CA1082231A - Process for the preparation of ethylene glycol - Google Patents
Process for the preparation of ethylene glycolInfo
- Publication number
- CA1082231A CA1082231A CA283,414A CA283414A CA1082231A CA 1082231 A CA1082231 A CA 1082231A CA 283414 A CA283414 A CA 283414A CA 1082231 A CA1082231 A CA 1082231A
- Authority
- CA
- Canada
- Prior art keywords
- oxalate
- hydrogen
- copper
- ethylene glycol
- chromite
- 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
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 69
- 239000001257 hydrogen Substances 0.000 claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 56
- 239000012808 vapor phase Substances 0.000 claims abstract description 19
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940039748 oxalate Drugs 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 44
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 32
- -1 oxalate ester Chemical class 0.000 claims description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- CXQXWHWPDDUDPI-UHFFFAOYSA-N [Cu+2].[Zn+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O Chemical compound [Cu+2].[Zn+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O CXQXWHWPDDUDPI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229940083542 sodium Drugs 0.000 claims description 6
- 235000015424 sodium Nutrition 0.000 claims description 6
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- VGZOEDUWOQJGDE-UHFFFAOYSA-N [Cu+2].[Ba+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O Chemical compound [Cu+2].[Ba+2].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O VGZOEDUWOQJGDE-UHFFFAOYSA-N 0.000 claims 4
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 claims 3
- 230000036647 reaction Effects 0.000 claims 3
- 229920000136 polysorbate Polymers 0.000 claims 1
- 150000003901 oxalic acid esters Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 150000002148 esters Chemical class 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000012263 liquid product Substances 0.000 description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 2
- BGLAMXJBTZOWLK-UHFFFAOYSA-N 3-[[4-acetyl-2,3,6-trihydroxy-5-(3-methylbut-2-enyl)phenyl]methyl]-4-hydroxy-5,6-dimethylpyran-2-one Chemical compound OC1=C(C(C)=O)C(CC=C(C)C)=C(O)C(CC=2C(OC(C)=C(C)C=2O)=O)=C1O BGLAMXJBTZOWLK-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate trihydrate Substances [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 229960004275 glycolic acid Drugs 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000004028 organic sulfates Chemical class 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZNLAHAOCFKBYRH-UHFFFAOYSA-N 1,4-dioxane-2,3-dione Chemical compound O=C1OCCOC1=O ZNLAHAOCFKBYRH-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 101100116570 Caenorhabditis elegans cup-2 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100116572 Drosophila melanogaster Der-1 gene Proteins 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IGDGIZKERQBUNG-UHFFFAOYSA-N [Cu].[Ba] Chemical compound [Cu].[Ba] IGDGIZKERQBUNG-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- GJRRTUSXQPXVES-UHFFFAOYSA-N bis(2-methylpropyl) oxalate Chemical compound CC(C)COC(=O)C(=O)OCC(C)C GJRRTUSXQPXVES-UHFFFAOYSA-N 0.000 description 1
- VFGRALUHHHDIQI-UHFFFAOYSA-N butyl 2-hydroxyacetate Chemical compound CCCCOC(=O)CO VFGRALUHHHDIQI-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XAHVPYNDLCTDTE-UHFFFAOYSA-N dipentyl oxalate Chemical class CCCCCOC(=O)C(=O)OCCCCC XAHVPYNDLCTDTE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- CWGGWXROONYCTQ-UHFFFAOYSA-N ethene;oxalic acid Chemical group C=C.OC(=O)C(O)=O CWGGWXROONYCTQ-UHFFFAOYSA-N 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- LJFCDOMDEACIMM-UHFFFAOYSA-N zinc chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[Zn+2] LJFCDOMDEACIMM-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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US715,747 | 1976-08-18 | ||
| US05/715,747 US4112245A (en) | 1976-08-18 | 1976-08-18 | Process for the preparation of ethylene glycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082231A true CA1082231A (en) | 1980-07-22 |
Family
ID=24875318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,414A Expired CA1082231A (en) | 1976-08-18 | 1977-07-25 | Process for the preparation of ethylene glycol |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4112245A (index.php) |
| JP (1) | JPS5323911A (index.php) |
| BE (1) | BE857722A (index.php) |
| CA (1) | CA1082231A (index.php) |
| DE (1) | DE2736070C3 (index.php) |
| ES (1) | ES461485A1 (index.php) |
| FR (1) | FR2362103A1 (index.php) |
| GB (1) | GB1570948A (index.php) |
| IT (1) | IT1079910B (index.php) |
| NL (1) | NL170845C (index.php) |
Families Citing this family (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1099070B (it) * | 1978-09-14 | 1985-09-18 | Montedison Spa | Processo per la idrogenazione catalitica degli esteri ossalici |
| IN154274B (index.php) * | 1980-09-02 | 1984-10-13 | Ube Industries | |
| JPS57122940A (en) * | 1981-01-26 | 1982-07-31 | Ube Ind Ltd | Hydrogenation catalyst of oxalic diester |
| JPS57123143A (en) * | 1981-01-26 | 1982-07-31 | Ube Ind Ltd | Production of glycolic ester |
| BR8201302A (pt) * | 1981-03-12 | 1983-01-25 | Union Carbide Corp | Processo para a preparacao de etileno glicol |
| IT1190783B (it) * | 1981-04-29 | 1988-02-24 | Davy Mckee Oil & Chem | Processo per l'idrogenolisi di esteri di acidi carbossilici |
| JPS58207945A (ja) * | 1982-05-28 | 1983-12-03 | Ube Ind Ltd | シユウ酸ジエステルの水素添加用触媒 |
| LU84912A1 (fr) * | 1983-07-14 | 1985-04-17 | Oleofina Sa | Procede de production d'alcools |
| GB8331793D0 (en) * | 1983-11-29 | 1984-01-04 | Davy Mckee Ltd | Process |
| CA1238627A (en) * | 1984-01-27 | 1988-06-28 | Koichi Hirai | Process for producing ethylene glycol, catalyst composition therefor and process for producing the catalyst composition |
| GB8514002D0 (en) * | 1985-06-04 | 1985-07-10 | Davy Mckee Ltd | Process |
| US4628129A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol |
| US4628128A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol by catalytic hydrogenation |
| US4652685A (en) * | 1985-11-15 | 1987-03-24 | General Electric Company | Hydrogenation of lactones to glycols |
| US4649226A (en) * | 1986-03-27 | 1987-03-10 | Union Carbide Corporation | Hydrogenation of alkyl oxalates |
| GB8717989D0 (en) * | 1987-07-29 | 1987-09-03 | Davy Mckee Ltd | Catalyst |
| EP0614875A1 (en) * | 1993-03-12 | 1994-09-14 | Ube Industries, Ltd. | Method of producing a glycolic acid ester |
| US6191321B1 (en) | 1998-09-30 | 2001-02-20 | Shell Oil Company | Process for preparing 1,3-propanediol from methyl 3-hydroxypropionate |
| DE102007020146A1 (de) * | 2007-04-26 | 2008-10-30 | Bayer Materialscience Ag | Verfahren zur Reinigung und Oxidation eines Chlorwasserstoff enthaltenden Gases |
| US7615671B2 (en) | 2007-11-30 | 2009-11-10 | Eastman Chemical Company | Hydrogenation process for the preparation of 1,2-diols |
| GB0803663D0 (en) * | 2008-02-28 | 2008-04-09 | Davy Process Techn Ltd | Process |
| CN101475441B (zh) * | 2008-12-18 | 2012-05-09 | 中国石油化工股份有限公司 | 草酸酯生产乙二醇的方法 |
| BRPI0913770B1 (pt) * | 2008-12-18 | 2017-09-12 | China Petroleum & Chemical Corporation | Process for the production of ethylene glycol from an oxalate |
| CN101475442B (zh) * | 2008-12-18 | 2011-11-30 | 中国石油化工股份有限公司 | 由草酸酯生产乙二醇的方法 |
| CN101879448B (zh) | 2010-06-24 | 2012-05-23 | 天津大学 | 用于草酸酯加氢制乙二醇的规整结构催化剂及其制备方法 |
| US8829248B2 (en) | 2010-08-18 | 2014-09-09 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US9227896B2 (en) | 2010-08-18 | 2016-01-05 | Eastman Chemical Company | Process for the separation and purification of a mixed diol stream |
| US8466328B2 (en) | 2010-08-18 | 2013-06-18 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US8709376B2 (en) | 2010-09-23 | 2014-04-29 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8785686B2 (en) | 2010-09-23 | 2014-07-22 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| WO2012113267A1 (zh) * | 2011-02-25 | 2012-08-30 | 中国石油化工股份有限公司 | 草酸酯通过流化床催化反应生产乙二醇的方法 |
| CN102775274B (zh) * | 2011-05-13 | 2015-01-21 | 中国石油化工集团公司 | 一种草酸酯加氢制乙二醇的系统及方法 |
| US8765999B2 (en) | 2012-03-27 | 2014-07-01 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst |
| US8703999B2 (en) | 2012-03-27 | 2014-04-22 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst |
| US8829234B2 (en) | 2012-03-27 | 2014-09-09 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and heterogeneous catalyst |
| US8927766B2 (en) | 2012-03-27 | 2015-01-06 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of a propionic acid and a homogeneous catalyst |
| US9040748B2 (en) | 2012-06-08 | 2015-05-26 | Eastman Chemical Company | Hydrocarboxylation of aqueous formaldehyde using a dehydrating recycle stream to decrease water concentration |
| US10086364B2 (en) | 2014-06-26 | 2018-10-02 | University Of Wyoming | Methods of catalytic hydrogenation for ethylene glycol formation |
| US10800987B2 (en) | 2014-06-27 | 2020-10-13 | University Of Wyoming | Composite iron-sodium catalyst for coal gasification |
| CN104478658B (zh) * | 2014-11-26 | 2017-05-03 | 西南化工研究设计院有限公司 | 一种加氢反应过程中降低氢气循环量的工艺及设备 |
| JP6790066B6 (ja) * | 2015-07-29 | 2020-12-16 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | モノエチレングリコールの製造方法 |
| US10266467B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Synthesis of glycols via transfer hydrogenation of alpha-functional esters with alcohols |
| US10266466B2 (en) | 2017-08-02 | 2019-04-23 | Eastman Chemical Company | Iron-catalyzed transfer hydrogenation of esters to alcohols |
| US10435349B2 (en) | 2017-08-02 | 2019-10-08 | Eastman Chemical Company | Iron-catalyzed cross-coupling of methanol with secondary or tertiary alcohols to produce formate esters |
| US10570081B2 (en) | 2017-08-02 | 2020-02-25 | Eastman Chemical Company | Process for making formic acid utilizing lower-boiling formate esters |
| US10544077B2 (en) | 2017-08-02 | 2020-01-28 | Eastman Chemical Company | Process for making formic acid utilizing higher-boiling formate esters |
| CN112759505B (zh) * | 2019-10-21 | 2024-01-30 | 中国石油化工股份有限公司 | 一种制备乙二醇的方法及系统 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2091800A (en) * | 1931-09-15 | 1937-08-31 | Rohm & Haas | Method of hydrogenating esters |
| US2060880A (en) * | 1933-09-23 | 1936-11-17 | Du Pont | Process of producing ethylene glycol |
| US2285448A (en) * | 1937-10-30 | 1942-06-09 | Du Pont | Preparation of polyhydric alcohols |
| GB575380A (en) | 1940-08-16 | 1946-02-15 | Du Pont | Improvements in and relating to the production of ethylene glycol |
-
1976
- 1976-08-18 US US05/715,747 patent/US4112245A/en not_active Expired - Lifetime
-
1977
- 1977-07-25 CA CA283,414A patent/CA1082231A/en not_active Expired
- 1977-08-02 IT IT50539/77A patent/IT1079910B/it active
- 1977-08-08 NL NLAANVRAGE7708734,A patent/NL170845C/xx not_active IP Right Cessation
- 1977-08-09 ES ES461485A patent/ES461485A1/es not_active Expired
- 1977-08-10 DE DE2736070A patent/DE2736070C3/de not_active Expired
- 1977-08-11 BE BE180114A patent/BE857722A/xx not_active IP Right Cessation
- 1977-08-16 FR FR7725037A patent/FR2362103A1/fr active Granted
- 1977-08-17 GB GB34552/77A patent/GB1570948A/en not_active Expired
- 1977-08-17 JP JP9861377A patent/JPS5323911A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2736070B2 (de) | 1981-04-30 |
| NL170845B (nl) | 1982-08-02 |
| NL170845C (nl) | 1983-01-03 |
| IT1079910B (it) | 1985-05-13 |
| BE857722A (fr) | 1978-02-13 |
| NL7708734A (nl) | 1978-02-21 |
| FR2362103A1 (fr) | 1978-03-17 |
| JPS5323911A (en) | 1978-03-06 |
| DE2736070A1 (de) | 1978-02-23 |
| ES461485A1 (es) | 1978-06-01 |
| DE2736070C3 (de) | 1982-04-15 |
| US4112245A (en) | 1978-09-05 |
| FR2362103B1 (index.php) | 1984-02-03 |
| JPS5542971B2 (index.php) | 1980-11-04 |
| GB1570948A (en) | 1980-07-09 |
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Legal Events
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| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19970722 |