JP2017519007A - 低vocグリコールエーテルエステルを生成するプロセス - Google Patents
低vocグリコールエーテルエステルを生成するプロセス Download PDFInfo
- Publication number
- JP2017519007A JP2017519007A JP2016572640A JP2016572640A JP2017519007A JP 2017519007 A JP2017519007 A JP 2017519007A JP 2016572640 A JP2016572640 A JP 2016572640A JP 2016572640 A JP2016572640 A JP 2016572640A JP 2017519007 A JP2017519007 A JP 2017519007A
- Authority
- JP
- Japan
- Prior art keywords
- glycol ether
- process according
- glycol
- reaction
- crude product
- 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.)
- Granted
Links
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 56
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 33
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 33
- -1 glycol ether ester Chemical class 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000012043 crude product Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 34
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 29
- 238000000605 extraction Methods 0.000 claims description 23
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 241001550224 Apha Species 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000004886 process control Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 2
- OVHVRKVWWGAWHO-UHFFFAOYSA-N benzoic acid;2-butoxyethanol Chemical group CCCCOCCO.OC(=O)C1=CC=CC=C1 OVHVRKVWWGAWHO-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 235000019645 odor Nutrition 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- NMBQBIACXMPEQB-UHFFFAOYSA-N 2-butoxyethyl benzoate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1 NMBQBIACXMPEQB-UHFFFAOYSA-N 0.000 description 5
- 230000009965 odorless effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000006641 Fischer synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000013529 heat transfer fluid Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- TZHGOJUYMUTMTF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC1=CC=CC=C1 TZHGOJUYMUTMTF-UHFFFAOYSA-N 0.000 description 1
- LCVQGUBLIVKPAI-UHFFFAOYSA-N 2-(2-phenoxypropoxy)propan-1-ol Chemical compound OCC(C)OCC(C)OC1=CC=CC=C1 LCVQGUBLIVKPAI-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- BQBAJOJHJZUQLY-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propyl benzoate Chemical compound CCCCOC(C)COC(C)COC(C)COC(=O)C1=CC=CC=C1 BQBAJOJHJZUQLY-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- NAJFMEJXVQHNLR-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propyl benzoate Chemical compound COC(C)COC(C)COC(C)COC(=O)C1=CC=CC=C1 NAJFMEJXVQHNLR-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- QRUOTIJTSNETKW-UHFFFAOYSA-N 4-ethoxybutan-1-ol Chemical compound CCOCCCCO QRUOTIJTSNETKW-UHFFFAOYSA-N 0.000 description 1
- NTRCGACLCLJKBB-UHFFFAOYSA-N 4-hexoxybutan-1-ol Chemical compound CCCCCCOCCCCO NTRCGACLCLJKBB-UHFFFAOYSA-N 0.000 description 1
- VVOBKXXECUQKBZ-UHFFFAOYSA-N 4-propoxybutan-1-ol Chemical compound CCCOCCCCO VVOBKXXECUQKBZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000007309 Fischer-Speier esterification reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940090047 auto-injector Drugs 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 210000004916 vomit Anatomy 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
(1)触媒量のリン酸の存在下において、エチレングリコールn−ブチルエーテルと安息香酸とを反応させ、共沸蒸留によって副生成物の水を除去し、第1の粗生成物を形成するステップ。反応ステップ中の反応物質の損失を最小限に抑えるために、系の温度及び圧力条件は、反応混合物の温度が、その沸点よりも低くなるようなものである。
(2)第1の粗生成物を80℃以下に冷却するステップ。
(3)炭酸ナトリウム水溶液を添加することによって、リン酸触媒及び少なくとも一部の安息香酸を中和して、中和粗生成物混合物を得るステップ。
(4)中和粗生成物混合物から、リン酸ナトリウム等の塩及び有機副生成物の塩を抽出し、その後で相分離及び傾瀉を行って有機相を回収するステップ。
(5)有機相を精製するステップ。これは、残留水分、エチレングリコールn−ブチルエーテル、及びより低沸、すなわち、沸点の低い有機物、例えば、ブタナールを、加熱により真空下で、不活性ガス、例えば窒素での揮散により、除去することを伴う。反応容器に結果として得られた材料を、次いで、減圧で蒸留して、最終的な頂部生成物が得られる。
(1)エチレングリコールn−ブチルエーテル、安息香酸、及び触媒量のリン酸を混合して、反応混合物を形成し、エチレングリコールn−ブチルエーテルを安息香酸と反応させて、共沸蒸留によって副生成物である水を除去して第1の粗生成物を形成するが、ただし、反応混合物の温度は、その沸点よりも低いことを条件とすること、
(2)第1の粗生成物を80℃以下に冷却すること、
(3)炭酸ナトリウム水溶液を添加することによって、リン酸触媒及び少なくとも一部の安息香酸を中和して、塩を含む中和粗生成物混合物を得ること、
(4)中和粗生成物混合物から、リン酸ナトリウム等の塩及び有機副生成物の塩を抽出し、その後で相分離及び傾瀉を行って有機相を回収すること、ならびに
(5)残留水分、エチレングリコールn−ブチルエーテル、ならびにより低沸、すなわち、ブタナール及び他の沸点の低い有機物を、加熱により真空下で、不活性ガス、例えば窒素での揮散により、除去することを含む。反応容器に結果として得られた材料を、次いで、減圧で蒸留して、最終的な頂部生成物を得ることができる。
以下の実施例は、本発明を図示するために提供されており、その範囲を制限すると見なされるものではない。全ての圧力は、別途示されない限り、ゲージ圧ではなく絶対圧である。
Na2CO3(kg)=(2.35倍モル量のH3PO4)+(残留モル量の安息香酸)
Claims (15)
- グリコールエーテルエステルを調製するためのプロセスであって、(a)反応域において、安息香酸及び/または安息香酸無水物を、グリコールエーテルエステル生成物及び水を生成するのに十分な反応条件下において、グリコールエーテル供給物及び触媒量のリン酸と接触させて、反応混合物を形成することを含み、前記供給物は、グリコールエーテル及びブタナールを含み、前記水及びブタナールは、前記反応域で少なくとも部分的に蒸発し、分離域に送られて、そこで前記水及びブタナールは前記分離域から実質的に除去され、それによって前記グリコールエーテルエステルを含む第1の粗生成物が得られ、前記プロセスは、グリコールエーテルが共沸混合物の成分として以外には本質的に前記分離域を出ないような温度及び圧力条件下において行われる、プロセス。
- (b)前記第1の粗生成物をアルカリ性材料と接触させて、有機相及び水相を含む中和粗生成物混合物を得ることをさらに含み、前記中和粗生成物混合物は、グリコールエーテルエステル生成物と少なくとも1つの塩とを含み、前記接触が、前記少なくとも1つの塩を前記水相中に抽出するのに十分な条件下で行われる、請求項1に記載のプロセス。
- (c)前記中和粗生成物混合物を、塩含有水相と有機相とに相分離させること、及び前記有機相を回収することをさらに含む、請求項2に記載のプロセス。
- (d)残留水分、グリコールエーテル、及びより低沸、すなわち、沸点の低い有機物を、加熱、場合によっては不活性ガスの揮散により、真空下で除去することによって、前記有機相を精製して、最終的なグリコールエーテルエステル生成物を塔頂留出物として得ることをさらに含む、請求項3に記載のプロセス。
- ステップ(a)における前記分離域の最大温度は、前記反応混合物の沸点よりも低い、請求項1〜4のいずれかに記載のプロセス。
- ステップ(a)における前記分離域の頂部の温度は、少なくとも前記共沸混合物の沸点である、請求項1〜5のいずれかに記載のプロセス。
- 前記共沸混合物は、水及び前記グリコールエーテルによって形成される、請求項1〜6のいずれかに記載のプロセス。
- ステップ(b)において、前記第1の粗生成物に水、及び場合によっては抽出補助剤を添加することをさらに含む、請求項2〜7のいずれかに記載のプロセス。
- ステップ(c)において、前記有機相の回収は、前記塩含有水相を傾瀉除去することを含む、請求項3〜7のいずれかに記載のプロセス。
- 前記グリコールエーテルエステル生成物は、APHA色数が25未満である、請求項1〜9のいずれかに記載のプロセス。
- 前記グリコールエーテルエステル生成物は、5ppm未満、好ましくは1ppm未満、またはより好ましくは0.3ppm未満のブタナール含量を有する、請求項1〜10のいずれかに記載のプロセス。
- 前記分離域は、蒸留塔を備え、前記蒸留塔は、前記塔の頂部の温度を制御することを含むプロセス制御スキームを用いて動作される、請求項1〜11のいずれかに記載のプロセス。
- 前記グリコールエーテル供給物は、15〜1,000ppmのブタナール含量を有する、請求項1〜12のいずれかに記載のプロセス。
- 前記供給物中の前記グリコールエーテルは、エチレングリコールn−ブチルエーテルであり、前記エステルは、エチレングリコールn−ブチルエーテル安息香酸である、請求項1〜14のいずれかに記載のプロセス。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201462016301P | 2014-06-24 | 2014-06-24 | |
US62/016,301 | 2014-06-24 | ||
PCT/US2015/036387 WO2015200087A1 (en) | 2014-06-24 | 2015-06-18 | Process for producing low voc glycol ether esters |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020167591A Division JP2021004255A (ja) | 2014-06-24 | 2020-10-02 | 低vocグリコールエーテルエステルを生成するプロセス |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017519007A true JP2017519007A (ja) | 2017-07-13 |
JP6822846B2 JP6822846B2 (ja) | 2021-01-27 |
Family
ID=53524951
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016572640A Active JP6822846B2 (ja) | 2014-06-24 | 2015-06-18 | 低vocグリコールエーテルエステルを生成するプロセス |
JP2020167591A Withdrawn JP2021004255A (ja) | 2014-06-24 | 2020-10-02 | 低vocグリコールエーテルエステルを生成するプロセス |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020167591A Withdrawn JP2021004255A (ja) | 2014-06-24 | 2020-10-02 | 低vocグリコールエーテルエステルを生成するプロセス |
Country Status (8)
Country | Link |
---|---|
US (1) | US9809529B2 (ja) |
EP (1) | EP3160930B1 (ja) |
JP (2) | JP6822846B2 (ja) |
CN (1) | CN106458832B (ja) |
BR (1) | BR112016029033B1 (ja) |
CA (1) | CA2951928C (ja) |
ES (1) | ES2705759T3 (ja) |
WO (1) | WO2015200087A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112074555B (zh) * | 2018-06-06 | 2022-08-30 | 陶氏环球技术有限责任公司 | 水性涂料组合物 |
US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
EP3976736A4 (en) | 2019-05-24 | 2023-04-12 | Eastman Chemical Company | THERMAL PYROLYTIC OIL TO A GAS-FED CRACKER FURNACE |
CN110354834B (zh) * | 2019-07-02 | 2022-06-28 | 常州大学 | 一种镁铝锆复合氧化物催化剂的制备方法及其应用 |
CN110183326A (zh) * | 2019-07-03 | 2019-08-30 | 上海中溶科技有限公司 | 一种连续制备提纯苯甲酸乙二醇单丁醚酯的方法 |
CN110283073A (zh) * | 2019-07-03 | 2019-09-27 | 上海中溶科技有限公司 | 苯甲酸乙二醇单丁醚酯及其制备方法 |
US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4115415A (en) | 1973-11-19 | 1978-09-19 | Nisso Petrochemical Industries Co., Ltd. | Process for the production of alkylene glycol ether ester of organic carboxylic acid |
US4022808A (en) | 1973-11-19 | 1977-05-10 | Nippon Soda Company Limited | Process for the production of alkylene glycol ether of organic carboxylic acid |
US4489188A (en) | 1982-07-02 | 1984-12-18 | Eastman Kodak Company | Coalescent-containing coating composition |
US5618973A (en) | 1994-11-10 | 1997-04-08 | Union Carbide Chemicals & Plastics Technology Corporation | Esterification process |
DE10043545A1 (de) | 2000-09-05 | 2002-03-14 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Carbonsäureestern |
CN102256923B (zh) | 2008-12-16 | 2013-12-04 | 巴斯夫欧洲公司 | 制备羧酸酯的方法 |
ES2618654T3 (es) | 2011-04-08 | 2017-06-21 | Rohm And Haas Company | Éter-esteres de glicol con bajo o nulo nivel de VOC como agentes de coalescencia para dipersiones poliméricas acuosas |
EP2508572B1 (en) | 2011-04-08 | 2014-06-25 | Dow Global Technologies LLC | Low/zero voc glycol ether-esters and use as clean-up solvents and paint thinners |
EP2900627B1 (en) * | 2012-09-28 | 2017-01-11 | Dow Global Technologies LLC | Process for the production of high purity glycol esters |
-
2015
- 2015-06-18 CN CN201580032271.8A patent/CN106458832B/zh active Active
- 2015-06-18 EP EP15734759.2A patent/EP3160930B1/en active Active
- 2015-06-18 CA CA2951928A patent/CA2951928C/en active Active
- 2015-06-18 ES ES15734759T patent/ES2705759T3/es active Active
- 2015-06-18 BR BR112016029033-0A patent/BR112016029033B1/pt active IP Right Grant
- 2015-06-18 JP JP2016572640A patent/JP6822846B2/ja active Active
- 2015-06-18 US US15/318,032 patent/US9809529B2/en active Active
- 2015-06-18 WO PCT/US2015/036387 patent/WO2015200087A1/en active Application Filing
-
2020
- 2020-10-02 JP JP2020167591A patent/JP2021004255A/ja not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
CA2951928C (en) | 2022-08-16 |
JP2021004255A (ja) | 2021-01-14 |
JP6822846B2 (ja) | 2021-01-27 |
EP3160930B1 (en) | 2018-10-31 |
ES2705759T3 (es) | 2019-03-26 |
US9809529B2 (en) | 2017-11-07 |
EP3160930A1 (en) | 2017-05-03 |
BR112016029033A2 (pt) | 2017-08-22 |
CN106458832B (zh) | 2020-10-16 |
CN106458832A (zh) | 2017-02-22 |
CA2951928A1 (en) | 2015-12-30 |
WO2015200087A1 (en) | 2015-12-30 |
US20170129843A1 (en) | 2017-05-11 |
BR112016029033B1 (pt) | 2021-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6822846B2 (ja) | 低vocグリコールエーテルエステルを生成するプロセス | |
JP2021006569A (ja) | 低voc結合補助剤を生成するためのプロセス | |
TW200806617A (en) | Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol | |
CN105452230B (zh) | 用于制造环氧单体及环氧化物之方法 | |
JP2017518998A5 (ja) | ||
JP6379188B2 (ja) | 2−エチルヘキサナール及び3−ヘプチルホルマートを含む混合物からの3−ヘプタノールの製造方法 | |
JP4733275B2 (ja) | (メタ)アクリル酸エステルの精製方法 | |
CN106995459B (zh) | 制备含有硅酸2-乙基己酯的组合物的方法 | |
CN105152874B (zh) | 一种生产二丙二醇甲醚的方法 | |
CN105073722B (zh) | (甲基)丙烯酸缩水甘油酯的制造方法 | |
JP5053480B2 (ja) | 脂肪酸エステルの製造方法 | |
JP2009249302A (ja) | (メタ)アクリル酸エステルの回収方法 | |
CN106470966A (zh) | 萃取脱水方法 | |
JP4907872B2 (ja) | 脂肪酸エステルの製造方法および製造装置 | |
JP6753193B2 (ja) | 2−ヒドロキシ−2−メチル−1−プロピル(メタ)アクリレートおよび/または3−ヒドロキシ−3−メチル−1−ブチル(メタ)アクリレートの製造方法、ならびに、精製方法および組成物 | |
JP2009035522A (ja) | シクロペンチルアルコール化合物の製造方法 | |
JP2014530206A (ja) | アルキルパーフルオロアルケンエーテル製造において成分を分離する方法 | |
CN109923099A (zh) | 酚系(甲基)丙烯酸酯的制备 | |
WO2002074723A1 (fr) | Procede pour separer et recuperer de l'alcool propargylique | |
JPWO2013005636A1 (ja) | ジトリメチロールプロパンの製造方法 | |
JP2002003442A (ja) | 精製プロピオール酸の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20170111 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20170111 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20170321 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180604 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190515 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190618 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20190917 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191107 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20200602 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20201002 |
|
C60 | Trial request (containing other claim documents, opposition documents) |
Free format text: JAPANESE INTERMEDIATE CODE: C60 Effective date: 20201002 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20201013 |
|
C21 | Notice of transfer of a case for reconsideration by examiners before appeal proceedings |
Free format text: JAPANESE INTERMEDIATE CODE: C21 Effective date: 20201020 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201208 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210107 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6822846 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S802 | Written request for registration of partial abandonment of right |
Free format text: JAPANESE INTERMEDIATE CODE: R311802 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |