AU677900B2 - Hydrogenation of unsaturated fats, fatty acids or fatty acid esters - Google Patents
Hydrogenation of unsaturated fats, fatty acids or fatty acid esters Download PDFInfo
- Publication number
- AU677900B2 AU677900B2 AU18082/95A AU1808295A AU677900B2 AU 677900 B2 AU677900 B2 AU 677900B2 AU 18082/95 A AU18082/95 A AU 18082/95A AU 1808295 A AU1808295 A AU 1808295A AU 677900 B2 AU677900 B2 AU 677900B2
- Authority
- AU
- Australia
- Prior art keywords
- catalyst
- fatty acids
- fats
- solvent
- hydrogenation
- 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.)
- Expired - Fee Related
Links
- 239000000194 fatty acid Substances 0.000 title claims description 59
- 229930195729 fatty acid Natural products 0.000 title claims description 59
- 150000004665 fatty acids Chemical class 0.000 title claims description 41
- -1 fatty acid esters Chemical class 0.000 title claims description 32
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 27
- 235000021122 unsaturated fatty acids Nutrition 0.000 title description 12
- 235000021081 unsaturated fats Nutrition 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims description 102
- 238000000034 method Methods 0.000 claims description 59
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 42
- 239000003925 fat Substances 0.000 claims description 35
- 235000019197 fats Nutrition 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 4
- 229960001730 nitrous oxide Drugs 0.000 claims description 4
- 235000013842 nitrous oxide Nutrition 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 56
- 230000000694 effects Effects 0.000 description 34
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 19
- 229910052740 iodine Inorganic materials 0.000 description 19
- 239000011630 iodine Substances 0.000 description 19
- 230000007423 decrease Effects 0.000 description 17
- 229910052763 palladium Inorganic materials 0.000 description 15
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002609 medium Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000006317 isomerization reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000019486 Sunflower oil Nutrition 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002600 sunflower oil Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000002888 oleic acid derivatives Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- HKVGLVBQYVEJRZ-UHFFFAOYSA-N CC=C.O=C=O Chemical compound CC=C.O=C=O HKVGLVBQYVEJRZ-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005428 food component Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 238000012423 maintenance Methods 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
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000021085 polyunsaturated fats Nutrition 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229960004529 xenon Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
-
- 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
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
-
- 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
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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Description
1. 1 WO 95/22591 PCT/EP95/00456 1 Hardening of unsaturated fats, fatty acids or fatty acid esters Description The present invention relates to a method for the continuous hardening of unsaturated fats, fatty acids or fatty acid esters on a shaped catalyst in the fixed bed.
Renewable fats or oils of animal or vegetable origin come under the triglycerides. They form an essential ingredient of human food. Free fatty acids can be obtained by splitting of the triglycerides into fatty acids and glycerol. The fatty acids from vegetable or animal sources have chain lengths of 12 to 30 carbon atoms. Unsaturated fatty acids with up to three double bonds are mostly involved. The double bonds, in particular in triply unsaturated fatty acids, are the reason for the low thermal stability and easy oxidation of the unsaturated fatty acids.
Polyunsaturated fats are particularly important for human food, however it is frequently necessary, in order to improve the shelf life and to improve the handling properties of these fats, to hydrogenate the double bonds of the polyunsaturated fatty acids selectively down to one double bond. This is then termed "selective hardening" Natural fats exist almost completely in the cis-isomeric form. Trans-isomeric fats are of less value physiologically. They are sukpected, together with the through-hardened fats, of increasing the triglyceride or cholesterol level in human blood. The aim of the selective hardening of fats is therefore to suppress the formation of trans-isomers as well as the formation of completely through-hardened fats.
S WO 95/22591 PCT/EP95/00456 2 For applications in industry the double bonds must be removed as completely as possible by hydrogenation, with simultaneous maintenance of the acid character of the fatty acids. This complete hydrogenation of the double bonds of fatty acids is also referred to as through-hardening of the fatty acids.
The degree of saturation of fats and fatty acids, i.e.
their content in still remaining double bonds, can be determined by the iodine value Tgl-64 (Wijs method) of the A.O.C.S. Natural fats possess, depending on the degree of saturation, iodine values between 150 (soybean oil) and (beef fat) Fats and fatty acids are still hydrogenated mainly batchwise at temperatures of 100 3000 C under an increased hydrogen pressure of 1 35 bar in the presence of a suitable catalyst. Use is mainly made for this purpose of nickel catalysts in the form of finely-divided nickel either directly or on silicon oxide as a support. In addition to these nickel catalysts, however, supported noble metal catalysts are also known for the selective or complete hardening of fats, fatty acids and fatty acid esters. Supported noble metal catalysts are suitable in particular for the continuous hardening of fats and fatty acids in trickle bed reactors.
Thus e.g. DE 41 09 502 describes the continuous hardening of untreated fatty acids in the trickle bed on a palladium/ titanium oxide catalyst. The reaction media are here reacted in the form of a 2-phase mixture of liquid fatty acids and hydrogen gas on the fixed bed catalyst. The hydrogenating activity in this method permits space velocities of only 1.2 h 1 and should be improved in the interests of higher economic returns. It has been found in addition that the selective hardening in the trickle bed tends towards the formation of trans-isomers.
1; WO 95/22591 PCT/EP95/00456 3 The object of the present invention is therefore to indicate a method for the continuous hardening of fats, fatty acids or fatty acid esters which exhibits a substantially improved hydrogenating activity. The method is intended to be suitable both for the selective hardening of edible fats and oils with low trans-isomer formation and for the complete hardening of fats and free fatty acids for industrial applications.
The object is achieved by a method for the continuous hardening of unsaturated fats, fatty acids or fatty acid esters on a shaped catalyst in the fixed bed, which is characterised in that the fats, fatty acids or fatty acid esters are together with the hydrogen required for the hardening and in the presence of a supercritical medium or solvent conveyed over a catalyst and in so doing converted and that the fats, fatty acids or fatty acid esters are then separated from the supercritical medium or solvent by expansion and are therefore present as pure substance without solvent.
Supercritical solvents or media are used in many areas of industrial chemistry and also of food chemistry. The main area of use of supercritical media in food chemistry is the extraction of particular food components frcm natural raw material sources. Use is preferably made for the latter of supercritical carbon dioxide, which is distinguished by high purity, good environmental compatibility and relatively low costs. The hardening of fats, fatty acids or fatty acid esters in supercritical media has not become known yet to date.
The method according to the invention leads to surprisingly high hydrogenating activities of the catalysts used. It has been found that the hydrogenating activities of similar types of catalysts, when used in the method according to the invention, can be greater by a factor of 10 to 50 than I WO 95/22591 PCT/EP95/00456 4 when used in the conventional trickle bed hardening. In addition the method according to the invention exhibits a lower cis/trans-isomerisation.
The method works particularly advantageously with reaction temperatures between the critical temperature Tcr of the solvent and ten times the value, preferably between Tcr and 7 Tcr and at pressures between 0.8 times the pressure Pcr of the solvent at the critical point and 6 Pcr, preferably between Pcr and 4 Pcr Suitable solvents for the method according to the invention are acetone, ammonia, butane, carbon dioxide, chloroform, chlorotrifluoromethane, dichlorodifluoromethane, dichlorofluoromethane, 1,2-dichlorotetrafluoroethane, ethane, ethyl methyl ether, methane, nitrogen monoxide, dinitrogen monoxide, n-pentane, propane, sulphur hexafluoride, trichlorofluoromethane and xenon. By means of binary or ternary mixtures of these solvents the solvent properties can be adjusted to the substance to be dissolved. A further raising of the solvent power and the selectivity of the solvent properties of supercritical solvents can be achieved by the addition of small amounts (up to approx. 2 vol. of so-called modifiers. There are suitable as modifiers alcohols (methanol, ethanol), aldehydes, ketones, acids, hydrocarbons as well as fluorinated/chlorinated hydrocarbon and water.
Particularly suitable are solvents or solvent mixtures whose critical temperature lies in the range between -1200 C and 2500 C at critical pressures between 20 and 200 bar and which exhibit a density at the critical point of more than 0.1 g/cm 3 Preferentially suitable are carbon dioxide, nitrogen monoxide, dinitrogen monoxide, propane and pentane with densities at the critical point of between 0.2 and
I
'I WO 95/22591 PCT/EP95/00456 g/cm 3 They exhibit a good solvent power for organic materials. Under the reaction conditions of the method the densities of the supercritical solvent increase significantly with rising pressure in the reactor. Their solvent power thereby undergoes a further improvement. In the case of carbon dioxide, for example, the density doubles from some 0.5 g/cm 3 to some 1 g/cm 3 if the pressure is raised from Pcr to 5 Pcr (at the critical temperature in each case) The critical temperatures lie between -940 C for nitrogen monoxide and 196.50 C for pentane and thus permit a particularly gentle handling of organic materials.
Preferably used are carbon dioxide with a critical temperature of 310 C, a critical pressure of 72.8 bar and a critical density of 0.467 g/cm 3 and dinitrogen monoxide with a critical temperature of 36.40 C, a critical pressure of 71.5 bar and a critical density of 0.452 g/cm 3 The solvent properties of carbon dioxide can be enhanced by mixing wi.th propane mixture of 75 parts by volume of carbon dioxide and 25 parts by volume of propane) Use can be made for the method according to the invention of all known hydrogenating catalysts, i.e. also e.g.
nickel, platinum, palladium, rhodium, ruthenium catalysts or combinations thereof on SiO 2 A120 3 TiO 2 ZrO 2 MgO, activated carbon or on mixtures thereof such as e.g.
MgO x A1 2 0 3 The platinum group metals on shaped supports have proved particularly effective. The catalytic activity can be influenced by promoters. Thus it is known e.g. that silver as a promoter for nickel and palladium catalysts reduces the formation of trans-isomers. Sulphidized nickel catalysts in particular are used in engineering.
The supports should have a high specific surface in order to permit good dispersion of the catalyst metals.
Advantageous are specific surfaces between 10 and I I WO 95/22591 PCT/EP95/00456 6 1000 m 2 Particularly important for the method according to the invention is also the pore structure of the supports. They should have a total pore volume between 0.05 and 6.5 ml/g, which is composed predominantly of meso- and macropores. Micropores are undesirable and should make up only a small percentage of the total pore volume.
The terms micro-, meso and macropores are used here f i conformity with the definitions of the IUPAC. According to these definitions the pore groups incorporate the following diameter ranges: Micropores: d 2 nm Mesopores: d 2 50 nm Macropores: d 50 nm Meso- and macropores guarantee through their large pore diameters optimal accessibility to the catalytically active noble metal crystals deposited on their surfaces for the fat, fatty acid or fatty acid ester molecules. This accessibility is supported by the fact that the supercritical solvents used have a low viscosity.
The content in platinum group metals on the support should come to between 0.05 and 5 wt preferably between 0.1 and wt The platinum group metals must be deposited finely distributed on the support, in order to provide as great a metal surface as possible for the catalytic process. A measure of the size of the catalytically active metal surface is the adsorption of carbon monoxide. The latter should be, as a function of the content in platinum metal groups, between 0.05 and 5.0 ml CO/g of the finished catalyst elements. If it is assumed that one noble metal atom adsorbs one CO molecule and the latter behaves like an ideal gas with an assumed projected area of WO 95/22591 PCT/EP95/00456 7 6.25 x 10-20 m 2 /molecule, there can be calculated from the above-mentioned values an active surface of the platinum group metals on the finished catalyst of approx. 0.1 m 2 /g.
The catalyst supports can be of any shape. There are suitable in particular all shapes known for fixed bed catalysts, namely spheres, cylinders, hollow cylinders and open wheels as well as monolithic catalyst supports in the form of honeycomb elements with parallel flow channels or foam ceramics with an open pore system. The monolithic honeycomb ele ients can consist throughout of the highsurface support material (solid catalyst) or be composed of an inert support element with a coating of the high-surface support material (coating catalyst).
It is a particular advantage of the method according to the invention that compared with conventional methods smallsized catalyst supports can be used as support material, without the pressure loss through the catalyst bed becoming too great. This is made possible by the low viscosity of the supercritical solvent. With advantage, therefore, catalyst supports can be used with outer dimensions in the range between 0.1 and 3.0 mm, in particular between 0.2 and 1.0 mm. Very high catalyst activities can be achieved in this way. Spherical-shaped supports are preferred.
Because of the small dimensions of the catalysts, the latter exhibit in the bed a very high geometric surface relative to the total volume of the bed. This benefits the catalytic activity of the catalyst bed. This activity can be further improved if the platinum group metals are depoiited on these supports in an outer shell of 40 pm. The shell impregnation is of importance particularly for the selective fat hardening. Specifically, it prevents fat molecules which are diffused into the interior of the catalyst support from making protracted O 9)5/22591 PCT/EP95/00456 8 contact there with catalytically active metals and hence being fully through-hardened. For the complete hardening of fats or fatty acids use can conversely also be made of fully through-impregnated catalyst supports.
Various materials are suitable as catalyst supports. The materials must however satisfy the above-mentioned requirements as regards their physical properties and be resistant to the reaction media, in particular to the fatty acids. For the conventional fat hardening, activated carbon, silicon dioxide, aluminium oxide, mixed aluminium/ silicon oxides, barium sulphate, titanium oxide, glass beads coated with titanium oxide and ion-exchange resins have proved satisfactory. These support materials can also be used in the method according to the invention. The above-mentioned requirements are however met in an optimal manner by organosiloxane amine copolycondensates or by polymeric, secondary and/or tertiary organosiloxane amine compounds or by organosiloxane polycondensates. These support materials are described in the German patent specifications DE 38 00 563 CI, DE 38 00 564 C1, DE 39 25 359 C1 and DE 39 25 360 C1 and in the as yet unpublished patent application P 42 25 978.1. Platinum group metal-containing catalysts on these supports are disclosed in the patent specifications DE 41 10 705 C1 and DE 41 10 706 C1.
The following examples make clear the mode of operation of the method according to the invention for the hydrogenation of fats, fatty acids or fatty acid esters.
Figure 1 shows a diagrammatic view of the hydrogenation apparatus used for the examples. designates the hydrogenation reactor. An 840 mm long stainless steel tube with an inner bore of 15.7 mm is involved. This stainless steel tube is filled to about half its height with a catalyst layer from 10 to 30 mm in height. Above and WO 95/22591 PCT/EP95/00456 9 below the catalyst bed are located plugs of quartz wool.
They separate the actual catalyst bed from glass beads which occupy the remaining free volume of the stainless steel tube above and below the catalyst bed. The inert bed above the catalyst bed serves at the same time for mixing the supercritical medium or solvent with the reactants.
The reactor possesses an outer jacket through which, for the setting of the reaction temperature, silicone oil flows in countercurrent as a heating medium. This arrangement guarantees that the temperature gradient through the catalyst bed is very small.
The media required for the method are fed to the reactor from above. Nitrogen is used simply for the cleaning of the reactor before and after a hydrogenation. There are also charged to the supercritical mixture of hydrogen, carbon dioxide and optionally propane above the reactor any modifier required and the educt to be hydrogenated.
In contrast to the conventional trickle bed method, the vertical arrangement of the reactor tube selected here is not mandatory. In one possible embodiment of the method there exists with adequate dilution of the reactants in the supercritical medium or solvent a virtually homogeneous phase, which may be pumped over the catalyst bed at any orientation of the reactor tube. The vertical arrangement was selected here merely to simplify the description.
After passage through the reactor the reaction media enter a separator In this separator the reaction mixture of product, optionally surplus hydrogen and supercritical solvent is converted into a two-phase mixture by expansion to pressures below the critical pressure. During the expansion the solvent and the hydrogen pass into the gaseous state, whereby the solvent power of the solvent is reduced to practically zero. The product of the WO 95/22591 PCT/EP95/00456 hydrogenation reaction therefore precipitates out of the reaction mixture as a liquid or solid and can therefore be separated from the gaseous solvent and the remaining hydrogen. The now gaseous solvent and the remaining hydrogen can either be released to the atmosphere or be compressed again and recycled into the process. The expansion of the reaction medium after passage through the reactor can also be carried out in a plurality of stages with pressure reduction. The reaction products can consequently be precipitated in a plurality of fractions, depending on solubility in the supercritical medium.
An optionally necessary substance separation, e.g. by distillation, can therefore be dispensed with.
The hydrogenation apparatus of Figure 1 was used in the following examples for the continuous hydrogenation of ethyl esters of various fatty esters, whose main constituent was linoleic acid ethyl ester. The educt had the following detailed composition: Table 1: Composition of the educt Linoleic acid ethyl ester C18:2: 76.8 wt Oleic acid ethyl ester cis-form C18:l(c): 13.2 wt trans-form C18:l(t): 0 wt Stearic acid ethyl ester C18:O: 2.7 wt Palmitic acid ethyl ester C16:0: 7.3 wt Pure carbon dioxide or a carbon dioxide-propene gas mixture was used as the supercritical solvent.
I I ,I WO 95/22591 PCT/EP95/00456 11 Linoleic acid ethyl ester is an ester of the doubly unsaturated linoleic acid with 18 carbon atoms.
The double bonds of this fatty acid are hydrogenated in a consecutive reaction, i.e. after one another. There are therefore contained in the reaction product, in addition to residues of the linoleic acid C18:2, the monounsaturated oleic acid C18:1 and the completely saturated stearic acid C18:O. The monounsaturated oleic acid can be present in two isomeric forms, namely as cis-form C18:l(c) and as transform C18:l(t). Oleic acid from natural sources exhibits predominantly the cis-form. During the hydrogenation the oleic acid is partially isomerised to the trans-form.
For the analysis of the reaction product the liquid was removed hourly from the separator and a sample of the latter examined in a gas chromatograph and the reaction products formed were identified and determined quantitatively. From these measurements it was possible to determine the selectivity of the formation of oleic acid compared with stearic acid and the degree of the cis/transisomerisation.
As a measure of the integral activity A of the catalysts in the method according to the invention there were calculated from the iodine value of the samples a) the iodine value decrease, standardized to one hour, b) the specific iodine value decrease, standardized to one hour and 1 g of active metal, and c) the specific hydrogenating activity in number of moles of hydrogen which were converted per gram of active metal am per hour. The iodine value (IV) is a measure of the number of double bonds not yet saturated in the product and is given in grams of iodine which are adsorbed by 100 g of the samples. It is determined according to the official method Tgl-64 (Wijs method) of the A.O.C.S. From the iodine value IVeduct of the educt and I 1.
WO 95/22591 PCT/EP95/00456 12 the iodine number IVproduct of the product the specific hydrogenating activity A is calculated as: (IVeduct IVproduct) x 2 mol 2 1
A
100 x g am x Miodine L g am x h J flow rate of the educt in [g/h] g am gram of active metal [g] Miodine molecular weight of iodine in [g mol] The specific cis/trans-isomerisation B is given dimensionless as per cent of trans-isomer in the product formed according to GC analysis in relation to the iodine value decrease.
trans-isomer B IVeduct IVproduct Four different catalyst systems were used, which are given with their properties in Table 2. In the case of the Pd/C catalyst a shell catalyst (20 Am shell) on a mesoporous spherical carbon is involved. Pd/OFP denotes a palladium catalyst on a support of an organofunctional polysiloxane according to Example 2 of patent specification DE 41 10 706 C1.
There was used as a base metal catalyst the commercial catalyst RCH Ni 55/5 TST of Hoechst. This is a supported catalyst with a content of some 54 wt of nickel on kieselguhr containing 4 wt of manganese.
In Table 2 the catalyst systems investigated are characterised by details of the shape and size of the support material and by details of its pore structure. As I lie 1, WO 95/22591 PCT/EP95/00456 13 regards the nickel catalyst, the table contains only the parameters contained in the data sheets.
The pore volumes given in Table 2 were determined in the case of micro- and mesopores by the evaluation of nitrogen adsorption isotherms to DIN 66133. The pore volume of the macropores was determined by Hg porosimetry, likewise to DIN 66133.
Table 2 also contains data on the nature of the distribution of the platinum group metals through the cross-section of the catalyst supports and on the fineparticle character of the platinum group metals measured by their carbon monoxide adsorption.
Table 2 Properties of the catalysts: Catalyst Support Shape Size [mm] Pores [ml/g] Micro Meso Macro total Pd/C C Spheres 0.4 0.8 0.19 0.42 0.14 0.75 Pd/OFP OFP Spheres 0.3 0.8 1.54 0.72 2.26 Pt/OFP OFP Spheres 0.4 0.8 1.48 0.68 2.16 Ni/SiO 2 SiO 2 Granulate 0.45 1.0 Catalyst Catalytic metal Metal Metal content CO absorption distribution [ml CO/g cat.] Pd/C Pd/OFP Pt/OFP Ni/Si, 20 pm shell 20 pm shell throughimpregnated homogeneous 0.39 0.65 0.22 Example 1 The educt consisting of ethyl esters of various fatty acids which is characterised in Table 1 was hydrogenated according to the invention in the presence of a supercritical medium with the use of the catalysts of Table 2 in the reaction conditions given in Table 3. The space I 1, WO 95/22591 PCT/EP95/00456 14 velocity given in Table 3 (LHSV liquid hourly space velocity) is the liquid volume of the reaction educt which is metered hourly per catalyst volume.
The results regarding specific hydrogenation activity A, iodine value decrease per hour and the specific cis/transisomerisation are listed in Table 3. Table 3 also contains a comparison with trickle bed hardenings from various literature sources.
As Table 3 shows, there can be achieved in the presence of a supercritical medium or solvent in the hardening of fats and oils, fatty acids or fatty acid esters with suitable catalysts far better activities and also lower cis/transisomerisations than in the known continuous trickle bed hardening. Catalyst 2 (Pd/OFP) exhibits, with significantly reduced formation of trans-isomers, 65 times and 292 times better metal-specific hydrogenating activities in comparison with commercial Pd/C (cat. 5) and Ni/SiO 2 (cat.
6) catalysts respectively. As regards the metal-specific iodine value decrease, the factors are 149 and 837 respectively. Compared with the Pd/polystyrene catalyst (cat. 4) also, activities higher by orders of magnitude are again found in the method according to the invention, but also significantly smaller cis/trans-isomerisations. The Pd/C (cat. 1) and Pt/OFP (cat. 3) catalysts likewise exhibit in the method according to the invention very good activities and selectivities, better than comparable catalysts in the trickle bed hardening (cat. 4 These results were moreover also obtained at 600 C, while most of the other tests cited were carried out at far higher temperature.
It is known from the literature that platinum is not very suitable as an active component in the hydrogenation of fats, fatty acids and fatty acid esters. It can be seen from Table 3, however, that the Pt/OFP catalyst exhibits 9. WO 95/22591 PCT/EP95/00456 perfectly good hydrogenating activities in the presence of a supercritical medium or solvent and is distinguished in particular by a small formation of trans-isomers.
Palladium catalysts are conversely known in the trickle bed hardening for the formation of trans-isomers (see catalysts 4 and 5 in Table In the hydrogenation method according to the invention the formation of trans-isomers is however sharply reduced by the palladium catalysts.
The commercial nickel catalyst (catalyst 10) was used both in the hydrogenation method according to the invention and in the conventional trickle bed method. In the conventional trickle bed method working parameters of 1700 C, a hydrogen pressure of 20 bar and a space velocity of 5 h were selected. In the method according to the invention the temperature was able to be reduced to 1200 C. Despite this, a 25 to 30% higher hydrogenating activity was observed with significantly reduced cis/trans-isomerisation.
The data in Table 3 demonstrate the advantage of the hydrogenation according to the invention in the presence of supercritical media or solvents. The catalysts on OFP supports with their optimal pore structure lead moreover to particularly good results.
Whereas catalysts 1, 2 and 3 are despite their small particle diameter well suited to industrial applications of the hydrogenation method according to the invention, this is not the case with catalysts 4, 5 and 6 in the conventional trickle bed hardening. Their particle diameters are too small for this method and lead to a high pressure loss in the trickle bed. Typical particle sizes for the application in the trickle bed therefore amount to 1 to 5 mm and result in a further decline in the specific hydrogenating activity compared with the values of catalysts 4, 5 and 6 in Table 3.
-Y -I= WO 95/22591 PCT/EP95/00456 16 The hydrogenation method according to the invention operates conversely with a reaction mixture consisting of supercritical medium or solvent, hydrogen and the fats, fatty acids or fatty acid esters to be hydrogenated, which possesses by virtue of the supercritical conditions for the solvent a low viscosity and therefore also does not lead to a disproportionately large pressure loss in the catalyst bed with small particle diameters in the range between 0.1 and 1 mm.
I
Table 3: Comparison of various catalyst systems in bed hardening the supercritical and trickle Cat. Catalyst Hydrogenating IV specific cis/trans- Reaction parameters Source no. designation/particle size activity A decrease IV isomerisation B Idecrease t/hxg am] 1 0.59; pd/C 3.2 27J 461f;4 0.23 60' C, 100 bar CO 2 0.3 0.8 mms superstoichiometric H 2 2 1V Pd/OFP 14.3 1151 209273 0.11 LHSV 10 h- 1 according 0.4 0.8 mm to invention 3 2% Pt/OFP 1.5 230 20909 0.08 Linoleic acid ethyl 0.4 0.8 mm ester 54% Ni/~iO 2 0.04 512 560 0.12 120' C, 100 bar CO 2 according 0.45-1.0Owe LHSV 5 h- 1 to superstoichiometric H 2 invention linoleic acid ethyl 0.03 429 470 0.25 1700 C, 20 bar H 2 t-rickle LHSV 5 h- 1 bed linoleic acid ethyl hardening 4 4% Pd/ polystyrene 0.53 2'70 3375 0.3 1000 C, 3.45 bar H 2
JAOCS,
LHSV 6 hi 1 0.3 0.8 mm soybean oil Vol. 66 1% Pd/C 0.22 28 1400 1.5 1000 C, 3.45 bar H.,No7 0.18 0.42 mm LHSV 14 h- 1 soybean oil July 1989 6 50t Ni/SiO 2 C .049 250 250 0.4 1500 C 3.45 bar H 2 0.03 mm LHSV 10 h- 1 oil 7 2% Pd/TiO, 0.12 57.8 2890 1700 C, 20 bar H 2 1 DE 4109502 LHSV 1.07, a 2% Pd/C 0.23 57.2 5720 -dist. fatty acid Degussa AG 9 0.5% Pd/ 'U 2 0 3 0.10 48 9600 Go60 C, 21.1 bar H 2
DOS
LHSV 1 h- 1 Fatty acid (oleic acid) 231098S WO 95/22591 PCT/EP95/00456 18 Example 2 Using the Pd/OFP catalyst no. 2 of Table 3, a direct comparison was made between the conventional trickle bed hardening and the hardening according to the invention in the presence of a supercritical medium or solvent.
Both tests were carried out under exactly identical reaction conditions in the hydrogenation apparatus described. In order to simulate the conventional trickle bed hardening, the supercritical solvent CO 2 was replaced by nitrogen. The space velocity (LHSV) in the tests was h in each case. The results are given in Table 4.
The Pd/OFP catalyst also produces very good activities in the conventional trickle bed hardening under increased nitrogen pressure and exhibits a moderate tendency to the formation of trans-isomers. This is due to the good diffusion properties of the OFP support with its pore structure consisting only of meso- and macropores.
However, in the hydrogenation method according to the invention, in the presence of a supercritical medium or solvent, quite significantly better performance data are achieved with the same catalyst.
Table 4: Comparison of the hardening method according to the invention under supercritical conditions with the conventional trickle bed hardening Cat, no. Catalyst Hydrogenating IV decrease specific IV cis/trans- JReaction parameters Method designation! activity A decrease isonerisation B particle size [1/hxg am] 2 Pd/OFP 22.8 1821 331091 0.078 I600 C, 100 bar CO. according to stoichiometric H 2 the invention LHSV 15 h- 1 linoleic acid ethyl ester 2 11 Pd/OFP 9.2 730.5 132818 0.226 see above but N 2 conventional instead of CO 2 trickle bed hardening j am =active metal WO 95/22591 PCT/EP9S/00456 Example 3 In a third test series the dependence of the hydrogenating activity and the cis/trans-isomerisation on the space velocity was determined. Table 5 contains the results for the space velocities (LHSV) 5, 10, 15, 30 and 60 h Conventional trickle bed hardenings are diffusion-limited, i.e. the hydrogenation ability is limited by the diffusion velocity of the reactants towards the catalytically active centres and away from them. A raising of the space velocity therefore does not lead to a stronger catalytic reaction.
The results of Table 5 show conversely that the hydrogenation method according to the invention is still controlled kinetically even at space velocities of 60 h i.e. the catalytic reaction is not limited by diffusion processes in the catalyst, but simply depends on the velocity at which the reaction mixture is fed to the catalyst bed.
The catalyst activity therefore increases linearly with rising space velocity. Parallel with this a reduced formation of trans-isomers is observed.
Above a space velocity of 15 h 1 the catalyst activity no longer increases linearly but still increases significantly. At the same time slightly more trans-isomers are formed.
II-
Table 5: Dependence during the of the activity and cis/trans-isomerisation on the space velocity super 2,ritical hydrogenation with Pd/OFP Cat. Catalyst LHSV Hydrogenating IV specific IV cis/trans- Reaction parameters no. designation/particle [h-11 activity A decrease decrease isomerisation B size [1/bxg am] 2 it Pd/OFP S 6.7 526 95636 0.161 600 C, 1.00 bar CO. 0.4 0.8 mm superstoichiometric
H,
linoleic acid ethyl 2 1%r Pd/OFP 10 14.3 1151 209273 0.105 600 C, 100 bar CO 2 0.4 0.8 mm superstoichiometric I H2 linoleic acid ethyl 2 1% Pd/OFP 15 22.0 1821 331091 0.078 600 C, 100 bar CO 2 0.4 -0.8 mm superstoichiometric
H
2 linoleic acid ethyl 2 30 35.0 2581 5665C0 0.199 2 1 60 f 5 2.
3 3862 847650 .8 1 WO~ 95/22591 ]?CT/EP95/00456 22 Example 4 In a method comparison between the method according to the invention and the traditional trickle bed hardening, catalyst 2 was used for the selective hardening of sunflower oil. The sunflower oil used had the following composition:
C
1 8: 3 1 wt
C
1 8 64.8 wt
C
18 1 21.0 wt Balance: saturated fatty acids with differing chain length There was used as supercritical solvent a gas mixture of 75 vol. carbon dioxide and 25 vol. propane. The results of this test series are given in Table 6.
The superiority of the method according to the invention is also found in the selective hardening of triglycerides (here: sunflower oil), in terms both of the activity and of the selectivity. The increase in the hydrogenating activity with the space velocity (LHSV) points to the fact that the reaction is not limited by the mass transport. Simi3ar hydrogenating capacities can be achieved as in the selective hardening of linoleic acid ethyl esters (see Table Example In a further method comparison between the method according to the invention and the traditional trickle bed hardening, catalysts 2 and 10 were used for the through-hardening of fatty acid. The fatty acid used had the iodine value of 88.1 and an acid value of 202.0. It had the following composition: II i, c~ I-r 01 'WO 95/22591 PCT/P95/00456 23
C
18 2 14.5 wt
C
18 77.5 wt Balance: saturated fatty acids with differing chain length The acid value (AV) is used for determining the content of free organic acids in fats (procedure see Deutsches Arzneibuch, 7th edition, 1968) and is a measure of the selectivity of the hardening. The acid number should remain as constant as possible during the hardening. Only the iodine value (IV) as a test value for the unsaturated fatty acids content in fats should be reduced. The aim of the industrial hardening is the reduction of the iodine value to values below 1 in order to improve colour, smell and thermal stability.
There can be achieved with the Pd/OFP catalyst (see Table 7) in the presence of a supercritical phase hydrogenating activities which are almost three times higher than in the trickle bed phase. The acid value as a test value for the selectivity of the hardening also remains on a higher level in the supercritical hardening, apparently as a result of the significantly lower temperature.
The hydrogenating activities of the Pd/OFP catalyst in the presence of a supercritical phase are 34 79 times higher than in comparison with traditional catalysts (nos 7, 8 and 9) in the trickle bed phase. The acid values cannot be included in this comparison, since fatty acids of different quality with different acid values were used.
With a space velocity (LHSV) also of 6.2 h iodine values well below 1 can still be achieved with the 1% Pd/OFP catalyst.
I
WiO 95/22591 PCT/EP95/00456 24 Even with traditional Ni/SiO 2 catalysts higher activities and selectivities can be achieved in the presence of a supercritical phase. Critical for this is probably the carrying out of the reaction at far lower temperature, which results in a reduced deactivation through 'ickel soap formation.
Example 6 For the selective hardening of linoleic acid ethyl esters both in the trickle bed phase and in the method according to the invention, a cordierite monolith with an aluminium oxide washcoat and a palladium covering was used. The cell count of the monolith came to 400 CPSI, corresponding to approx. 62 cells/cm 2 The monolith used possessed a Pd covering of 78 mg for a catalyst volume of 8.6 ml.
The test results are given in Table 8. There can be achieved with the method according to the invention, at significantly lower temperature, both a higher activity and a higher selectivity (lower cis/trans-isomerisation) than in the trickle bed phase.
~I
Table 6: Comparison of various catalyst systems in the supercritical and trickle bed hardening of sunflower oil Cat. no. Catalyst designation/ Hydrogenating IV decrease [h- 1 specific IV cis/trans- Reaction parameters Method particle size activity A decrease isomerisation B [1/h-g am] 2 1% Pd/OFP 14.9 1087 209900 0.27 600 C, 100 bar according CO0/propane to the i stoichiometric H 2 invention LHSV 16.7 h- 1 2 21.4 1559 301100 0.21 see above, according LHSV 26.3 h- 1 to the invention 2 "3.5 127.4 24600 0.32 600 C, 5 bar H 2 trickle LHSV 14.9 h- 1 bed I IBIL r~-a i I Table 7: Comparison of various catalyst systems in the supercritical and trickle bed hardening for the through-hardening of fatty acids with an initial iodine value of 88.1 and an acid value of 202.0 Cat. no. Catalyst Hydrogenating IV decrease specific Final Acid Reaction paramleters Method designation/particle size activity A IV iodine value decrease value [1/h-g am] 2 1% Pd/OFP 7.9 458 112700 0.29 100.8 1200 C, 140 bar C02, according 0.4 0.8 mm super stoichiometric H2 to the LHSV 6.2 h- 1 invention 2 2.7 191 42000 42.1 197.8 1700 C, 20 bar H 2 trickle LHSV 5.0 h- 1 bed 54% Ni/SiO 2 0.45 1.0 mm 0.03 387 420 22.3 198.3 1200 C, 140 bar CO 2 according super stoichiometric H 2 to the LHSV 5.0 h" 1 invention 0.01 203 223 23.5 197.2 1700 C. trickle bar H 2 LHSV 5.0 h- 1 bed 7 2% Pd/TiO 2 0.12 57.8 2890 0.16 202.6 1700 C, according bar H 2 LHSV 1.07 h-1 to DE 41 00 502 8 2% Pd/C 0.23 57.2 5720 0.74 203.4 dist. fatty acid 9 0.5% Pd/A1 2 0 3 0.10 48 9600 39 600 C, according 21.1 bar H 2 to POS LHSV 1 h-3 23 10 958 fatty acid (oleic acid) -I 'i Table 8: Comparison of various catalyst systems in the supercritical and trickle bed hardening Cat- no. Catalyst Hydrogenating II pcfc cstas ecinMethod designation/ activity A, decrease IV isomerisation B parameters particle size [h- 1 decrease [l/hg am] 11 Pd/monolith 2.00 530 6800 0.27 600 C, according 100 bar C0 2 super to the stoichiometric H 2 invention LHSV 10 h- 1 linoleic acid ethyl ester 12 1.79 472 6058 0.38 1700 C, trickle bar H 2 bed LHSV 10 h- 1 conditions linoleic acid ethyl ester
Claims (9)
1. Method for the continuous hydrogenation of fats, fatty acids or fatty acid esters on a shaped catalyst in the fixed bed, characterised in that the fats, fatty acids or fatty acid esters together with the hydrogen required for the hydrogenation and in the presence of a supercritical medium or solvent are reacted on a catalyst and that the fats or fatty acids are then separated from the latter by expansion of the super- critical medium or solvent.
2. Method according to claim 1, characterised in that the hydrogenation is carried out on the catalyst at temperatures between the critical temperature Tcr of the solvent and 7 -Tcr and at pressures between 0.8 times the critical pressure Pcr of the solvent and 6 Pcr"
3. Method according to claim 2, characterised in that there are used as solvent supercritical carbon dioxide, nitrogen monoxide, dinitrogen monoxide, propane or pentane or binary or ternary mixtures thereof, optionally with the addition of modifiers.
4. Method according to claim 3, characterised in that there are used as catalysts platinum group metals, nickel or copper optionally together with promoters on shaped supports.
Method according to claim 4, characterised in that the supports are spherical-shaped and possess diameters in the range between 0.1 and 3.0 mm and that the platinum group metals are deposited on these supports in an outer shell with a thickness of 10 to 40 pm. 29
6. Method according to claim 5, characterised in that in the case of the material of the supports organosiloxane polycondensates, organosiloxane amine copolycondensates or polymeric, secondary and/or tertiary organosiloxane amine compounds are involved.
7. Method according to claim 3, characterised in that the catalyst is deposited as a coating on an inert monolithic support element in the form of a foam ceramic or of a metallic or ceramic honeycomb element.
8. Method according to claim 3, characterised in that the catalyst is shaped to a monolithic honeycomb element.
9. Method for the continuous hydrogenation of fats, fatty acids or fatty acid esters, substantially as hereinbefore described with reference to any one of the Examples but excluding the Comparative Examples. Hydrogenated fats, fatty acids or fatty acid esters produced by the method of any one of claims 1 to 9. Dated 16 September, 1996 Degussa Aktiengesellschaft Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON go a o *o oe [N:\libC]00043:MER
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4405029A DE4405029C2 (en) | 1994-02-17 | 1994-02-17 | Process for curing unsaturated fats, fatty acids or fatty acid esters |
DE4405029 | 1994-02-17 | ||
PCT/EP1995/000456 WO1995022591A1 (en) | 1994-02-17 | 1995-02-09 | Hydrogenation of unsaturated fats, fatty acids or fatty acid esters |
US08/689,836 US5734070A (en) | 1994-02-17 | 1996-08-14 | Hardening of unsaturated fats, fatty acids or fatty acid esters |
Publications (2)
Publication Number | Publication Date |
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AU1808295A AU1808295A (en) | 1995-09-04 |
AU677900B2 true AU677900B2 (en) | 1997-05-08 |
Family
ID=25933862
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AU18082/95A Expired - Fee Related AU677900B2 (en) | 1994-02-17 | 1995-02-09 | Hydrogenation of unsaturated fats, fatty acids or fatty acid esters |
Country Status (11)
Country | Link |
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EP (1) | EP0745116B1 (en) |
JP (1) | JPH09509440A (en) |
CN (1) | CN1140465A (en) |
AU (1) | AU677900B2 (en) |
BR (1) | BR9506806A (en) |
CA (1) | CA2182781A1 (en) |
DE (2) | DE4405029C2 (en) |
DK (1) | DK0745116T3 (en) |
ES (1) | ES2126884T3 (en) |
PL (1) | PL315969A1 (en) |
WO (1) | WO1995022591A1 (en) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1092708C (en) * | 1994-07-01 | 2002-10-16 | 马格尼斯·哈洛德 | Hydrogenation of substrate and products manufactured according to process |
SE504029C2 (en) * | 1994-07-01 | 1996-10-21 | Magnus Haerroed | Hydration of lipids without stereo or positional isomerization |
US6265596B1 (en) | 1995-07-03 | 2001-07-24 | Poul Moller Ledelses - Og Ingeniorradgivning Aps | Partially hydrogenated fatty substances with a low content of trans fatty acids |
US5825308A (en) | 1996-11-26 | 1998-10-20 | Immersion Human Interface Corporation | Force feedback interface having isotonic and isometric functionality |
FI105274B (en) * | 1996-03-15 | 2000-07-14 | Upm Kymmene Oy | Method for hydrogenation of non-hormone-containing unsaturated plant steroids and regeneration of spent catalyst |
GB9607917D0 (en) * | 1996-04-17 | 1996-06-19 | Swan Thomas & Co Ltd | Supercritical hydrogenation |
ID18866A (en) * | 1996-11-11 | 1998-05-14 | Hoffmann La Roche | CATALYTIC HYDROGENATION |
US6103393A (en) * | 1998-02-24 | 2000-08-15 | Superior Micropowders Llc | Metal-carbon composite powders, methods for producing powders and devices fabricated from same |
DE19719431A1 (en) * | 1997-05-12 | 1998-11-19 | Degussa | Process for the continuous catalytic conversion of organic compounds |
DE10215862A1 (en) * | 2002-04-11 | 2003-10-30 | Cognis Deutschland Gmbh | Process for the separation of supercritical or near critical mixtures |
BRPI0413177A (en) | 2003-07-31 | 2006-10-03 | Cargill Inc | low trans-fatty acid fatty compositions; low temperature hydrogenation, for example, of edible oils |
US7585990B2 (en) | 2003-07-31 | 2009-09-08 | Cargill, Incorporated | Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils |
GB0406125D0 (en) | 2004-03-18 | 2004-04-21 | Univ Cambridge Tech | Methods of amination |
WO2005095306A1 (en) * | 2004-03-31 | 2005-10-13 | Härröd Research Ab | Selective hydrogenation of functional groups in substrates and partially hydrogenated fatty acids and fatty acid derivatives |
ES2245901B1 (en) * | 2004-07-15 | 2007-04-01 | Universitat Politecnica De Catalunya | PARTIAL HYDROGENATION PROCESS OF HIGH PRESSURE STEAM AND REACTOR INSPURED TRIGLICERIDES FOR THE PERFORMANCE OF THIS PROCESS. |
JP5110607B2 (en) * | 2007-02-28 | 2012-12-26 | 独立行政法人産業技術総合研究所 | Biodiesel fuel production method and biodiesel fuel composition |
DE102008016105A1 (en) | 2008-03-28 | 2009-10-01 | Cognis Oleochemicals Gmbh | Process and apparatus for the catalytic hydrogenation of unsaturated fatty acids and fatty acid derivatives |
ES2350669B1 (en) * | 2009-06-03 | 2011-11-15 | Universitat Politècnica De Catalunya | CONTINUOUS PROCESS OF HYDROGENERATION OF VEGETABLE OILS IN LIQUID PRESSURE AND TEMPERATURE PHASE OBTAINING A FAT WITH LOW CONTENT IN TRANS ISOMERO |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1481958A (en) * | 1974-11-08 | 1977-08-03 | Coal Ind | Supercritical extraction and concurrent catalytic hydrogenation of coal digests |
WO1994006738A1 (en) * | 1992-09-14 | 1994-03-31 | Unichema Chemie B.V. | Process for the production of alcohols |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4109502A1 (en) * | 1991-03-22 | 1992-09-24 | Degussa | CATALYST FOR HARDENING FATTY ACIDS AND METHOD FOR THE PRODUCTION THEREOF |
-
1994
- 1994-02-17 DE DE4405029A patent/DE4405029C2/en not_active Expired - Fee Related
-
1995
- 1995-02-09 ES ES95909690T patent/ES2126884T3/en not_active Expired - Lifetime
- 1995-02-09 PL PL95315969A patent/PL315969A1/en unknown
- 1995-02-09 EP EP95909690A patent/EP0745116B1/en not_active Revoked
- 1995-02-09 CA CA002182781A patent/CA2182781A1/en not_active Abandoned
- 1995-02-09 DE DE59504267T patent/DE59504267D1/en not_active Expired - Fee Related
- 1995-02-09 CN CN95191599A patent/CN1140465A/en active Pending
- 1995-02-09 BR BR9506806A patent/BR9506806A/en not_active Application Discontinuation
- 1995-02-09 JP JP7521550A patent/JPH09509440A/en not_active Ceased
- 1995-02-09 WO PCT/EP1995/000456 patent/WO1995022591A1/en not_active Application Discontinuation
- 1995-02-09 AU AU18082/95A patent/AU677900B2/en not_active Expired - Fee Related
- 1995-02-09 DK DK95909690T patent/DK0745116T3/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1481958A (en) * | 1974-11-08 | 1977-08-03 | Coal Ind | Supercritical extraction and concurrent catalytic hydrogenation of coal digests |
WO1994006738A1 (en) * | 1992-09-14 | 1994-03-31 | Unichema Chemie B.V. | Process for the production of alcohols |
Also Published As
Publication number | Publication date |
---|---|
PL315969A1 (en) | 1996-12-23 |
DE4405029A1 (en) | 1995-08-24 |
EP0745116B1 (en) | 1998-11-18 |
CA2182781A1 (en) | 1995-08-24 |
JPH09509440A (en) | 1997-09-22 |
CN1140465A (en) | 1997-01-15 |
WO1995022591A1 (en) | 1995-08-24 |
ES2126884T3 (en) | 1999-04-01 |
DK0745116T3 (en) | 1999-08-02 |
BR9506806A (en) | 1997-09-30 |
EP0745116A1 (en) | 1996-12-04 |
AU1808295A (en) | 1995-09-04 |
DE59504267D1 (en) | 1998-12-24 |
DE4405029C2 (en) | 1996-04-04 |
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