US2094611A - Process for producing alcohols from hydroxy carboxylic compounds - Google Patents
Process for producing alcohols from hydroxy carboxylic compounds Download PDFInfo
- Publication number
- US2094611A US2094611A US757071A US75707134A US2094611A US 2094611 A US2094611 A US 2094611A US 757071 A US757071 A US 757071A US 75707134 A US75707134 A US 75707134A US 2094611 A US2094611 A US 2094611A
- Authority
- US
- United States
- Prior art keywords
- hydrogenation
- catalyst
- hydrogen
- process according
- pressure
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title description 79
- 230000008569 process Effects 0.000 title description 63
- 150000001298 alcohols Chemical class 0.000 title description 25
- 150000001875 compounds Chemical class 0.000 title description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title description 8
- 239000003054 catalyst Substances 0.000 description 73
- 238000005984 hydrogenation reaction Methods 0.000 description 67
- 229910052739 hydrogen Inorganic materials 0.000 description 40
- 239000001257 hydrogen Substances 0.000 description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 33
- 235000019441 ethanol Nutrition 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 29
- 150000002148 esters Chemical class 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 239000004359 castor oil Substances 0.000 description 22
- 235000019438 castor oil Nutrition 0.000 description 22
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 22
- 239000002253 acid Substances 0.000 description 18
- 150000002739 metals Chemical class 0.000 description 17
- VJQGGZWPOMJLTP-UHFFFAOYSA-N octadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCC(O)O VJQGGZWPOMJLTP-UHFFFAOYSA-N 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 150000002334 glycols Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 12
- 229960003656 ricinoleic acid Drugs 0.000 description 12
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 7
- 150000001261 hydroxy acids Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- VGZOEDUWOQJGDE-UHFFFAOYSA-N [Cu+2].[Ba+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O Chemical class [Cu+2].[Ba+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O VGZOEDUWOQJGDE-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- QOQZSVKKTPUAJM-UHFFFAOYSA-N ethyl 2-hydroxyoctadecanoate Chemical compound CCCCCCCCCCCCCCCCC(O)C(=O)OCC QOQZSVKKTPUAJM-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RDPKTGUAERYFIA-UHFFFAOYSA-N [Cr](=O)([O-])[O-].[Zn+2].[Cu+2].[Cd+2].[Cr](=O)([O-])[O-].[Cr](=O)([O-])[O-] Chemical compound [Cr](=O)([O-])[O-].[Zn+2].[Cu+2].[Cd+2].[Cr](=O)([O-])[O-].[Cr](=O)([O-])[O-] RDPKTGUAERYFIA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AZXVZUBIFYQWJK-KWRJMZDGSA-N ethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC AZXVZUBIFYQWJK-KWRJMZDGSA-N 0.000 description 2
- 239000010685 fatty oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OMPIYDSYGYKWSG-UHFFFAOYSA-N Citronensaeure-alpha-aethylester Natural products CCOC(=O)CC(O)(C(O)=O)CC(O)=O OMPIYDSYGYKWSG-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- BELQXUYAYAYLPH-UHFFFAOYSA-N [Cr](=O)([O-])[O-].[Ag+2] Chemical compound [Cr](=O)([O-])[O-].[Ag+2] BELQXUYAYAYLPH-UHFFFAOYSA-N 0.000 description 1
- WNVXPUKIBYOUIG-UHFFFAOYSA-N [Mn+2].[O-][Cr]([O-])=O Chemical compound [Mn+2].[O-][Cr]([O-])=O WNVXPUKIBYOUIG-UHFFFAOYSA-N 0.000 description 1
- LRFQSNDOLFTQCR-UHFFFAOYSA-M [O-][Cr](O)(=O)=O.N.[Cu+] Chemical compound [O-][Cr](O)(=O)=O.N.[Cu+] LRFQSNDOLFTQCR-UHFFFAOYSA-M 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QFKJCKFAYFUXRQ-UHFFFAOYSA-N barium;hydrate Chemical compound O.[Ba] QFKJCKFAYFUXRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- CUZMQPZYCDIHQL-VCTVXEGHSA-L calcium;(2s)-1-[(2s)-3-[(2r)-2-(cyclohexanecarbonylamino)propanoyl]sulfanyl-2-methylpropanoyl]pyrrolidine-2-carboxylate Chemical compound [Ca+2].N([C@H](C)C(=O)SC[C@@H](C)C(=O)N1[C@@H](CCC1)C([O-])=O)C(=O)C1CCCCC1.N([C@H](C)C(=O)SC[C@@H](C)C(=O)N1[C@@H](CCC1)C([O-])=O)C(=O)C1CCCCC1 CUZMQPZYCDIHQL-VCTVXEGHSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- 229940057975 ethyl citrate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- -1 hydroxy stearin Chemical compound 0.000 description 1
- 229940072106 hydroxystearate Drugs 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 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
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- JQOAZIZLIIOXEW-UHFFFAOYSA-N zinc;chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Cr+3].[Cr+3].[Zn+2] JQOAZIZLIIOXEW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Definitions
- This invention relates to catalytic processes for the production of organic compounds of an alcoho1iccharacter. More particularly it relates to a process for the catalytic reduction by means of elementary hydrogen of hydroxy-carboxylic acids, their esters, and their anhydrides to the corresponding glycols. Specifically, the invention relates to the use of certain catalysts especially well suited to the hydrogenation of hydroxy acids and their .derivatives to the corre- ,sponding glycols, and to processes for the production of octadecanediol from castor oil and its derivatives.
- This invention has as an object to provide a process for the conversion of hydroxy-carboxylic acids, their esters, and their anhydrides to the corresponding glycols. It is a further object of the invention to disclose processes for the hydrogenation of castor oil, ricinoleic acid, hydroxystearic acid, and derivatives of the same, and the products produced by such hydrogenation. A more specific object is the preparation of octadecanediol which is a new compound.
- the processes of my invention are characterized by the use of an excess of hydrogen and temperatures and pressures much inexcess of those ordinarily employed.
- the invention is carried out by bringing the hydroxyrcarboxylic compound and hydrogen into intimate contact with a suitable alcohol-forming catalyst at relatively high temperatures and pressures.
- a suitable alcohol-forming catalyst there are, however, several modifications of the general process. For example, a mixture of the compound to be hydrogenated, solid catalyst, and
- gaseous hydrogen maybe brought together at high temperatures and pressures with suitable agitation in a closed autoclave capable of Withstanding the necessary pressure.
- the catalyst is preferably a composition containing copper, either in the elementary form or combined with oxygen as a lower oxide.
- Other hydrogenating metal oxides may be employed in conjunction with copper, or suitable catalyst supports such as kieselguhr. silica gel, and activated carbon may be used.
- the hydroxy-carboxylic compounds and hydrogen are passed under high pressures and elevated temperatures over mixed hydrogenation catalysts containing substantial quantities of diflicultly reducible oxides of hydrogenating metals prepared in a suitable granular form and held in place in a pressure-resisting tube.
- Example I A hydrogenation catalyst is prepared as follows: 23 g. of cadmium nitrate, 24g. of copper nitrate and 245 g. of zinc nitrate are dissolved in 500 cc. of water and mixed at ordinary temperature with an equal volume of water containing 126 g. of ammonium bichromate and cc. of 28% ammonium hydroxide. After stirring, the mixture is exactly neutralized with additional ammonium hydroxide and allowed to settle. After several washes by decantation, the precipitate is dried, ignited at 400 C. and compressed into tablets or grains suitable for use in catalytic gas apparatus.
- Example II Castor oil maintained under 2700 pounds per square inch hydrogen pressure was passed at a temperature of 400 C., together with hydrogen, at a space velocity of 4 volumes of oil per volume of catalyst per hour and at a molecular ratio of 12 moles of hydrogen per mole of combined ricinoleic acid over-25 cc. of the zinc-copper-cadmium chromite catalyst describe: in Example I.
- Fraction 5 was refractionated at 0.5 mm., the first 10 g. of distillate being discarded. The remainder distilled at to 182 C., with the bath temperature at 225 to 235 C. The latter part of the distillate melted at 66 to 67 C., and was quite pure octadecanediol-1,12.
- octadecanediol is a white solid melting at 66 to 67 C., and boiling at 180 to 182 C. at a pressure of 0.5 mm.
- the glycol has an acetyl number corresponding to a dihydric alcohol. It contains one primary and one secondary alcohol group. The compound appears to be crystalline but is very waxy in character. It dissolves in alcohol or ether. It is not readily soluble in water but may be emulsified at temperatures above the melting point.
- Example III A good commercial grade of ricinoleic acid produced by saponiflcation of castor oil was hydrogenated continuously to produce high yields of glycol.
- the zinc-copper-cadmium chromite catalyst described in Example I was heated to a temperature of about 380 C.
- the acid was pumped over 100 cc. of the catalyst at the rate of about 200 cc. per hour.
- the hydrogen pressure was 2500 to 3000 pounds per square inch, and the rate of flow of the hydrogen about 15 cubic feet per hour. Under these conditions the ricinoleic acid is hydrogenated in the vapor phase.
- nitrate and-176 grams of chromic acid were dissolved in 2760 cc. of water and 88 g. of anhydrous .ainmonia was added to the solution with agitation during a period of to minutes.
- the precipitate was filtered, washed once on the filter and dried, after which it was ignited at 500 C.
- the resulting copper chromite powder was extracted twice by stirring it for 15 minutes each time with a solution of 200 g. of glacial acetic acid in 1800 cc. of water. After extraction, it was washed free from acid, filtered, dried and screened through a 20 mesh screen. Two hundred seventy-five grams of this catalyst and 4330 -g. of ethyl hydroxystearate were placed in an autoclave and hydrogen was introduced to a pressure of 3000 pounds per square inch. The mixture was then heated to 350 C. and agitated for 9 hours, after which hydrogen absorption had ceased. The decrease in saponification number of the ester during this treatment corresponded to hydrogenation of the carboxyl groups while recovery and separation of the product yielded 12% stearyl alcohol and- 80% octadecanediol.
- Example V Twenty-six grams of barium nitrate and 218 g. of cupric nitrate were dissolved in 0.8 liter of water by heating to 70 C. A solution of 128 g. of ammonium bichromate and 0.15 liter of 28% ammonium hydroxide in 600 cc. of water was added with stirring. The precipitate was filtered; dried and ignited at 400 C. The ignition residue was then extracted twice with 10% acetic acid, washed and dried. Twenty grams of this copper barium chromite was agitated with 340 g. of ethyl alpha-hydroxy isobutyrate under a hydrogen pressure of 2500 pounds per square inch. Hydrogen absorption was rapid at about 200 C. and the reaction was complete in about one hour. On distillation of the product, there was obtained a 91% yield of 2-methyl propane diol-1,2.
- Example VI One hundred fifty grams of ethyl citrate'and 12 g. of the copper barium chromite catalyst prepared as described in Example V were charged into a steel reaction tube built to withstand high pressure. The tube was agitated for 4.5 hours at a temperature of 240 C. and a hydrogenation From the reaction product there was isolated 25 g. of a trihydric alcohol (trimethyiol propane) and an oily residue containing a substantial quantity of a cyclic ether alcohol, the constitution of which was not fully determined.
- a trihydric alcohol trimethyiol propane
- Example VII Fifteen hundred grams of copper nitrate dissolved in 4 liters of water was mixed with a solution containing 1000 g. of ammonium chromate in an equal volume of water. Ammonium hy-, droxide was added to neutralize the acidity developed during precipitation of the copper ammonium chromate. The precipitate was washed by decantation, filtered, and dried, after which it was ignited at a temperature of 400 .C. The ignition residue was then extracted twice with 10% acetic acid, washed and dried.
- Example IX Sixteen grams of a copper chromite catalyst prepared as described in Example IV, 0.4 g. of magnesium oxide, and 200 g. of ethyl hydroxystearate were charged into a steel reaction tube
- Example X Copper carbonate was prepared by dissolving 720 g. of copper nitrate trihydrate in 1 liter of water and heating the solution to 40 C. and slowly adding with agitation during a period of one hour a solution consisting of 300 g. of sodium carbonate dissolved in 3 liters of water. The precipitate thus formed was washed four times by decantation using 5liters of distilled water for each wash, after which it was filtered, dried at C., and ground to a fine powder.
- the catalytic reduction of hydroxy acids, their esters, and their anhydrides to alcohols or glycols requires the use of temperatures and pressures appreciably higher than customarily employed for other hydrogenation reactions.
- the temperature may range from above 200 C. up to 500 C.
- the preferred temperature range is 240 to 400 C., depending somewhat on the catalyst-- pressures in excess of atmospheres, while the preferred pressure is 50 to 400 atmospheres.
- the maximum pressure which can be used is limited only by the strength ,of the reaction apparatus.
- suitable catalysts may be selected from among a number of different hydrogenating metals and oxides.
- Mild-acting hydrogenating catalysts such as metallic copper and zinc oxide which are well known to be suitable for the synthesisof methanol from carbon monoxide and hydrogen are in general also suitable catalysts for the production of glycols.
- metallic copper and zinc oxide which are well known to be suitable for the synthesisof methanol from carbon monoxide and hydrogen are in general also suitable catalysts for the production of glycols.
- very energetic catalysts such as metallic nickel and iron which are known to catalyze the formation of hydrocarbons from oxides of carbon
- ferrous metal catalysts when employed in the hydrogenation of hydroxy acids and their esters, tendto carry the reaction too far with the formation of hydrocarbons.
- the catalyst a composition comprising a member of the group of non-ferrous hydrogenating metals such as copper, tin, silver, cadmium, zinc, lead, their oxides and chromites, and oxides and chromites of manganese, and magnesium.
- a member of the group of non-ferrous hydrogenating metals such as copper, tin, silver, cadmium, zinc, lead, their oxides and chromites, and oxides and chromites of manganese, and magnesium.
- the above mentioned mild-acting catalysts may be termed the alcohol-forming catalysts to distinguish them from the more energetic hydrocarbon-forming elements of the platinum and ferrous metal'groups.
- Elementary nickel, cobalt, and iron, when suitably supported on kieselguhr, may be used to effect the reduction of carboxylic compounds with hydrogen, but in these cases the product contains besides alcoholic bodies a preponderance of hydrocarbons, and this disadvantage in most cases will prove so serious as to preclude the use of these catalysts unless the hydrocarbons themselves are the desired end products.
- Catalysts suitable for use in the liquid phase batch method of hydrogenation are preferably prepared in a powder form.
- the preferred catalyst for this purpose is usually a copper chromite prepared by igniting a double copper amaooaeu monium chromate to its spontaneous decomposition temperature as described in U. 8. Patent 1,746,783. Many modifications of this procedure have been practiced involving the use of acid. extraction, hydrogen reduction, and the use of a supplementary support such as kieselguhr, but these are modifications in degree only.
- the es- :sential feature is the use oi copper oxide intimately associated or combined with chromium sesquioxide and the chromite method of preparation is a convenient method for effecting the desired association.
- the method is not limited to copper but may be practiced in the preparation also of zinc chromite, silver chromite, manganese chromite, etc.-
- certain metal oxides belonging to the class of difllcultly reducible hydrogenating oxides may be conveniently employed on account of their rugged character and the ease with which they may be-shaped into hard granules for loading into stationary apparatus.
- diflicultly reducible is meant that the oxides are not substantially reduced to metal by prolonged exposure in a state of purity to the action of hydrogen at atmospheric pressure and at a temperature of 400 to 450 C.
- oxides suitable for use as catalysts in the hydrogenation of hydroxy-carboxylic compounds are zinc oxide, manganese oxide, and magnesium oxide. These oxides may be employed either alone or in combination with each other or with other metals or oxides which have a promoting action.
- the dimcultly reducible hydrogenating oxides also are prepared in the form of chromites as already indicated in the examples.
- Hydroxy acids and their derivatives are particularly susceptible to partial dehydration, and it has been found that this undesirable side reaction may be largely prevented by employing a mild inorganic base added to the hydrogenation catalyst.
- a mild inorganic base added to the hydrogenation catalyst.
- products having much higher hydroxyl values are obtained if a little magnesia, zinc oxide, lime, or barium hydrate is added to the catalyst or to the reaction system.
- the alkali earth buffer is incorporated into the catalyst at the time of its precipitation.
- the rate at which the ester may be pumped over the catalyst with satisfactory results is a function of the catalytic activity and also of the molecular weight of the ester.
- An active hydrogenating catalyst will ordinarily convert eight times its volume of ester per hour. Higher rates of flow of the ester may be employed at the expense of slightly lower conversion.
- the processes of the present invention are applicable to a large number of hydroxy-carboxylic acids, their esters and anhydrides, for example, lactic, ricinoleic, hydroxy-butyric and -isobutyric, hydroxy-valeric, hydrcxy-stearic acids, etc.- As indicated, these acids may be employed for hydrogenation in the form of the free acid or as their esters or anhydrides. The same glycols are obtained on hydrogenation irrespective of the form in which the hydroxy-carboxylic compound is treated.
- the ester may be a mono-alkyl ester or an ester of a polyhydric alcohol such as glycerol.
- the hydroxy acid may be unsaturated as in the case of ricinoleic acid or fully saturated as in the case of hydroxy-stearic acid.
- the hydrogenation of these acids and their derivatives lead to a very interesting new glycol, i. e., octadecanediol-LIZ.
- Castor oil is a glyceride of ricinoleic acid, and complete or partial reduction of the carboncarbon unsaturation may occur as in the usual hydrogenation process of the prior art, but in the present process this is only incidental to the more-important reaction of hydrogenation of the ester groupwhich results in the formation of alcohols.
- the hydrogenation with nickel may precede the carboxylic hydrogenation carried out for the purposes of converting the carboxyl groups to' carbinol groups, as, for example, in the conversion of ethyl. ricinoleate to the hydroxy stearate followed by conversion to octadecanediol.
- the hydrogenation products obtained by the hydrogenation of castor oil under the conditions of the present invention consist of a mixture of higher alcohols and other products and this mixture in itself constitutes a new composition of matter, which in some instances finds use in the arts without any separation of the product into its components. In such cases, as well as when it is not feasible to separate the alcohols from the other hydrogenation products, the presence of the alcohols and the amount thereof formed may be demonstrated conclusively by determination of the acetyl or hydroxyl values.
- Example I Depending on the conditions of hydrogenation, a part of the secondary hydroxyl group of octadecanediol may be split off, giving a monohydric alcohol as one of the products.
- the method for isolating the glycol disclosed in Example I involves saponification and extraction.
- a more simple procedure for commercial operation consists in hydrogenating ricinoleic acid or its esters rather completely and separating the glycol produced by direct vacuum fractional distillation of the crude hydrogenated product. The wax residue may then be put through the hydrogenation step again, together with fresh raw material.
- octadecanediol As a component of soap, octadecanediol contributes to detergent power in the presence of hard water and tends to counteract the harshness of soaps.
- the derivatives of octadecanediol such as esters thereof find use as softeners, for example, in nitrocellulose compositions, and the sulfonated octadecanediol is a. valuable wetting-out agent and detergent.
- a process for producing alcohols from hydroxy carboxylic compounds which comprises bringing hydrogen and amember of the class consisting of the hydroxy carboxylic acids, and their esters into contact with a mild-acting hydrogenation catalyst at a temperature in excess of 200 C. and at a pressure in excess of 10 atmospheres.
- Process according to claim 1 characterized in that the temperature is maintained between 240 and 400 C.
- the catalyst is a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites.
- the catalyst comprises essentially a mixed chromite of cadmium, copper and zinc.
- catalyst comprises essentially a mixture of difficultly reducible hydrogenating metal oxides.
- the catalyst comprises essentially a chrosure slightly in excessof atmospheric and at a v temperature between 50 and 200 C. in the presence of a nickel catalyst in order to saturate the carbon-carbon bond, then subjecting the products produced by the second hydrogenation step to separation and purification.
- A' process for producing a glycol which comprises bringing hydrogen and a hydroxy carboxylic acid into contact with a mild-acting hydrogena'tion catalyst at a temperature in excesspheres.
- the' catalyst is a hydrogenation catalyst .01 the class consisting of mild acting hydrogenatin that the catalyst contains as essential ingredients chromites of copper and barium.
- the catalyst is a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such-metals, oxides and chromites.
- Process according to claim 20 characterize in thatthe catalyst contains as essential ingredients chromites of copper and barium.
- a process for producing a glycol which comprises bringing hydrogen and ricinoleic acid into contact with a mild-acting hydrogenation catalyst at a temperature in-excess of 200 C.
- a process for producing alcohols from castor oil which comprises saponifying castor oil to form an acid, passing said acid and hy-- drogen over a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides, and chro- 2,094,041 of 200 C. and at a pressure in excess of -10 atmosmites at a temperature in excess oi! 200 C. and at a pressure in excess or 10 atmospheres.
- a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides, and chro- 2,094,041 of 200 C. and at a pressure in excess of -10 atmosmites at a temperature in excess oi! 200 C. and at a pressure in excess or 10 atmospheres.
- a process for producing alcohols from castor oil which comprises saponifyin'g castor oil to form an acid, then passing said acid and hydrogen over a mixture 01' the chromites of zinc, copper, and cadmium at a temperature of about 380 C. and at a pressure of about 2500 to 3000 pounds per square inch.
- a process for producing alcohols 'from ricinoleyl derivatives which comprises passing ricinoleic acid .and hydrogen over a hydrogenation catalyst of the class consistingo! mild acting hydrogenating metals, their oxides and chromites, theoxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites at a temperature in excess of 200 ,C. and at a pressure in excess oi! 10 atmospheres, separating the glycol produced by direct vacuum distillation of the crude hydrogenated product.
- Process according to claim 24 character- 40. Process according to claim 24 characterized in that the hydrogenated reaction products are subjected to further hydrogenation to remove the carbon-carbon unsaturation and then recovering the octadecanediol formed.
- a process of producing a glycol which comprises bringing hydrogen and an ester of ricinoleic acid into contact with a mild-acting hydrogena tion catalyst at a temperature in excess of 200 C. and at a pressure in excess 01' 10 atmospheres.
- the process according to claim 43 characterized in that the reaction is carried out at a temperature between 300 and 400 C. and at a pressure between 100 and 250 atmospheres.
- a process for producing alcohols from castor oil which comprises passing castor oil and hydrogen over a mixture of the chromites or zinc; copper, and cadmium at a temperature 01 about 300-400 C. and at a pressure of about 2700 pounds per square inch.
- a process for producing a glycol whichv comprises bringing hydrogen and castor oil into contact with a mild-acting hydrogenation catalyst at a temperature in excess of 200 C. and'at a pressure in excess of 10 atmospheres.
- the catalyst is a hydrogenation catalyst of the class consisting of mild acting hydrogenatlng metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites.
- a mixture of alcohols obtainable by the carboxyl hydrogenation of castor oil followed by the hydrogenation of the resulting product with a nickel catalyst in order to remove the carbon-carbon unsaturation.
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Description
Patented Oct. 5, 1937 UNITED STATES 2,094,611 rnoccss FOR PRODUCING ALCOHOLS FROM POUNDS HYDROXY CARBOXYLIC COM- Wilbur .A. Lazier, 'Marshallton, DeL, assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing.
Application December Serial No. 757,071
64 Claims. (Cl. 260-4565) This invention relates to catalytic processes for the production of organic compounds of an alcoho1iccharacter. More particularly it relates to a process for the catalytic reduction by means of elementary hydrogen of hydroxy-carboxylic acids, their esters, and their anhydrides to the corresponding glycols. Specifically, the invention relates to the use of certain catalysts especially well suited to the hydrogenation of hydroxy acids and their .derivatives to the corre- ,sponding glycols, and to processes for the production of octadecanediol from castor oil and its derivatives.
This application is a continuation-in-part of my co-pending application Serial No. 584,576, which was filed January 2, 1932, as a continuation-in-part of applications Serial Nos. 520,473 and 520,474, both filed March 5, 1931. Application Serial No. 520,474 has since matured into U. S. Patent 1,839,974. The present application is also a continuation-in-part, of the following co-pending applications: Serial No. 629,754 filed August 20, 1932, which in turn was a continuation-in-part of Serial No. 445,224 filed April 17, 1930; Serial No. 584,574 filed January 2, 1932; and Serial No. 715,509 filed March 14, 1934.
For many years the only known methods for the reduction of hydroxy-carboxylic acids, esters, and their anhydrides to. the corresponding glycols were purely chemical reactions involving the consumption of expensive reducing agents. The most successful procedure was that outlined by Bouveault and Blane (Chem. Zentr. 1904, II, 184; 1905, II, 1700). This process involves preparing an ester of the acid to be reduced and the use of metallic sodium and absolute alcohol as the reducing agent. Thus it has been possible to prepare alcoholic derivatives ofthe simple aliphatic carboxylic acids. This method, however, is so costly as to render its use prohibitive for the manufacture of various glycols which might otherwise be very useful in the arts.
By suitable modifications, of processes fully described in the co-pending specifications to which reference has already been made, it has now become possible to realize on a commerfial scale a technically and economically successful catalytic hydrogenation of hydroxy acids, their esters, and their anhydrides, whereby glycols are formed which correspond in the number of carbon atoms to the acids or acid derivatives subjected to the hydrogenation treatment. Other products such as the corresponding saturated hydrocarbons and esters of the newly formed glycols may also be prepared in this way by'minor I variations in the procedure, but the invention is primarily concerned with the production of glycols which are the intermediate products between the esters of the glycols and the corresponding hydrocarbons resulting from exhaustive hydrogenation.
In my co-pending application Serial No. 520,473, filed March 5, 1931, there is contained a description of the successful hydrogenation of natural glyceryl esters known as fats and fatty oils, and there is specifically described in Example 4 the hydrogenation of castor oil. The hydrogenation process therein described effects the hydrogenation of the ester group of the glyceride, thereby yielding alcohols. This type of hydrogenation is to be distinguished sharply from the process of hardening fats by hydrogenation as practiced at a much earlier date, and which consists in agitating a glyceride of an unsaturated fatty acid with a suspended nickel catalyst in the presence of gaseous hydrogen under a pressure slightly in excess of atmospheric pressure. In the process of hydrogenating fats and fatty oils as practiced in the prior art, the temperatures employed are usually 50 to C; and are never greater than 200 C., while the pressures customarily used are substantially atmospheric.
This invention has as an object to provide a process for the conversion of hydroxy-carboxylic acids, their esters, and their anhydrides to the corresponding glycols. It is a further object of the invention to disclose processes for the hydrogenation of castor oil, ricinoleic acid, hydroxystearic acid, and derivatives of the same, and the products produced by such hydrogenation. A more specific object is the preparation of octadecanediol which is a new compound.
The processes of my inventionare characterized by the use of an excess of hydrogen and temperatures and pressures much inexcess of those ordinarily employed. In general, the invention is carried out by bringing the hydroxyrcarboxylic compound and hydrogen into intimate contact with a suitable alcohol-forming catalyst at relatively high temperatures and pressures. There are, however, several modifications of the general process. For example, a mixture of the compound to be hydrogenated, solid catalyst, and
gaseous hydrogen maybe brought together at high temperatures and pressures with suitable agitation in a closed autoclave capable of Withstanding the necessary pressure. -In this case the catalyst is preferably a composition containing copper, either in the elementary form or combined with oxygen as a lower oxide. Other hydrogenating metal oxides may be employed in conjunction with copper, or suitable catalyst supports such as kieselguhr. silica gel, and activated carbon may be used. In another modification, of the process the hydroxy-carboxylic compounds and hydrogen are passed under high pressures and elevated temperatures over mixed hydrogenation catalysts containing substantial quantities of diflicultly reducible oxides of hydrogenating metals prepared in a suitable granular form and held in place in a pressure-resisting tube. Contrary to expectation, it has been found that under high hydrogen pressures, hydroxy acids and their derivatives are, much less susceptible to decomposition by heat than would be supposed from their behavior when heated in air. Under reducing. conditions and in the presence of a suitable catalyst the decomposition, if such it may be termed, takes place in a controlled manner and with the absorption of hydrogen and the production of the corresponding dihydric alcohols.
The following examples are illustrative of some of the methods that may be employed in the practice of my invention:
Example I A hydrogenation catalyst is prepared as follows: 23 g. of cadmium nitrate, 24g. of copper nitrate and 245 g. of zinc nitrate are dissolved in 500 cc. of water and mixed at ordinary temperature with an equal volume of water containing 126 g. of ammonium bichromate and cc. of 28% ammonium hydroxide. After stirring, the mixture is exactly neutralized with additional ammonium hydroxide and allowed to settle. After several washes by decantation, the precipitate is dried, ignited at 400 C. and compressed into tablets or grains suitable for use in catalytic gas apparatus.
Twenty-five cc. of the mixed chromite catalyst prepared as described above was loaded into an alloy steel reaction vesselcapable of being heated and withstanding high pressures. The tube was fitted with a preheater, a pump for injecting liquid ester at a constant rate, a T- connection for introducing hydrogen under pressure, a suitable condenser and trap for separating liquid products, and exit control valve. Ethyl ricinoleate was passed with hydrogen over the catalyst at a rate of about 200 cc. per hour. The average pressure was 2570 pounds per square inch, the average temperature 370 C., and the rate of hydrogen flow 7.7 cubic feet per hour. The saponification value of the condensed product indicated a conversion to alcohols amounting to about 65%. In order to remove the remaining oleflnic unsaturation, the products were subjected to a further -hydrogenation with a nickel catalyst in the liquid phase at C. After distilling off the ethyl alcohol there remained a white solid material consisting of about equal parts of octadecanediol and stearyl alcohol, together with a lesser amount of the esters of these alcohols. v
Example II Castor oil maintained under 2700 pounds per square inch hydrogen pressure was passed at a temperature of 400 C., together with hydrogen, at a space velocity of 4 volumes of oil per volume of catalyst per hour and at a molecular ratio of 12 moles of hydrogen per mole of combined ricinoleic acid over-25 cc. of the zinc-copper-cadmium chromite catalyst describe: in Example I. The
decrease in saponiflcation value was about 60%. while the iodine number was lowered from 65 to 55. The product was quite fluid and possessed a pleasant alcoholic odor. By further hydrogenation with nickel in the liquid phase by the prior art method, namely, at a temperature of 50 to C., and at a pressure slightly in. excess of atmospheric pressure, the product was readily converted to a white solid material, containing a large proportion of a dihydric alcohol. The crude product had an acid number of: 3. a saponiflcation number of 80, an iodine number of 4, and an acetyl number of 171.
The following procedure was used to separate out the octadecanediol from the crude mixture; One thousand grams of the white solid material was saponified by refluxing for 8 hours with a solution of 70 g. of sodium hydroxide dissolved in 2.5 liters of water. The soapy mass was evaporated and dried. The residue was broken up and continuously extracted with ether in small batches. The various portions of ether extract were combined, and the ether distilled 01f.v The residue was washed with hot water and dried. Four hundred thirty-one grams of product was obtained, of which 376 g. was fractionated through a 15 inch lagged Vigreux column at 0.1 mm. pressure, (gauge reading) with the following results:
Fraction 5 was refractionated at 0.5 mm., the first 10 g. of distillate being discarded. The remainder distilled at to 182 C., with the bath temperature at 225 to 235 C. The latter part of the distillate melted at 66 to 67 C., and was quite pure octadecanediol-1,12.
Analysis: Calculated for C18H38o2: C, 75.52; H, 13.29.
Found: C, 75.66, 75.65; H, 12,96, 13.26.
octadecanediol is a white solid melting at 66 to 67 C., and boiling at 180 to 182 C. at a pressure of 0.5 mm. The glycol has an acetyl number corresponding to a dihydric alcohol. It contains one primary and one secondary alcohol group. The compound appears to be crystalline but is very waxy in character. It dissolves in alcohol or ether. It is not readily soluble in water but may be emulsified at temperatures above the melting point.
Example III A good commercial grade of ricinoleic acid produced by saponiflcation of castor oil was hydrogenated continuously to produce high yields of glycol. The zinc-copper-cadmium chromite catalyst described in Example I was heated to a temperature of about 380 C. The acid was pumped over 100 cc. of the catalyst at the rate of about 200 cc. per hour. The hydrogen pressure was 2500 to 3000 pounds per square inch, and the rate of flow of the hydrogen about 15 cubic feet per hour. Under these conditions the ricinoleic acid is hydrogenated in the vapor phase. There was produced a viscous product containing about 40% of esters and practically no free acid, the remainder being, with the exception of a small amount of glycerol, practically all long-chain higher alcohols. t The reaction products were susceptible of further hydrogenation and purification in the same manner as described in Example II to produceloctariecanediol.
nitrate and-176 grams of chromic acid were dissolved in 2760 cc. of water and 88 g. of anhydrous .ainmonia was added to the solution with agitation during a period of to minutes. The precipitate was filtered, washed once on the filter and dried, after which it was ignited at 500 C.
. pressure of 600 atmospheres.
The resulting copper chromite powder was extracted twice by stirring it for 15 minutes each time with a solution of 200 g. of glacial acetic acid in 1800 cc. of water. After extraction, it was washed free from acid, filtered, dried and screened through a 20 mesh screen. Two hundred seventy-five grams of this catalyst and 4330 -g. of ethyl hydroxystearate were placed in an autoclave and hydrogen was introduced to a pressure of 3000 pounds per square inch. The mixture was then heated to 350 C. and agitated for 9 hours, after which hydrogen absorption had ceased. The decrease in saponification number of the ester during this treatment corresponded to hydrogenation of the carboxyl groups while recovery and separation of the product yielded 12% stearyl alcohol and- 80% octadecanediol.
Example V Twenty-six grams of barium nitrate and 218 g. of cupric nitrate were dissolved in 0.8 liter of water by heating to 70 C. A solution of 128 g. of ammonium bichromate and 0.15 liter of 28% ammonium hydroxide in 600 cc. of water was added with stirring. The precipitate was filtered; dried and ignited at 400 C. The ignition residue was then extracted twice with 10% acetic acid, washed and dried. Twenty grams of this copper barium chromite was agitated with 340 g. of ethyl alpha-hydroxy isobutyrate under a hydrogen pressure of 2500 pounds per square inch. Hydrogen absorption was rapid at about 200 C. and the reaction was complete in about one hour. On distillation of the product, there was obtained a 91% yield of 2-methyl propane diol-1,2.
Example VI One hundred fifty grams of ethyl citrate'and 12 g. of the copper barium chromite catalyst prepared as described in Example V were charged into a steel reaction tube built to withstand high pressure. The tube was agitated for 4.5 hours at a temperature of 240 C. and a hydrogenation From the reaction product there was isolated 25 g. of a trihydric alcohol (trimethyiol propane) and an oily residue containing a substantial quantity of a cyclic ether alcohol, the constitution of which was not fully determined.
Example VII Fifteen hundred grams of copper nitrate dissolved in 4 liters of water was mixed with a solution containing 1000 g. of ammonium chromate in an equal volume of water. Ammonium hy-, droxide was added to neutralize the acidity developed during precipitation of the copper ammonium chromate. The precipitate was washed by decantation, filtered, and dried, after which it was ignited at a temperature of 400 .C. The ignition residue was then extracted twice with 10% acetic acid, washed and dried.
Two hundred grams of gamma hydroxy valeric ester was subjected to hydrogenation in the pres- Example VIII Three hundred and twenty grams of a copperbarium-chromite catalyst prepared as described in Example V and 4000 grams of 12-hydroxy stearin (hardened castor oil) were placed in a stirring autoclave and hydrogen was introduced to a pressure of 3000 pounds per square inch which was maintained throughout the run. The
;mixture was then heated to 260 C. and agitated for seven hours, after which hydrogen absorption had ceased. After removal of the products from the autoclave and filtering, the alcohols thus obtained solidified to a hard solid having a melting point of about. 65 C. The decrease in saponification number of the oil during hydrogenation corresponded to a 92% conversion of the carboxyl groups, while the hydroxyl value of 347 obtained by analysis of the product indicated a substantially complete conversion of the hydroxy stearin to the corresponding octadecanediol-1,12.
' Example IX Sixteen grams of a copper chromite catalyst prepared as described in Example IV, 0.4 g. of magnesium oxide, and 200 g. of ethyl hydroxystearate were charged into a steel reaction tube Example X Copper carbonate was prepared by dissolving 720 g. of copper nitrate trihydrate in 1 liter of water and heating the solution to 40 C. and slowly adding with agitation during a period of one hour a solution consisting of 300 g. of sodium carbonate dissolved in 3 liters of water. The precipitate thus formed was washed four times by decantation using 5liters of distilled water for each wash, after which it was filtered, dried at C., and ground to a fine powder. An intimate mixture consisting of 25% of copper carbonate prepared as described and 75% of copper barium chromite prepared as described in Example V was made by grinding the two components in a mortar. Sixteen grams of the above catalyst mixture and 200 g. of castor oil were heated in a steel reaction tube to a temperature of 260 C. under a'hydrogen pressure of 3000 pounds per square inch with continuous agitation for a period of 12 hours, during which time a reduction in saponification value of the oil occurred equivalent to 99% conversion of the carboxyl group while the iodine number was reduced to less than 1.0. The hydroxyl value of the prodcontact of the material treated with the catalyst have been indicated in the above examples, it will be apparent that these factors may be varied within wide limits within the scope of my invention. The catalytic reduction of hydroxy acids, their esters, and their anhydrides to alcohols or glycols requires the use of temperatures and pressures appreciably higher than customarily employed for other hydrogenation reactions. The temperature may range from above 200 C. up to 500 C. The preferred temperature range is 240 to 400 C., depending somewhat on the catalyst-- pressures in excess of atmospheres, while the preferred pressure is 50 to 400 atmospheres. The maximum pressure which can be used is limited only by the strength ,of the reaction apparatus.
I and hydrogen.
Whereas the critical factors and inventive steps in the hydrogenation of hydroxy-carboxylic compounds to glycols are the use of high temperatures and pressures, it necessarily follows that suitable catalysts -may be selected from among a number of different hydrogenating metals and oxides.
Mild-acting hydrogenating catalysts such as metallic copper and zinc oxide which are well known to be suitable for the synthesisof methanol from carbon monoxide and hydrogen are in general also suitable catalysts for the production of glycols. On the other hand; there are certain very energetic catalysts such as metallic nickel and iron which are known to catalyze the formation of hydrocarbons from oxides of carbon These ferrous metal catalysts, when employed in the hydrogenation of hydroxy acids and their esters, tendto carry the reaction too far with the formation of hydrocarbons. Therefore, if the hydrogenation is to be operated for the production of alcohols and glycols to the substantial exclusion of hydrocarbons, it is preferable to select as the catalyst a composition comprising a member of the group of non-ferrous hydrogenating metals such as copper, tin, silver, cadmium, zinc, lead, their oxides and chromites, and oxides and chromites of manganese, and magnesium. Especially good results are obtained with finely divided copper oxide, either wholly or partially reduced and preferably supported upon an inert surface-extending material such as kieselguhr, or promoted by such oxide promoters as manganese oxide, zinc oxide, magnesium oxide, or chromium oxide. The above mentioned mild-acting catalysts may be termed the alcohol-forming catalysts to distinguish them from the more energetic hydrocarbon-forming elements of the platinum and ferrous metal'groups. Elementary nickel, cobalt, and iron, when suitably supported on kieselguhr, may be used to effect the reduction of carboxylic compounds with hydrogen, but in these cases the product contains besides alcoholic bodies a preponderance of hydrocarbons, and this disadvantage in most cases will prove so serious as to preclude the use of these catalysts unless the hydrocarbons themselves are the desired end products.
Catalysts suitable for use in the liquid phase batch method of hydrogenation are preferably prepared in a powder form. The preferred catalyst for this purpose is usually a copper chromite prepared by igniting a double copper amaooaeu monium chromate to its spontaneous decomposition temperature as described in U. 8. Patent 1,746,783. Many modifications of this procedure have been practiced involving the use of acid. extraction, hydrogen reduction, and the use of a supplementary support such as kieselguhr, but these are modifications in degree only. The es- :sential feature is the use oi copper oxide intimately associated or combined with chromium sesquioxide and the chromite method of preparation is a convenient method for effecting the desired association. The method, however, is not limited to copper but may be practiced in the preparation also of zinc chromite, silver chromite, manganese chromite, etc.-
For use in the continuous flow method of hydrogenation certain metal oxides belonging to the class of difllcultly reducible hydrogenating oxides may be conveniently employed on account of their rugged character and the ease with which they may be-shaped into hard granules for loading into stationary apparatus. By the term diflicultly reducible" is meant that the oxides are not substantially reduced to metal by prolonged exposure in a state of purity to the action of hydrogen at atmospheric pressure and at a temperature of 400 to 450 C. Such oxides suitable for use as catalysts in the hydrogenation of hydroxy-carboxylic compounds are zinc oxide, manganese oxide, and magnesium oxide. These oxides may be employed either alone or in combination with each other or with other metals or oxides which have a promoting action. Preferably the dimcultly reducible hydrogenating oxides also are prepared in the form of chromites as already indicated in the examples.
Hydroxy acids and their derivatives are particularly susceptible to partial dehydration, and it has been found that this undesirable side reaction may be largely prevented by employing a mild inorganic base added to the hydrogenation catalyst. For example, products having much higher hydroxyl values are obtained if a little magnesia, zinc oxide, lime, or barium hydrate is added to the catalyst or to the reaction system. Preferably the alkali earth buffer is incorporated into the catalyst at the time of its precipitation.
In carrying out the hydrogenation of hydroxycarboxylic compounds in a continuous reaction system, the rate at which the ester may be pumped over the catalyst with satisfactory results is a function of the catalytic activity and also of the molecular weight of the ester. An active hydrogenating catalyst will ordinarily convert eight times its volume of ester per hour. Higher rates of flow of the ester may be employed at the expense of slightly lower conversion.
The processes of the present invention are applicable to a large number of hydroxy-carboxylic acids, their esters and anhydrides, for example, lactic, ricinoleic, hydroxy-butyric and -isobutyric, hydroxy-valeric, hydrcxy-stearic acids, etc.- As indicated, these acids may be employed for hydrogenation in the form of the free acid or as their esters or anhydrides. The same glycols are obtained on hydrogenation irrespective of the form in which the hydroxy-carboxylic compound is treated. The ester may be a mono-alkyl ester or an ester of a polyhydric alcohol such as glycerol. The hydroxy acid may be unsaturated as in the case of ricinoleic acid or fully saturated as in the case of hydroxy-stearic acid. The hydrogenation of these acids and their derivatives lead to a very interesting new glycol, i. e., octadecanediol-LIZ.
Castor oil is a glyceride of ricinoleic acid, and complete or partial reduction of the carboncarbon unsaturation may occur as in the usual hydrogenation process of the prior art, but in the present process this is only incidental to the more-important reaction of hydrogenation of the ester groupwhich results in the formation of alcohols. As an added step in my invention, I
- sometimes prefer after conducting the reaction as indicated above to favor alcohol formation, to hydrogenate the reaction products at low pres sure and temperature with a nickelcatalyst in the usual manner known to the art. This brings all the reaction products up to the same level of hydrogen saturation, yielding new compositions, the most important of which is octadecanediol. Alternatively, the hydrogenation with nickel may precede the carboxylic hydrogenation carried out for the purposes of converting the carboxyl groups to' carbinol groups, as, for example, in the conversion of ethyl. ricinoleate to the hydroxy stearate followed by conversion to octadecanediol.
The hydrogenation products obtained by the hydrogenation of castor oil under the conditions of the present invention consist of a mixture of higher alcohols and other products and this mixture in itself constitutes a new composition of matter, which in some instances finds use in the arts without any separation of the product into its components. In such cases, as well as when it is not feasible to separate the alcohols from the other hydrogenation products, the presence of the alcohols and the amount thereof formed may be demonstrated conclusively by determination of the acetyl or hydroxyl values.
Depending on the conditions of hydrogenation, a part of the secondary hydroxyl group of octadecanediol may be split off, giving a monohydric alcohol as one of the products. The method for isolating the glycol disclosed in Example I involves saponification and extraction. A more simple procedure for commercial operation consists in hydrogenating ricinoleic acid or its esters rather completely and separating the glycol produced by direct vacuum fractional distillation of the crude hydrogenated product. The wax residue may then be put through the hydrogenation step again, together with fresh raw material.
From the foregoing it will be apparent that I have developed an economic method for obtaining octadecanediol- 1,12 from castor oil, ricinoleic acid, ethyl ricinoleate, ethyl hydroxy stearate, hydroxystearin, etc., without the use of expensive chemical reagents and at a'small. cost per unit of product. In addition, I have made possible the preparation of novel alcohols and other derivatives from castor oil. Octadecanediol, the new saturated alcohol described above, has many unique properties which make it of value for many industrial applications, whether it be in pure or in crude form. It is suitable for use as a cosmetic base when combined with face creams, especially those of the vanishing type. Its waxy properties may be utilized in paper or other finishes or in furniture, floor or automobile polishes. It is suitable for use in compounding rubber or in synthetic resins and as a softener for coating compositions. As a component of soap, octadecanediol contributes to detergent power in the presence of hard water and tends to counteract the harshness of soaps. The derivatives of octadecanediol such as esters thereof find use as softeners, for example, in nitrocellulose compositions, and the sulfonated octadecanediol is a. valuable wetting-out agent and detergent.
The above examples and descriptions are intended to be illustrative only and not as limiting the scope of the invention. Any modifications or variations thereof wh ch conform to the spirit of the invention are intended to be included within the scope of the claims.
I claim:
1. A process for producing alcohols from hydroxy carboxylic compounds, which comprises bringing hydrogen and amember of the class consisting of the hydroxy carboxylic acids, and their esters into contact with a mild-acting hydrogenation catalyst at a temperature in excess of 200 C. and at a pressure in excess of 10 atmospheres.
2. Process according to claim 1 characterized in that the temperature is maintained between 200 and 500", C.
3. Process according to claim 1 characterized in that the temperature is maintained between 240 and 400 C.
4.'Process according to claim .1 characterized in that thepressure is maintained between and 400 atmospheres.
5. Process according to claim 1 characterized in that the catalyst is a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites.
6. Process according to claim 1 characterized in that the catalyst is a mild-acting alcohol forming hydrogenation catalyst.
'7. Process according to claim 1 characterized in that the catalyst is a catalyst containing copper as an essential ingredient.
8. Process according to claim 1 characterized in that the catalyst comprises essentially a mixed chromite of cadmium, copper and zinc.
9. Process according to claim 1 characterized in that the catalyst comprises essentially a (hillcultly reducible hydrogenating metal oxide.
10. Process according to claim 1 characterized in that the catalyst comprises essentially a mixture of difficultly reducible hydrogenating metal oxides.
11. Process according to claim 1 characterized in that the catalyst comprises essentially a chrosure slightly in excessof atmospheric and at a v temperature between 50 and 200 C. in the presence of a nickel catalyst in order to saturate the carbon-carbon bond, then subjecting the products produced by the second hydrogenation step to separation and purification.
16. A' process for producing a glycol, which comprises bringing hydrogen and a hydroxy carboxylic acid into contact with a mild-acting hydrogena'tion catalyst at a temperature in excesspheres. Y 17. Process according to claim 16 characterized that the' catalyst is a hydrogenation catalyst .01 the class consisting of mild acting hydrogenatin that the catalyst contains as essential ingredients chromites of copper and barium.
20. .4 process for producing a glycol, which comprises bringing hydrogen and an ester of hydroxy carboxylic acid into contact with a mildacting hydrogenation catalyst. at a temperature in excess of 200 C. and at a pressure in excess 01' atmospheres.
21. Process according to claim 20 characterized in that the catalyst is a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such-metals, oxides and chromites.
22. Process according to claim 20 characterized in that the catalyst contains a small amount of an alkali earth buffer.
23. Process according to claim 20 characterize in thatthe catalyst contains as essential ingredients chromites of copper and barium.
24. A process for producing a glycol, which comprises bringing hydrogen and ricinoleic acid into contact with a mild-acting hydrogenation catalyst at a temperature in-excess of 200 C.
and at a pressure in excess of 10 atmospheres.
25. The process according to claim 24 characterized in that the catalyst is a difllcultly reducibleoxide of a hydrogenating metal.
26. The process according to claim 24 characterized in that the catalyst is a mixture of difllcultly reducible oxides by hydrogenating metals.
27. The process according to claim 24 characterized in that the catalyst comprises essentially a chromite of a hydrogenating metal.
28. The process according to claim 24 characterized in that the catalyst comprises essentially a mixture of chromites of hydrogenating metals.
29. The process according to claim 24 characterized in that the reaction is carried out in the vapor phase and hydrogen is present in excess.
30. The process according to claim 24 characterized in that the reaction is carried out at a temperature between 300 and 400 C.
31. The process according to claim 24 characterized in that the reaction is carried out at a pressure between 100 and 250 atmospheres.
32. The process according to claim 24 characterized in that the reaction is carried out at a temperature between 300 and 400 C. and at a pressure between 100 and 250 atmospheres.
33. A process for producing alcohols from castor oil, which comprises saponifying castor oil to form an acid, passing said acid and hy-- drogen over a hydrogenation catalyst of the class consisting of mild acting hydrogenating metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides, and chro- 2,094,041 of 200 C. and at a pressure in excess of -10 atmosmites at a temperature in excess oi! 200 C. and at a pressure in excess or 10 atmospheres.
34. The process according to claim 33 characterized in that the hydrogenated reaction products are subjected to further hydrogenation to remove the carbon-carbon unsaturation. 35. A process for producing alcohols from castor oil, which comprises saponifyin'g castor oil to form an acid, then passing said acid and hydrogen over a mixture 01' the chromites of zinc, copper, and cadmium at a temperature of about 380 C. and at a pressure of about 2500 to 3000 pounds per square inch.
36. A process for producing alcohols 'from ricinoleyl derivatives which comprises passing ricinoleic acid .and hydrogen over a hydrogenation catalyst of the class consistingo! mild acting hydrogenating metals, their oxides and chromites, theoxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites at a temperature in excess of 200 ,C. and at a pressure in excess oi! 10 atmospheres, separating the glycol produced by direct vacuum distillation of the crude hydrogenated product.
37. Process according to claim 24 character- 40. Process according to claim 24 characterized in that the hydrogenated reaction products are subjected to further hydrogenation to remove the carbon-carbon unsaturation and then recovering the octadecanediol formed.
41. Process according to claim 24 characterized in that the hydrogenated reaction products are subjected to further hydrogenation under a pressure slightly in .excess of atmospheric and 'at a temperature between 50 and 250 C.- in the presence of a nickel catalyst to saturate the carbon-carbon bond; then separating and purifying the octadecanediol formed.
42. A composition containing essentially an alcohol which is obtainable by the hydrogenation of ricinoleic acid, at a temperature in excess of.
200 C. and at a pressure in excess of 10 atmospheres, in the presence of a mild-acting hydrogenation catalyst.
43. A process of producing a glycol which comprises bringing hydrogen and an ester of ricinoleic acid into contact with a mild-acting hydrogena tion catalyst at a temperature in excess of 200 C. and at a pressure in excess 01' 10 atmospheres.
44. The process according to claim 43 characterized in that the catalyst is a difflcultly reducible oxide of a hydrogenating metal.
45. The process according to claim 43 characterized in that the catalyst is a mixture of difllcultly reducible oxides of hydrogenating metals.
46. The process according to claim 43 characterized in that the catalyst comprises essentially a chromite of a hydrogenating metal.
47. The process according to claim 43 characterized in that the catalyst comprises essentially a mixture of chromites of hydrogenating metals.
48. The process according to claim 43 characterized in that the reaction is carried out in the vapor phase and hydrogen is present in excess.
49. The process according to claim 43 characterized in that the reaction is carried out at a temperature between 300 and 400 C.
50. The process according to claim 43 characterized in that the reaction is carried out at a pressure between 100 and 250 atmospheres.
51. The process according to claim 43 characterized in that the reaction is carried out at a temperature between 300 and 400 C. and at a pressure between 100 and 250 atmospheres.
52. A process for producing alcohols from castor oil, which comprises passing castor oil and hydrogen over a mixture of the chromites or zinc; copper, and cadmium at a temperature 01 about 300-400 C. and at a pressure of about 2700 pounds per square inch.
53. A composition containing essentially octadecanedio1-1,12. I
54. Octadecanediol-1,12.
55. A process for producing a glycol whichv comprises bringing hydrogen and castor oil into contact with a mild-acting hydrogenation catalyst at a temperature in excess of 200 C. and'at a pressure in excess of 10 atmospheres.
56. The process according to claim 55 characterired in that the catalyst .is a hydrogenation catalyst of the class consisting of mild acting hydrogenatlng metals, their oxides and chromites, the oxides and chromites of manganese and magnesium, and mixtures of such metals, oxides and chromites.
57. The process according to claim 55 characterized in that the catalyst contains a small amount of an alkaline earth bufler.
, 58. The process according to claim 55 characterized in that the catalyst contains as essential ingredients chromites of copper and barium.
59. The process according to claim 55 characterized in that the hydrogenated reaction products are subjected to further hydrogenation to remove the carbon-carbon unsaturation and then recovering the octadecanediol formed.
60. The process according to claim 55 characterized' in that the hydrogenated reaction. products are subjected to further hydrogenation under a pressure slightly inexcess of atmospheric and at a temperature between and 250 C.;in the presence of a nickel catalyst to saturate the carbon-carbon bond, then separating and purifying the octadecanediol formed.
61. A mixture of alcohols obtainable by the carboxyl hydrogenation of castor oil.
62. A mixture of alcohols obtainable by the carboxyl hydrogenation of castor oil followed by the hydrogenation of the resulting product with a nickel catalyst in order to remove the carbon-carbon unsaturation.
63. A mixture of alcohols obtainable by the carboxyl hydrogenation of the mixture of acids obtained by the hydrolysis of castor oil. v
64. A mixture of alcohols obtainable by the carboxyl hydrogenation of the mixture of acids obtained by the hydrolysis of castor oil followed by the hydrogenation of the resulting product with a nickel catalyst in order to remove the WILBUR A. LAZIERn
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2451333A (en) * | 1945-04-28 | 1948-10-12 | Du Pont | Synthesis of polyhydroxy compounds |
US2524566A (en) * | 1947-06-11 | 1950-10-03 | Shell Dev | Production of copper-magnesia hydrogenation catalyst and its use in hydrogenation reactions |
US2599468A (en) * | 1949-11-17 | 1952-06-03 | Rohm & Haas | Nonadecyl glycols |
US2607805A (en) * | 1949-06-10 | 1952-08-19 | Du Pont | Hydrogenation of glycolic acid to ethylene glycol |
US2911444A (en) * | 1957-11-29 | 1959-11-03 | Hooker Chemical Corp | Hydrogenation of esters of perfluorinated dicarboxylic acids |
US2922764A (en) * | 1954-10-28 | 1960-01-26 | Elgin Nat Watch Co | Ricinoleyl lubricants |
US2975218A (en) * | 1956-09-14 | 1961-03-14 | Ruhrchemie Ag | Production of dialcohols |
US3052730A (en) * | 1959-03-03 | 1962-09-04 | Givaudan Corp | Process for making citronellol and intermediate therefor and novel intermediates made thereby |
US4214106A (en) * | 1977-04-07 | 1980-07-22 | Hoechst Aktiengesellschaft | Process for the preparation of ethylene glycol |
US4268695A (en) * | 1978-10-21 | 1981-05-19 | Chemische Werke Huls Aktiengesellschaft | Process for the continuous preparation of butane-1,4-diol |
US4409395A (en) * | 1981-01-26 | 1983-10-11 | Ube Industries, Ltd. | Process for the production of glycollic acid esters |
US4851593A (en) * | 1987-10-13 | 1989-07-25 | Sherex Chemical Company | Dihydroxy or polyhydroxy compounds and process for producing same |
EP1010682A1 (en) * | 1998-12-16 | 2000-06-21 | Mitsubishi Gas Chemical Company, Inc. | Method of producing isobutylene glycol |
US20050283029A1 (en) * | 2002-11-01 | 2005-12-22 | Xiangsheng Meng | Process for preparation of 1,3-propanediol |
-
1934
- 1934-12-11 US US757071A patent/US2094611A/en not_active Expired - Lifetime
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2451333A (en) * | 1945-04-28 | 1948-10-12 | Du Pont | Synthesis of polyhydroxy compounds |
US2524566A (en) * | 1947-06-11 | 1950-10-03 | Shell Dev | Production of copper-magnesia hydrogenation catalyst and its use in hydrogenation reactions |
US2607805A (en) * | 1949-06-10 | 1952-08-19 | Du Pont | Hydrogenation of glycolic acid to ethylene glycol |
US2599468A (en) * | 1949-11-17 | 1952-06-03 | Rohm & Haas | Nonadecyl glycols |
US2922764A (en) * | 1954-10-28 | 1960-01-26 | Elgin Nat Watch Co | Ricinoleyl lubricants |
US2975218A (en) * | 1956-09-14 | 1961-03-14 | Ruhrchemie Ag | Production of dialcohols |
US2911444A (en) * | 1957-11-29 | 1959-11-03 | Hooker Chemical Corp | Hydrogenation of esters of perfluorinated dicarboxylic acids |
US3052730A (en) * | 1959-03-03 | 1962-09-04 | Givaudan Corp | Process for making citronellol and intermediate therefor and novel intermediates made thereby |
US4214106A (en) * | 1977-04-07 | 1980-07-22 | Hoechst Aktiengesellschaft | Process for the preparation of ethylene glycol |
US4268695A (en) * | 1978-10-21 | 1981-05-19 | Chemische Werke Huls Aktiengesellschaft | Process for the continuous preparation of butane-1,4-diol |
US4409395A (en) * | 1981-01-26 | 1983-10-11 | Ube Industries, Ltd. | Process for the production of glycollic acid esters |
US4851593A (en) * | 1987-10-13 | 1989-07-25 | Sherex Chemical Company | Dihydroxy or polyhydroxy compounds and process for producing same |
EP1010682A1 (en) * | 1998-12-16 | 2000-06-21 | Mitsubishi Gas Chemical Company, Inc. | Method of producing isobutylene glycol |
US6194618B1 (en) | 1998-12-16 | 2001-02-27 | Mitsubishi Gas Chemical Company, Inc. | Method of producing isobutylene glycol |
US20050283029A1 (en) * | 2002-11-01 | 2005-12-22 | Xiangsheng Meng | Process for preparation of 1,3-propanediol |
US7126034B2 (en) | 2002-11-01 | 2006-10-24 | Cargill, Incorporated | Process for preparation of 1,3-propanediol |
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