusted to the value at which the reaction gas is to come into contact with the catalyst
- the total pressure of the reaction gas i. the pressure prevailing in the reaction gas at the catalyst can be greater than or equal to 1 bar and less than 1 bar.
- the total pressure of the reaction gas is 1, 0 bar to 50 bar, preferably 1, 0 to 20 bar, more preferably 1, 0 to 10 bar, most preferably 1, 0 to 6.0 bar.
- the catalyst may be in the form of a fluidized bed.
- the catalyst is in the form of a fixed bed.
- the catalyst is disposed in a reaction zone.
- the reaction zone can be arranged in a heat exchanger reactor which has at least one primary space and at least one secondary space.
- the primary and the secondary space are separated by a partition wall.
- the primary space comprises the reaction zone in which at least the catalyst is arranged.
- the secondary space is flowed through by a fluid heat transfer medium. Heat is exchanged through the partition for the purpose of controlling and controlling the temperature of the reaction gas in contact with the catalyst (to temper the reaction zone).
- reaction zone may be located in an adiabatic reactor.
- heat of reaction is not removed via a dividing wall by thermal contact with a heat transfer medium, such as a fluid heat carrier, but remains predominantly in the reaction zone.
- Adaabasie increases the temperature of the reaction or product gas in an exothermic reaction over the reactor length.
- the vanadium-phosphorus oxide has a phosphorus / vanadium atomic ratio of from 0.9 to 2.0, preferably from 0.9 to 1.5, more preferably from 0.9 to 1.3, and most preferably from 1.0 to 1, 2 on.
- the vanadium-phosphorus oxide has a BET specific surface area of at least 10 m 2 / g, preferably from 10 to 50 m 2 / g and most preferably from 10 to 40 m 2 / g. All data in this document on specific surfaces refer to determinations according to DIN 66131 (determination of the specific surface area of solids by gas adsorption (N2) according to Brunauer-Emmet-Teller (BET)).
- the catalysts used in the process according to the invention are distinguished by particularly high selectivities of the formation of the compound of the formula (I) with simultaneously high conversion of formaldehyde.
- the active composition may be doped with vanadium and phosphorus-different promoter elements.
- Suitable promoter elements of this type are the elements of Groups 1 to 15 of the Periodic Table which are different from P and V.
- Doped vanadium phosphorous oxides disclose WO 97/12674, WO 95/26817, US-A 5,137,860, US-A 5,296,436, US-A 5,158,923, US-A 4,795,818 and WO 2007/012620.
- Preferred promoters according to the invention are the elements lithium, potassium, sodium, rubidium, cesium, thallium, molybdenum, zinc, hafnium, zirconium, titanium, chromium, manganese, nickel, copper, iron, boron, silicon, tin, niobium, cobalt and bismuth. among which, in addition to iron, in particular niobium, molybdenum, zinc and bismuth are preferred.
- the active materials may contain one or more promoter elements.
- the total content of promoters in the catalytic active composition based on their weight, preferably not more than 5 wt .-% (the individual promoter element each counted as electrically neutral oxide in which the promoter element the same charge number (oxidation number) as in Active mass has).
- the vanadium-phosphorus oxide corresponds to the general formula (III),
- X 1 is Fe, Mo, Bi, Co, Ni, Si, Zn, Hf, Zr, Ti, Cr, Mn, Cu, B, Sn and / or Nb, preferably Fe, Nb, Mo, Zn and / or Hf stands,
- X 2 is Li, K, Na, Rb, Cs and / or TI
- b is 0.9 to 2.0, preferably 0.9 to 1.5, particularly preferably 0.9 to 1, 3 and very particularly preferably 1, 0 to 1, 2,
- d is> 0 to 0.1
- e is> 0 to 0.1
- n stands for the stoichiometric coefficient of the element oxygen, which is determined by the stoichiometric coefficients of the elements other than oxygen and their charge number in (III).
- the catalyst can be present as Vollkatalysatorform analyses or shell catalysts. It is also possible to use pulverulent active material as catalyst.
- the Vollkatalysatorform analyses may consist essentially of active material (undiluted Vollkatalysatorformsammlung).
- the active composition may also be present in dilute form in the unsupported catalyst body (dilute unsupported catalyst bodies), with at least one substantially inert composition being present in the unsupported catalyst bodies. is included.
- the diluent material is preferably selected from finely divided alumina, silica, aluminosilicates, zirconia, titania. Undiluted Vollkatalysatorform analyses are inventively preferred.
- the Vollkatalysatorformmaschine can have any shape.
- Preferred regularly shaped unsupported catalyst bodies are spheres, solid cylinders, hollow cylinders and trilobes, the longitudinal extent of which is advantageously 1 to 10 mm in all cases.
- Preferred irregularly shaped Vollkatalysatorform analyses are z. B. fragments regularly shaped Vollkatalysatorform Sciences.
- the preparation of the unsupported catalyst bodies preferably takes place starting from the catalyst precursor composition and comprises a shaping process and the thermal treatment described below.
- the molding process preferably includes tabletting, extrusion and / or extrusion.
- the thermal treatment specified in more detail below may be carried out at least partially before the molding process and / or at least partially after the molding process. Preference is given to adding the catalyst precursor composition at least with a shaping aid, such as graphite or mineral fibers, prior to molding.
- the outer diameter of cylindrical Vollkatalysatorform Orchestran is technically expediently 3 to 10 mm, preferably 4 to 8 mm and especially 5 to 7 mm.
- Their height is advantageously 1 to 10 mm, preferably 2 to 6 mm and especially 3 to 5 mm.
- the same dimensions are also preferred in the case of hollow-cylindrical unsupported catalyst bodies, wherein the internal diameter of the opening running from top to bottom is advantageously 1 to 8 mm, preferably 2 to 6 mm and very particularly preferably 2 to 4 mm.
- a wall thickness of 1 to 3 mm is useful for hollow cylinders in terms of application.
- Shelled catalysts comprise bodies applied to the surface of inert carrier form.
- the surface of an inert support molding is coated with a powdery active composition or with a powdery not yet or only partially thermally treated catalyst precursor composition with concomitant use of a liquid binder.
- At least part of the thermal treatment takes place after the coating, when the inert carrier shaped body is coated with not or only partially thermally treated catalyst precursor composition.
- Inert carrier form body also differ from the active mass usually also by having a much lower specific surface area. In general, their specific surface is less than 3 m 2 / g Colour body.
- the inert carrier form body are for example quartz, silica glass, sintered silica, sintered or smelted clay, porcelain, sintered or melt silicates such as aluminum silicate, magnesium silicate, zinc silicate, zirconium silicate and steatite particular (eg Steatite C 220 from. CeramTec).
- the geometry of the inert carrier shaped bodies can in principle be irregularly shaped, with regularly shaped carrier shaped bodies such as, for example, spheres or hollow cylinders being preferred according to the invention.
- the longitudinal extension of the abovementioned inert carrier shaped bodies for the purposes according to the invention is 1 to 10 mm.
- the coating of the inert shaped carrier bodies with the pulverulent active composition or the pulverulent not yet or only partially thermally treated catalyst precursor composition is preferably carried out in a suitable rotatable container, e.g. in a coating drum.
- a liquid binder which contains an adhesive liquid is expediently sprayed on the inert carrier moldings in terms of application technology and the surface of the carrier tablets moved in the coating drum is dusted with the powdery mass (cf., for example, EP-A 714 700).
- the adhesive liquid is usually at least partially removed from the coated carrier form body (for example, by passing hot gas through the coated carrier tablets, as described in WO 2006/094766).
- liquid binders e.g. Water and aqueous solutions (e.g., of glycerol in water).
- the coating of the carrier form body can also be carried out by spraying a suspension of the powdery mass to be applied in liquid binder (for example water) onto the surface of the inert carrier shaped bodies (generally under the action of heat and a drying drag gas).
- the coating can also be carried out in a fluidized bed or powder coating plant.
- the layer thickness of the active composition applied to the surface of the inert carrier molding is 10 to 2000 ⁇ m, preferably 10 to 500 ⁇ m, more preferably 100 to 500 ⁇ m, particularly preferably 200 to 300 ⁇ m.
- Suitable shell catalysts are, inter alia, those whose inert carrier molding has the shape of a hollow cylinder with a length in the range of 3 to 6 mm, an outer diameter in the range of 4 to 8 mm and a wall thickness in the range of 1 to 2 mm.
- all are suitable in DE-A 102010028328 and in DE-A 102010023312 as well as all ring geometries disclosed in EP-A 714 700 for possible inert carrier shaped bodies of annular catalysts.
- an unsupported full catalyst catalyst article is obtained by reacting a pentavalent vanadium compound, preferably V2O5, with an organic, reducing solvent, preferably isobutanol, in the presence of a pentavalent phosphorus compound, preferably ortho- and / or or pyrophosphoric acid, to a catalyst precursor composition, forming the catalyst precursor composition into solid catalyst precursor moldings and maintaining them in a molecular oxygen atmosphere at a temperature generally 250 ° C, preferably 300 ° C, more preferably 350 ° C, but not normally 700 ° C , preferably does not exceed 650 ° C, and most preferably does not exceed 600 ° C.
- the inventively high average oxidation state of the vanadium is achieved by the treatment in the molecular oxygen-containing atmosphere.
- the treatment is preferably carried out prior to introducing the catalyst into the reactor as part of a “thermal treatment.” It can also be carried out at least partially in the reactor as part of the "activation”.
- the preparation of the catalyst may comprise the steps of: a) reacting a pentavalent vanadium compound (eg, V2O5) with an organic, reducing solvent (eg, alcohol, such as iso-butanol) in the presence of a pentavalent phosphorus compound (eg, ortho and / or pyro - phosphoric acid) with heating to 75 to 205 ° C, preferably to 100 to 120 ° C; b) cooling the reaction mixture to advantageously 40 to 90 ° C; c) isolating the formed solid V, P, O containing catalyst precursor composition (eg by filtration); d) drying and / or thermal pretreatment of the catalyst precursor composition (optionally until incipient preformation by dehydration from the catalyst precursor composition); e) addition of shaping aids, such as, for example, finely divided graphite or mineral fibers, and then shaping to a full catalyst precursor molding by, for example, tabletting; Then at least one thermal treatment of the formed Vollkatalysatorvorpet
- the temperature usually exceeds 250 ° C, preferably 300 ° C, more preferably 350 ° C, but usually not 700 ° C, preferably not 650 ° C and most preferably not 600 ° C.
- the catalyst precursor may be both a full catalyst precursor body and a catalyst precursor composition.
- the catalyst precursor is used in an oxidizing atmosphere having a molecular oxygen content of generally 2 to 21% by volume, and preferably 5 to 21% by volume at a temperature of 200 to 350 ° C, and preferably from 250 to 350 ° C over a period of 0.5 to 4 hours, preferably 1 to 2 hours left.
- mixtures of oxygen, inert gases (eg nitrogen or argon), hydrogen oxide (water vapor) and / or air and air are used.
- the temperature may be kept constant during the step (i), rising or falling on average.
- Step (i) is generally preceded by a heating phase.
- the catalyst precursor is used in a non-oxidizing atmosphere containing ⁇ 0.5% by volume of molecular oxygen and 20 to 75% by volume, preferably 30 to 60% by volume, of hydrogen oxide (water vapor) .-% at a temperature of 300 to 500 ° C and preferably from 350 to 450 ° C over a period of> 0.5 hours, preferably 2 to 10 hours and more preferably 2 to 4 hours leave.
- the non-oxidizing atmosphere generally contains nitrogen and / or noble gases, such as, for example, argon, in addition to the abovementioned hydrogen oxide, although this is not intended to be limiting.
- the non-oxidizing atmosphere preferably contains> 40% by volume of nitrogen.
- the temperature may be kept constant during the step (ii), rising or falling on average. If step (ii) is carried out at a temperature higher or lower than step (i), a heating or cooling phase is usually added between steps (i) and (ii).
- step (iii) the catalyst precursor is heated in an oxidizing atmosphere having an oxygen content of 2 to 21% by volume to a temperature of 250 to 700 ° C, preferably 300 to 650 ° C, particularly preferably 350 to 600 ° C and leave under these conditions until the desired average oxidation state of the vanadium is established.
- the period over which the heat treatment in step (iii) is maintained is preferably selected in the process according to the invention in such a way that the mean oxidation state of the vanadium has a value of +4.40 to +5.0, preferably +4 , 48 to +5.0, more preferably more than +4.60 to +5.0, more preferably more than +4.65 to +4.99, most preferably more than +4.69 to +4.99 established.
- step (iii) is generally dependent on the nature of the catalyst precursor, the set temperature, and the selected gas atmosphere, particularly the oxygen content.
- steps (i), (ii) and (iii) further steps are possible during the thermal treatment.
- a further step for example, changes in the temperature (heating, cooling), changes in the gas atmosphere (conversion of the gas atmosphere), further hold times, transfers of the catalyst precursor into other apparatuses (eg for the production of catalyst precursor mass of unsupported catalyst precursor bodies) or interruptions of the entire thermal treatment.
- the catalyst precursor usually has a temperature of ⁇ 100 ° C. before the start of the thermal treatment, this is usually to be heated before step (i).
- the heating can be carried out using various gas atmospheres.
- the heating is carried out in an oxidizing atmosphere as defined under step (i).
- an activating gas containing molecular oxygen and substantially free of organic compounds is passed over the catalyst at a temperature of 200 to 450 ° C. Activation can take from a few minutes to a few days.
- the pressure of the activating gas mixture and its residence time on the catalyst during activation are preferably set similarly, such as the pressure of the reaction gas and its residence time on the catalyst in the preparation of the compound of the formula (I).
- the Aktiviergasgemisch contains molecular oxygen and at least one inert Aktiviergas istteil selected from N2, CO, CO2, H2O and noble gases such as Ar.
- the activating gas contains from 0.5 to 22% by volume, preferably from 1 to 20% by volume and in particular from 1.5 to 18% by volume of molecular oxygen.
- air is used as a constituent of the activating gas mixture.
- the residence time of the reaction gas in contact with the catalyst is not limited. It is generally in the range from 0.3 to 15.0 s, preferably 0.7 to 13.5 s, particularly preferably 1, 0 to 12.5 s.
- the ratio of flow rate to reaction gas based on the volume of the catalyst is 200-5000 hr.sup.- 1 , preferably 250-4000 h.sup.- 1 and even more preferably 300-3500 hr.sup.- 1 .
- the load of the catalyst of formaldehyde (expressed in gFormaidehyd (gKatai sator y * hour)) is generally from 0.01 -3.0 hr 1, preferably from 0.015 to 1, 0 hr 1, and even more preferably 0.02 to 0, 5 hr 1 .
- the content of the reaction gas to compound of the formula (II) in the process according to the invention is 1, 5 to 20% by volume, preferably 2 to 18% by volume, particularly preferably 3 to 15% by volume.
- the content of oxygen in the reaction gas in the process according to the invention is 0.1 to 10% by volume, preferably 0.3 to 7.5% by volume, particularly preferably 0.5 to 5.0% by volume. In the presence of oxygen, the deactivation of the catalyst is delayed.
- the content of formaldehyde and / or formaldehyde source in the reaction gas in the process according to the invention is 0.5 to 10% by volume, preferably 1 to 9.0% by volume, more preferably 2.0 to 8.0% by volume. , calculated as formaldehyde.
- the process according to the invention also comprises the provision of the formaldehyde from a formaldehyde source selected from trioxane, paraformaldehyde, formalin, methylal, aqueous paraformaldehyde solution or aqueous formaldehyde solution, or by heterogeneously catalyzed partial gas phase phase oxidation of methanol.
- a formaldehyde source selected from trioxane, paraformaldehyde, formalin, methylal, aqueous paraformaldehyde solution or aqueous formaldehyde solution, or by heterogeneously catalyzed partial gas phase phase oxidation of methanol.
- Trioxane is a heterocyclic compound formed by trimerization of formaldehyde which decomposes on heating to monomeric formaldehyde. Since the reaction gas is brought into contact with the catalyst at elevated temperature (generally more than 250 ° C.), trioxane represents a suitable source of formaldehyde. Since trioxane dissolves in water and in alcohols such as methanol, corresponding processes can also be used for the process according to the invention Trioxane solutions are used as sources of formaldehyde. A content of sulfuric acid in trioxane solutions of 0.25 to 0.50 wt .-% favors the cleavage to formaldehyde.
- the trioxane may also be dissolved in a liquid mainly consisting of the compound of formula (II) and the resulting solution evaporated for purposes of generating the reaction gas and the trioxane contained therein cleaved at the elevated temperature in formaldehyde.
- Aqueous formaldehyde solution can be obtained commercially, for example, with a formaldehyde content of from 35 to 50% by weight as formalin.
- formalin contains small amounts of methanol as a stabilizer. These can be based on the weight of the Formalin, 0.5 to 20 wt .-%, preferably 0.5 to 5 wt .-% and particularly preferably 0.5 to 2 wt .-% amount.
- the forminin can be used directly to provide the reaction gas.
- all aqueous formaldehyde solutions having from 1 to 100% by weight may be used in the process described here.
- Paraformaldehyde is the short chain polymer of formaldehyde whose degree of polymerization is typically 8 to 100. It is a white powder that breaks down at low pH or under heating in formaldehyde.
- paraformaldehyde solution Upon heating paraformaldehyde in water, it decomposes to yield an aqueous formaldehyde solution which is also suitable as a source of formaldehyde. Sometimes it is referred to as an aqueous "paraformaldehyde solution" to delineate it from aqueous formaldehyde solutions produced by diluting formalin, but in fact paraformaldehyde as such is substantially insoluble in water.
- Methylal (dimethoxymethane) is a reaction product of formaldehyde with methanol, which is a colorless liquid at normal pressure and 25 ° C. In aqueous acids, it is hydrolytically cleaved to form formaldehyde and methanol. After conversion to the vapor phase, both methylal and the hydrolyzate formed in aqueous acid can be used directly to provide the reaction gas.
- formaldehyde is produced by heterogeneously catalyzed partial gas phase oxidation of methanol. It is particularly preferred according to the invention to provide the formaldehyde by heterogeneously catalyzed partial gas phase phase oxidation of methanol.
- the formaldehyde is supplied to the reaction gas in this embodiment as a product gas of a heterogeneously catalyzed partial gas phase oxidation of methanol to formaldehyde, optionally after a partial or total amount of contained in the product gas, possibly unreacted methanol has been separated.
- the presence of oxygen in the reaction gas delays the deactivation of the catalyst, the activity of the catalyst may decrease over long periods of time. In order to increase the activity of the catalyst again can between each two production steps in which the compound of formula (I) is prepared, a
- Regeneration step are performed.
- a regeneration gas containing molecular oxygen and substantially free of organic compounds is passed over the catalyst at a temperature of 200 to 450 ° C.
- the regeneration step can extend over a few minutes to a few days.
- the pressure of the regeneration gas and its residence time on the catalyst in the regeneration step are adjusted in a similar manner to the pressure of the reaction gas and its residence time on the catalyst in the production step.
- the regeneration gas contains molecular oxygen and at least one inert Regeneriergas istteil selected from N2, CO, CO2, H2O and noble gases such as Ar.
- the oxygen-containing regeneration gas contains from 0.5 to 22% by volume, preferably from 1 to 20% by volume, and in particular from 1.5 to 18% by volume, of molecular oxygen.
- air is used as a constituent of the regeneration gas.
- the compound of the formula (I) is obtained by fractional condensation of the product gas.
- the temperature of the product gas is initially reduced by direct and / or indirect cooling and then passed into a condensation zone within which the product gas condenses in a fractionally increasing manner.
- the condensation zone is within a condensation column equipped with separable internals (e.g., mass transfer trays) and optionally with cooling circuits.
- the compound of formula (I) is obtained in the form of a first fraction which predominantly, preferably at least 90 wt .-%, particularly preferably at least 95 wt .-% from Compound of formula (I) exists.
- the fractional condensation in particular with regard to the number of theoretical plates, in such a way that in addition to the compound of the formula (I) in the form of the first fraction, the unreacted compound of the formula (II) is obtained in the form of a second fraction which consists predominantly, preferably at least 90 wt .-%, particularly preferably at least 95 wt .-% of the compound of formula (II).
- the compound of formula (I) is obtained by absorption into an absorbent and subsequent Rectification of the loaded absorbent from the product gas. This reduces the temperature of the product gas by direct and / or indirect cooling and brings it in an absorption zone with a normal pressure at higher than the compound of formula (I) boiling organic absorbent in contact. Suitable organic absorbents are, for example, those mentioned in DE-A 102009027401 and DE-A 10336386.
- compound of the formula (II) is generally absorbed into the absorbent.
- the absorption zone is within an absorption column, which is preferably equipped with separation-effective internals.
- the compound of the formula (I) is obtained by rectification from the loaded absorbent. In the rectification, by appropriate selection of the number of theoretical plates (theoretical plates), the compound of the formula (I) is obtained in the form of a first fraction which is predominantly, preferably at least 90% by weight, more preferably at least 95% by weight. % consists of the compound of formula (I).
- the fractional condensation in particular with regard to the number of theoretical plates, in such a way that in addition to the compound of the formula (I) in the form of the first fraction, the unreacted compound of the formula (II) is obtained in the form of a second fraction which predominantly, preferably at least 90 wt .-%, particularly preferably at least 95 wt .-% consists of the compound of the formula (II).
- the molar ratio of the compound of the formula (II) to formaldehyde in a preferred embodiment of the process according to the invention is greater than 1 and may be up to 10.
- the molar ratio of the compound of the formula (II) to formaldehyde in the reaction gas is preferably from 1.1 to 5 and more preferably from 1.5 to 3.5.
- Recycling is to be understood as meaning that at least part of the compound of the formula (II) present in the product gas is used as at least part of the compound of the formula (II) comprised by the reaction gas.
- the inventive method comprises the production of acetic acid by partial oxidation of ethanol, wherein reacting a gas mixture comprising ethanol and molecular oxygen in contact with at least one solid oxidation catalyst whose active composition preferably has a vanadium oxide to a product gas mixture.
- ethanol is heterogeneously catalysed with molecular oxygen to give acetic acid and water vapor.
- the conditions, in particular temperature and pressure, are adjusted so that ethanol, acetic acid and water are gaseous or predominantly gaseous.
- the product gas mixture can be used directly as part of the reaction gas according to the invention.
- the process according to the invention comprises the production of acetic acid by homogeneously catalyzed carbonylation of methanol, methanol and carbon monoxide being reacted in the liquid phase at a pressure of at least 30 bar (absolute).
- the reaction takes place in the presence of a catalyst which contains at least one of the elements Fe, Co, Ni, Ru, Rh, Pd, Cu, Os, Ir and Pt, an ionic halide and / or a covalent halide and optionally a ligand such as, for example PR 3 or NR 3 , wherein R 3 is an organic radical.
- the determination of the oxidation states of the catalysts was carried out by titrimetric dimensional analysis with potentiometric end point display (potentiograph with combined platinum electrode) under an inert gas atmosphere.
- aqueous H2SO4 100-200 mg of the catalyst to be investigated were dissolved in a mixture of 30 ml of aqueous H2SO4 and 10 ml of concentrated H3PO4 in boiling heat under inert gas.
- aqueous H2SO4 a mixture of equal volumes of water and concentrated H2SO4 was used.
- V 5+ content the freshly prepared solution of the catalyst was titrated with a 0.1 molar aqueous ammonium iron sulfate standard solution ((NH 4) 2 Fe (SO 4) 2).
- a 0.1 molar aqueous ammonium iron sulfate standard solution (NH 4) 2 Fe (SO 4) 2).
- a potential jump occurred (V 4+ to V 5+ ) if only V 4+ to V 5+ were present and two potential jumps occurred (V 3+ to V 4+ and V 4+ to V 5+ ) when in addition to V 4+ to V 5+ also V 3+ was present.
- 0.1 N 0.1 molar aqueous ammonium iron sulfate standard solution
- n (V 3+ ), n (V 4+ ) and n (V 5+ ) was calculated from the respective amounts of the custom solution added.
- the oxidation state is the molar fraction weighted oxidation state of the various vanadium ions.
- the reactor used (stainless steel No. 1.4541) had a tube length of 950 mm, an outer diameter of 20 mm and an inner diameter of 16 mm.
- Four copper shells (E-Cu F25, outer diameter 80 mm, inner diameter 16 mm, length 450 mm) were attached around the reactor.
- the half-shells were wrapped with a heating tape, which in turn was wrapped with insulating tape.
- the temperature measurement of the reactor heaters was carried out on the outside of the heating shell of the reactor.
- the temperature inside the reactor could be determined over the entire catalyst bed by means of a thermocouple located in a central sleeve (external diameter 3.17 mm, internal diameter 2.17 mm). At the bottom
- the catalyst chair consisted of a 5 cm long tube (outer diameter 14 cm, inner diameter 10 cm) over the upper opening of the wire mesh (1, 5 mm mesh size) was.
- 14 g of a bed of steatite balls having a diameter of 3-4 mm were applied to this catalyst chair (bed height 5 cm).
- On the repatriation was placed centrally the thermal sleeve.
- 105 g of catalyst in the form of chippings with a particle size of 2.0 to 3.0 mm were fed undiluted around the thermowell into the reaction tube (bed height 66 cm).
- Above the catalyst bed was 14 g of a bed of steatite balls with a diameter of 3-4 mm (bed height 5 cm).
- the reaction mixture was heated at reflux to about 100 to 108 ° C and left under these conditions for 14 h. Subsequently, it was drained into a nitrogen inertized and heated pressure suction filter and filtered off at a temperature of about 100 ° C at a pressure above the suction filter of up to 3.5 bar.
- the filter cake was dry-blown by flowing nitrogen continuously at 100 ° C and stirring with a centrally-located, height-adjustable stirrer for about one hour.
- the mixture was then heated to about 155 ° C and evacuated to a pressure of 150 mbar abs. The drying was continued to an isobutanol content of ⁇ 2% by weight in the dried catalyst precursor.
- the obtained dried powder was tempered for 2 hours under air in a rotary tube having a length of 6.5 m, an inner diameter of 0.9 m and internal helical coils.
- the speed of the rotary tube was 0.4 U / min.
- the powder was fed into the rotary kiln at a rate of 60 kg / h.
- the air supply was 100 m 3 / h.
- the temperatures of five equal heating zones, measured directly on the outside of the rotary kiln, were 250 ° C, 300 ° C, 340 ° C, 340 ° C and 340 ° C.
- the catalyst precursor was intimately mixed with 1 wt% graphite and compacted in a roller compactor.
- the fine material in the compact (particle size ⁇ 400 ⁇ m) was sieved off and fed back to the compaction.
- the coarse material with a particle size> 400 ⁇ m was intimately mixed with a further 2% by weight of graphite.
- the catalyst precursor powder thus obtained was compressed in a tableting machine into 5.5 ⁇ 3.2 ⁇ 3 mm hollow cylinders (outer diameter ⁇ height ⁇ diameter of the inner hole).
- the pressing forces were about 10 kN.
- each calcination zone The volume of gas circulating per unit time in each calcination zone was greater than the volume of the gas added or removed per unit time. Between two successive calcination zones, to reduce the gas exchange, there was a partition which was open in the region of the stream of the catalyst precursor. The length of each calcination zone was 1.45 m. The speed of the conveyor belt was adjusted according to the desired residence time of about 2 hours per calcining zone. The individual zones were operated as shown in the following table:
- the catalyst precursor a was filled in a circulating air oven (Elino). 4500 NL / h (standard liters per hour) of air were passed over the precursor while the temperature was raised from room temperature to 140 ° C (heating rate 2.5 ° C / min). This temperature was maintained for 168 minutes. Thereafter, the temperature was raised to 260 ° C (heating rate 5 ° C / min). This temperature was maintained for 84 minutes. Now 2500 NL / h of a N 2 / air mixture were run in a ratio of 1: 1 over the precursor while the temperature was raised to 325 ° C (heating rate 3.2 ° C / min). This temperature was maintained for 87 minutes.
- the hollow cylinders were crushed on a compactor (Powtec RCC 100x20).
- a compactor Pantec RCC 100x20
- the rollers on the compactor were removed and a 4 mm screen was installed.
- Rotor shaving head and screw rotated at 50 and 30 revolutions per minute respectively. Then the 2-3 mm fraction was isolated by sieving.
- Catalyst precursor a was charged to a convection oven (Elino). 4500 NL / h of air were passed over the precursor while the temperature was raised from room temperature to 140 ° C (heating rate 2.5 ° C / min). This temperature was maintained for 168 minutes. Thereafter, the temperature was raised to 380 ° C (heating rate 2.5 ° C / min). Now 1900 NL / h of a N2 / H2O mixture in the ratio 1: 1 were passed over the precursor while the temperature was raised to 425 ° C (heating rate 3.125 ° C / min). This temperature was maintained for 206 minutes. Finally, the oven was cooled to room temperature. The hollow cylinders were then split by hand in a porcelain mortar and the 2-3 mm fraction was isolated by sieving.
- the catalyst rings were split by hand in a porcelain mortar and by sieving the 2-3 mm fraction isolated.
- Catalyst 5 Catalyst 1 was placed in a convection oven (Elino). 4500 NL / h of air were passed over the precursor while the temperature was raised from room temperature to 550 ° C (heating rate 2.5 ° C / min). This temperature was held for 96 hours. Finally, the oven was cooled to room temperature. Subsequently, the hollow cylinders were split by hand in a porcelain mortar and by sieving the 2-3 mm fraction isolated.
- Catalyst 6 (refining Example 2 of U.S. Patent 4,132,670):
- an apparatus consisting of a 2.5 l glass precipitator with impeller stirrer, a baffle, a thermostat from Haake (model B5), intensive reflux condenser, water separator and Doppelcrobe- atmer used.
- a vertically mounted fixed bed reactor with an inside diameter of about 20 mm was loaded with the catalyst pellets and calcined in the first step for 6 hours at 300 ° C under air (GHSV of about 2.0 vol / vol / min).
- the second calcining step was also carried out under air at a temperature of 450 ° C for 12 hours. (GHSV of about 1, 0 vol / vol / min)
- the calcined pellets had a vanadium oxidation state of 4.23.
- a vertically mounted fixed bed reactor with an inner diameter of about 20 mm was loaded with the catalyst pellets and in the first step for 2 hours at 380 ° C. calcined under air (GHSV of about 2.0 vol / vol / min).
- the second calcining step was also carried out under air at a temperature of 450 ° C for 12 hours. (GHSV of about 1, 0 vol / vol / min)
- the calcined pellets had a vanadium oxidation state of 4.21.
- the catalysts 1-5 were tested in the pilot plant in the presence of a reaction gas with 2% by volume of O 2 (Examples 1-5). BET surface area and oxidation state of the vanadium of each charged catalyst, and conversion of formaldehyde and selectivity of the conversion to acrylic acid at the beginning (0 h) and after a running time of 30 h are listed in the following table.
- Example 5 was repeated except that no air was metered into the reaction gas (Example 6). The following results were obtained:
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US201361822948P | 2013-05-14 | 2013-05-14 | |
DE201310008206 DE102013008206A1 (en) | 2013-05-14 | 2013-05-14 | Process for the preparation of vinylidene-carboxylic acid (ester) s by reaction of formaldehyde with alkylcarboxylic acid (esters) n |
PCT/EP2014/059520 WO2014184098A1 (en) | 2013-05-14 | 2014-05-09 | Method for producing vinylidene carboxylic acid (esters) by reacting formaldehyde with alkyl carboxylic acid (esters) |
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EP2997005A1 true EP2997005A1 (en) | 2016-03-23 |
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EP14724697.9A Withdrawn EP2997005A1 (en) | 2013-05-14 | 2014-05-09 | Method for producing vinylidene carboxylic acid (esters) by reacting formaldehyde with alkyl carboxylic acid (esters) |
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Country | Link |
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US (1) | US9434673B2 (en) |
EP (1) | EP2997005A1 (en) |
JP (1) | JP2016522825A (en) |
KR (1) | KR20160007622A (en) |
CN (1) | CN105377800A (en) |
BR (1) | BR112015028463A2 (en) |
DE (1) | DE102013008206A1 (en) |
RU (1) | RU2015153252A (en) |
WO (1) | WO2014184098A1 (en) |
Cited By (1)
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CN114605250A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | V-based high-entropy phosphate and method for synthesizing acrylic acid and acrylic ester |
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WO2016156042A1 (en) | 2015-03-27 | 2016-10-06 | Basf Se | Shaped catalyst body for the catalytic oxidation of so2 into so3 |
DE102015222196A1 (en) | 2015-11-11 | 2016-05-19 | Basf Se | Process for the production of acrylic acid |
GB201616119D0 (en) | 2016-09-22 | 2016-11-09 | Johnson Matthey Davy Technologies Limited | Process |
GB201621985D0 (en) | 2016-12-22 | 2017-02-08 | Johnson Matthey Davy Technologies Ltd | Process |
GB201621975D0 (en) | 2016-12-22 | 2017-02-08 | Johnson Matthey Davy Technologies Ltd | Process |
CN107999070B (en) * | 2017-11-29 | 2020-09-08 | 万华化学集团股份有限公司 | Coated catalyst and preparation method and application thereof |
KR20220138677A (en) | 2021-04-06 | 2022-10-13 | 주식회사 디엔솔루션즈 | Ball-screw support device for machine tool |
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DE4442346A1 (en) | 1994-11-29 | 1996-05-30 | Basf Ag | Process for producing a catalyst consisting of a support body and a catalytically active oxide mass applied to the surface of the support body |
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DE10309286A1 (en) | 2003-03-04 | 2004-09-16 | Basf Ag | Process for the thermal stabilization of highly concentrated formaldehyde solutions |
DE10309288A1 (en) | 2003-03-04 | 2004-09-16 | Basf Ag | Process for providing highly concentrated gaseous formaldehyde |
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DE102004006649A1 (en) | 2004-02-11 | 2005-09-01 | Basf Ag | Process for the preparation of a highly concentrated formaldehyde solution |
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- 2014-05-09 KR KR1020157035189A patent/KR20160007622A/en not_active Application Discontinuation
- 2014-05-09 CN CN201480039609.8A patent/CN105377800A/en active Pending
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- 2014-05-09 RU RU2015153252A patent/RU2015153252A/en not_active Application Discontinuation
- 2014-05-09 BR BR112015028463A patent/BR112015028463A2/en not_active IP Right Cessation
- 2014-05-09 WO PCT/EP2014/059520 patent/WO2014184098A1/en active Application Filing
- 2014-05-09 EP EP14724697.9A patent/EP2997005A1/en not_active Withdrawn
- 2014-05-14 US US14/277,384 patent/US9434673B2/en not_active Expired - Fee Related
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CN114605250A (en) * | 2020-12-09 | 2022-06-10 | 中国科学院大连化学物理研究所 | V-based high-entropy phosphate and method for synthesizing acrylic acid and acrylic ester |
CN114605250B (en) * | 2020-12-09 | 2023-02-28 | 中国科学院大连化学物理研究所 | V-based high-entropy phosphate and method for synthesizing acrylic acid and acrylic ester |
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CN105377800A (en) | 2016-03-02 |
US9434673B2 (en) | 2016-09-06 |
US20140343318A1 (en) | 2014-11-20 |
JP2016522825A (en) | 2016-08-04 |
DE102013008206A1 (en) | 2014-11-20 |
WO2014184098A1 (en) | 2014-11-20 |
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BR112015028463A2 (en) | 2017-07-25 |
RU2015153252A (en) | 2017-06-20 |
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