CN104684878B - 新戊二醇的连续生产方法 - Google Patents
新戊二醇的连续生产方法 Download PDFInfo
- Publication number
- CN104684878B CN104684878B CN201380050357.4A CN201380050357A CN104684878B CN 104684878 B CN104684878 B CN 104684878B CN 201380050357 A CN201380050357 A CN 201380050357A CN 104684878 B CN104684878 B CN 104684878B
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- China
- Prior art keywords
- barium
- trialkylamine
- manganese
- catalyst
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 34
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 46
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 39
- 229910052788 barium Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000005270 trialkylamine group Chemical group 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 35
- 239000000654 additive Substances 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 9
- 150000003973 alkyl amines Chemical class 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 11
- 238000006668 aldol addition reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005882 aldol condensation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002085 persistent effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution 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
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 cyclic acetals Chemical class 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
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LCQPFOZNYVLABG-UHFFFAOYSA-N 1-Isobutanol Chemical compound C1=CC(CNC(=O)OC)=CC=C1OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(C)O1 LCQPFOZNYVLABG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 101001018259 Homo sapiens Microtubule-associated serine/threonine-protein kinase 1 Proteins 0.000 description 1
- 101000693728 Homo sapiens S-acyl fatty acid synthase thioesterase, medium chain Proteins 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 102100025541 S-acyl fatty acid synthase thioesterase, medium chain Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 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
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- OXQMIXBVXHWDPX-UHFFFAOYSA-N n,n,2-trimethylpropan-2-amine Chemical compound CN(C)C(C)(C)C OXQMIXBVXHWDPX-UHFFFAOYSA-N 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
本发明涉及生产新戊二醇的连续方法,该方法通过在催化剂叔烷基胺的存在下异丁醛和甲醛的加成获得羟基新戊醛,接着在125‑180℃的温度和30‑120kPa的超压下用钡和锰掺杂的亚铬酸铜催化剂进行气相氢化。
Description
本发明涉及通过在气相中用钡和锰掺杂的亚铬酸铜催化剂使羟基新戊醛氢化来制备新戊二醇的连续方法。
多羟基醇或多元醇作为形成聚酯或聚氨酯、合成树脂涂料、润滑剂和塑化剂的缩合组分具有重大的经济意义。在该背景下,目的多羟基醇具体是通过甲醛与异丁醛或正丁醛的混合羟醛加成而获得的那些多羟基醇。甲醛和适合的丁醛之间的羟醛加成首先形成醛中间产物,然后其必定被还原成多羟基醇。由此方法得到的工业上重要的多羟基醇是由甲醛和异丁醛的混合羟醛缩合形成的新戊二醇(NPG,2,2-二甲基丙烷-1,3-二醇)。
羟醛加成在碱性催化剂例如碱金属氢氧化物或脂肪胺的存在下进行,并最初生成可分离的羟基新戊醛(HPA)中间产物。接着可以根据坎尼扎罗(Cannizzaro)反应用过量的甲醛可以将该中间产物转化为新戊二醇,以形成一当量的甲酸盐。在该还原步骤的方案中,由此获得作为副产物的甲酸盐,该方法变型的经济效益还取决于甲酸盐的商业机会。
然而,工业上还实施的是在气相和液相中用金属催化剂催化氢化羟基新戊醛。在气相变型中,在氢化阶段上游连接的蒸发器中首先从高沸物中分离羟基新戊醛。接着优选地,氢化在雷尼镍催化剂或基于镍的负载型催化剂的存在下进行,所述催化剂还可另外包含其它活性金属如铜或铬以及额外的活化剂。所述气相变型在例如EP0278106A1;US4094914;Ullmann’s Encyclopedia of Industrial Chemistry(乌尔曼工业化学百科全书),publisher VCH,5th Ed.,1985,Vol.Al,p.308;Chemiker-Zeitung(Chemist journal,化学期刊),volume 100,(1976),No.12,pp.504-514中有提及。
关于液相中的氢化已有大量描述,例如在EP0484800A2中,使用基于铜、锌和锆的催化剂进行。羟基新戊醛的液相氢化常在亚铬酸铜催化剂的存在下进行。亚铬酸铜催化剂还包含作为活化剂的其它金属,例如钡、镉、镁、锰和/或稀土金属。根据US4855515,特别示出了在甲醛与异丁醛反应的羟醛缩合产物的氢化中的锰掺杂的亚铬酸铜催化剂。WO98/29374A1公开了将钡掺杂的亚铬酸铜用于甲醇溶液中羟基新戊醛的氢化。
根据DE1518784A1的教导,在已掺杂钡的亚铬酸铜催化剂的存在下,将羟基新戊醛和过量异丁醛的混合物氢化为新戊二醇和异丁醇。根据EP0006460A1,在氢化温度不断增加下进行的粗羟基新戊醛的两步高压氢化也使用由钡活化的亚铬酸铜催化剂。
EP0522368A1公开了在溶液中进行羟基新戊醛的氢化,所述溶液包含基于醇和反应产物的混合物的至少20wt%的低分子量醇例如甲醇或正丁醇,以及基于水、醇和反应产物的总量的量不超过40wt%的水。推荐亚铬酸铜催化剂作为氢化催化剂。
作为工业上生产的产品,新戊二醇具有重大的经济意义,并因此总是需要改善制备新戊二醇的已知方法,不管是通过改善产率,通过更好地利用工厂设备,还是通过降低能量输入。
出人意料地发现,如果氢化是在已用锰和钡都掺杂的亚铬酸铜催化剂的存在下在气相中连续进行,则可以以高选择性和产率通过氢化羟基新戊醛制备新戊二醇。
因此本发明涉及制备新戊二醇的连续方法,该方法通过在催化剂叔烷基胺的存在下异丁醛和甲醛的加成生成羟基新戊醛,接着在125-180℃的温度下在气相中氢化,其特征在于,所述氢化是在包含活化剂钡和锰的亚铬酸铜催化剂的存在下以及在30-120kPa的超大气压下进行。
出人意料地发现,使用包含活化剂钡和锰的亚铬酸铜催化剂,以及通过设置125-180℃,优选140-180℃的氢化温度,成功地将羟基新戊醛选择性氢化为新戊二醇。
在过低的氢化温度下,羟基新戊醛的氢化是不完全的。在过高的氢化温度下,也发生用作羟醛缩合催化剂的叔烷基胺的分解增加,其生成难以除去的副产物且因此是不期望的。
此外,非常令人惊喜的是,在仅30-120kPa的过低超大气压下成功地以高产率氢化为新戊二醇。因此本发明的方法仅需要压缩机输出方面非常低的投入,且因此是非常节能的。
异丁醛和甲醛水溶液的羟醛加成在作为羟醛加成催化剂的叔烷基胺的存在下进行,该叔烷基胺可包含相同或不同的烷基并因此可对称或不对称地组成,或者所述羟醛加成在具有多个三烷基胺官能团的叔烷基胺的存在下进行。所述反应在例如三甲胺、三乙胺、三正丙胺、三异丙胺、甲基二乙胺、甲基二异丙胺、三正丁胺、二甲基叔丁胺或N,N’-四甲基乙二胺的存在下进行。已证明三甲胺、三乙胺、三正丙胺和三正丁胺是特别适合的催化剂。
醛可以按摩尔比反应,但也可过量使用两个反应参与者中的一种。甲醛以醛含量通常为20-50wt%的水溶液使用。已发现本发明的方法中使用的掺杂的亚铬酸铜催化剂具有出乎意料的高耐甲醛性。因此,在羟醛加成阶段,甲醛与异丁醛1:1的摩尔比可以调节为倾向于甲醛,一般高达1.2:1,优选为1.1:1。通过降低异丁醛投入,抑制了氢化阶段的异丁醇形成,且基于异丁醛投入,新戊二醇产率增加。
异丁醛和甲醛之间的反应在20-100℃之间进行,有利地在80-95℃的温度下进行。一般而言,该反应在标准压力下进行,但也可以使用超大气压。基于异丁醛,反应混合物中用作羟醛加成催化剂的叔烷基胺以1-20mol%,优选为2-12mol%的量存在。
除了来自甲醛水溶液的水和同样存在于甲醛水溶液中的少量甲醇,可选地将异丁醇作为稀释剂加入反应混合物中。不严格要求加入异丁醇,但如果加入异丁醇,则基于总反应混合物中的有机组分,反应混合物中其含量范围设置为15-30wt%,优选15-25wt%。不需要额外的溶剂和稀释剂。加成反应的实际过程是在搅拌槽、级联搅拌槽或在可装有填料或其它内容物的反应管中进行,以改善反应物的混合。该反应放热地进行,并可以通过加热来加速。
可选地在蒸馏或萃取除去挥发组分如水、甲醇、异丁醇和残余量的甲醛、异丁醛和羟醛缩合催化剂之后,或无需提前除去,将由羟醛加成生成的粗产物置于一般在140-190℃的温度和标准压力下运行的蒸发装置中。在蒸发器中高沸物作为残余物剩余,并从该过程除去。
高沸物可以热回收,或例如根据DE102008033163A1的步骤,单独地还原裂解。所述高沸物是含氧化合物,如酯类或环缩醛类,其中,化学结合了多当量的新戊二醇。在所述高沸物中,新戊二醇的单异丁酸酯和二异丁酸酯以及由羟基新戊醛通过季先科(Tishchenko)反应形成的羟基新戊酸新戊二醇单酯歧化产物的比例特别高。
来自蒸发器的挥发性馏分主要包含羟基新戊醛,且根据可选的粗羟醛加成混合物的后处理,还包含水、稀释剂(如果加入的话)以及其它挥发组分如来自甲醛稳定化的甲醇。还存在由高沸物夹带的残余物和用作羟醛缩合催化剂的叔胺。如果在不进行可选的分离的情况下,将粗羟醛加成混合物置于蒸发器中,则馏分一般包含基于馏分的有机组分的15-30wt%,优选15-25wt%的异丁醇。
在本发明的一个优选方案中,将馏分中的水含量调节至基于总馏分的15-25wt%,优选18-25wt%的值,从而使之后的氢化阶段在所确定量的水的存在下进行。100wt%的剩余部分是有机组分。在随后的氢化步骤中通过在本发明优选的方案中确定的水的量改善前述的含氧高沸物到新戊二醇的选择性裂解。水组分也促进氢化步骤期间有利的热分布和有利的反应热分散,并降低局部出现温度突升的危险。在使用水含量低于15wt%的馏分且因此氢化在较低量的水的存在下进行的过程中,对降低高沸组分的有利影响明显不那么显著。在这种情况下,建议特地加入水以得到所需含量。如果水含量太高,则不必要地占用了有价值的反应器容积,而没有得到充分利用。
将所得挥发馏分氢化,而不进行进一步纯化或加工步骤。
在钡和锰掺杂的亚铬酸铜催化剂的存在下,于125-180℃,优选140-180℃的温度下,在气相中进行粗羟基新戊醛的氢化。超大气压为30-120kPa,优选为60-100kPa。特别地证明了140-180℃的反应温度和60-100kPa的超大气压是有价值的。在较低的超大气压下,观察不到令人满意的羟基新戊醛氢化。
羟基新戊醛的氢化在包含活化剂钡和锰的亚铬酸铜催化剂的存在下进行。根据H.Adkin,Org.React.8,1954,1-27,亚铬酸铜催化剂可以描述为等摩尔组合的氧化铜和亚铬酸铜,尽管其并不是必须包含亚铬酸铜。催化剂可以在没有载体的情况下,作为非负载型催化剂使用,或者可以在有载体如硅藻土、硅胶或氧化铝的情况下,以粉末或片形、星形、柱形、环形或成比例的大表面积的其它颗粒的形式使用。
对于制备方法,将铜、铬、锰和钡中每一个的不可溶的化合物混合为例如糊状形式,并成形成适合的主体如柱形或片形。成形之后,干燥并煅烧至500℃,其中固体压缩,且存在的金属有可能被转化为氧化物。
用析出溶质的水溶液起始也是有利的。过滤后,和固体混合物一样,固体被干燥并锻烧至500℃。接着,建议在低分子量有机酸如甲酸、乙酸、丙酸或正丁酸中搅拌固体,以除去可溶成分,然后洗涤至无酸,再次干燥,并锻烧至500℃。
加入添加剂如石墨或碱金属皂或碱土金属皂之后,然后可以产生成型主体如片形或环形。
所述钡和锰掺杂的亚铬酸铜催化剂包含在各情况中基于铜、铬、钡和锰的总含量的0.5-8wt%,优选3-5wt%的锰和0.5-8wt%,优选1-4wt%的钡。基于铜、铬、钡和锰的总含量,证明了钡含量范围为1-4wt%且锰含量范围为3-5wt%是特别有价值的。除了提到的活化剂之外,可选地可以存在其它活化剂如镉、镁、锶和/或稀土金属。
因此本发明也涉及亚铬酸铜催化剂,其包含分别基于铜、铬、钡和锰的总含量的量为0.5-8wt%的钡和量为0.5-8wt%的锰。
氢化是在气相中例如用固定设置的催化剂或在流化床中用流化催化剂连续地进行。
在连续方式中,已证明催化剂时空速V/Vh为0.2-2.0h-1,优选0.3-1.0h-1是有利的,催化剂时空速V/Vh表示为每单位催化剂体积和时间的通过体积。
由于羟基新戊醛起始化合物不再完全氢化,且观察到副产物形成增加,因此要避免亚铬酸铜催化剂的较高时空速。
优选地,氢化是在直通路内于气相中连续地进行。也可是循环气体方式,在这种情况下,已证明循环气流与新鲜气流的比为40-70是有利的。
优选用纯氢气进行氢化。然而,也可使用包含游离氢以及另外在氢化条件下惰性的成分的混合物。
纯新戊二醇是获自常规蒸馏方法后的氢化的反应混合物。在该过程中,除去的稀释剂可再次回到羟醛加成阶段。
本发明的氢化方法以高转化率和高选择性将羟基新戊醛转化为新戊二醇。值得注意的是氢化中超大气压非常低。
抑制了叔烷基胺裂解为挥发性含氮化合物,所述含氮化合物生成不期望的杂质,且在之后的蒸馏加工中很难除去,以及在新戊二醇的进一步加工期间有所干扰。
通过下面的一些实施例进一步说明本发明的方法。
实施例
实施例1锰和钡掺杂的亚铬酸铜催化剂的制备
于55℃下将2.8kg硝酸铜三水合物、稀硝酸中50%的溶液形式的400g硝酸锰和150g硝酸钡溶解于20升水中。分别将2.6kg重铬酸铵溶解于12升水和4升25%的氨溶液中。然后将重铬酸铵溶液缓慢逐滴加入硝酸铜溶液中。析出红棕色固体。为了使沉淀完全,将混合物再搅拌一小时,并冷却至室温。然后将固体滤出,并在干燥箱中于110℃干燥。将干燥的固体于350℃以2℃/分钟的加热速率煅烧4小时。固体煅烧并冷却后,用20升10%的乙酸搅拌。然后用水将固体洗涤至无酸,并再次于110℃下干燥以及于350℃以2℃/分钟的加热速率煅烧。将这种形式获得的固体用作催化剂。基于金属,该催化剂有以下组成:铜47.5%、铬46.5%、锰4.0%、钡2.0%。。
实施例2实施例1的催化剂作为固定床催化剂的用途
将实施例1的催化剂与3%的石墨混合,并形成5×5mm的片。将片状催化剂装载进2.5升管式反应器中,然后在下面的条件下以三个阶段活化。
加热速率:20℃/h至180℃
氮气进料:1000l(STP)/h
氢气进料:20l(STP)/h
持续时间:12小时
氮气进料:1000l(STP)/h
氢气进料:60l(STP)/h
持续时间:6小时
氮气进料:1000l(STP)/h
氢气进料:120l(STP)/h
持续时间:6小时
l(STP)=标准升,20℃的温度和100kPa的压力下的1升气体体积。
为了测试实施例1制备的亚铬酸铜催化剂的催化活性,使用通过用三正丙胺催化的异丁醛与甲醛的羟醛反应制备的粗羟基新戊醛溶液。将粗混合物置于在150℃和标准压力下运行的蒸发器中。挥发馏分具有以下组成,且在不需要与氢气一起进一步纯化的条件下,在氢化阶段连续地进料至管式反应器的顶部:
氢化起始混合物的组成,数据用百分比表示
甲醛 | 0.9 |
异丁醛 | 1.0 |
三正丙胺 | 7.0 |
异丁醇 | 14.5 |
羟基新戊醛 | 48.2 |
新戊二醇 | 1.6 |
季先科酯 | 2.7 |
水 | 24.1 |
季先科酯:羟基新戊酸新戊二醇单酯
从管式反应器的底部移出氢化材料,用管道输入高压分离器,并因此通过液面控制进料至非加压容器。根据下表1中的条件调节氢化温度和催化剂时空速。所有实验在80kPa的超大气压下进行。
由下面的公式确定转化率和选择性:
转化率(%)=((起始混合物中羟基新戊醛的量-氢化后羟基新戊醛的量)/起始混合物中羟基新戊醛的量)×100
选择性(%)=(氢化后新戊二醇的量/(起始混合物中羟基新戊醛的量-氢化后羟基新戊醛的量))×100
表1:使用实施例1的钡和锰掺杂的亚铬酸铜催化剂的羟基新戊醛连续气相氢化
温度/℃ | V/Vh/h-1 | 羟基新戊醛转化率/% | 新戊二醇选择性/% |
161 | 0.29 | 99.9 | 97.3 |
163 | 0.48 | 99.9 | 98.2 |
155 | 0.57 | 99.8 | 98.6 |
如实验结果所示,在钡和锰掺杂的亚铬酸铜催化剂存在下进行的羟基新戊醛的连续气相氢化提供了关于新戊二醇转化率和选择性的较好结果。
实施例3实施例1的催化剂耐甲醛性的研究
使用按实施例2中的实验设置。通过特地加入40%的甲醛水溶液,获得具有下列组成的起始混合物,然后于155℃、80kPa的超大气压以及V/Vh为0.3h-1下将其氢化(数据用百分比表示)。
起始混合物 | 1 | 2 | 3 |
甲醛 | 1.4 | 0.9 | 1.1 |
异丁醛 | 1.0 | 1.0 | 0.7 |
三正丙胺 | 7.0 | 7.0 | 6.1 |
异丁醇 | 14.4 | 14.5 | 15.0 |
羟基新戊醛 | 48.1 | 48.2 | 48.2 |
新戊二醇 | 1.6 | 1.6 | 1.8 |
季先科酯 | 2.8 | 2.7 | 2.9 |
水 | 23.7 | 24.1 | 24.2 |
获得以下结果:
起始混合物 | 羟基新戊醛转化率/% | 新戊二醇选择性/% |
1 | 99.8 | 98.5 |
2 | 99.8 | 98.2 |
3 | 99.9 | 97.8 |
Claims (14)
1.制备新戊二醇的连续方法,所述方法在催化剂三烷基胺的存在下,通过异丁醛和甲醛的加成生成羟基新戊醛,接着在125-180℃的温度下在气相中氢化,其特征在于,所述氢化是在包含活化剂钡和锰的亚铬酸铜催化剂的存在下以及在30-120kPa的超大气压下进行。
2.如权利要求1所述的方法,其特征在于,所述氢化是在基于所用总量的量为15-25wt%的水的存在下进行。
3.如权利要求1或2所述的方法,其特征在于,所述氢化是在140-180℃的温度和60-100kPa的超大气压下进行。
4.如权利要求1或2所述的方法,其特征在于,所用三烷基胺是对称三烷基胺。
5.如权利要求4所述的方法,其特征在于,所用对称三烷基胺是三甲胺、三乙胺、三正丙胺或三正丁胺。
6.如权利要求1或2所述的方法,其特征在于,所用三烷基胺是非对称三烷基胺或具有多个三烷基胺官能团的化合物。
7.如权利要求1或2所述的方法,其特征在于,所述亚铬酸铜催化剂包含在各情况中基于铜、铬、钡和锰的总含量的量为0.5-8wt%的钡和量为0.5-8wt%的锰。
8.如权利要求7所述的方法,其特征在于,所述亚铬酸铜催化剂包含在各情况中基于铜、铬、钡和锰的总含量的量为1-4wt%的钡和量为3-5wt%的锰。
9.如权利要求1或2所述的方法,其特征在于,所述氢化在循环气流与新鲜气流的比为40-70时进行。
10.如权利要求3所述的方法,其特征在于,所用三烷基胺是对称三烷基胺。
11.如权利要求10所述的方法,其特征在于,所用对称三烷基胺是三甲胺、三乙胺、三正丙胺或三正丁胺。
12.如权利要求3所述的方法,其特征在于,所述亚铬酸铜催化剂包含在各情况中基于铜、铬、钡和锰的总含量的量为0.5-8wt%的钡和量为0.5-8wt%的锰。
13.如权利要求3所述的方法,其特征在于,所述氢化在循环气流与新鲜气流的比为40-70时进行。
14.如权利要求2所述的方法,其特征在于,所述氢化是在基于所用总量的量为18-25wt%的水的存在下进行。
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PCT/EP2013/002930 WO2014067602A1 (de) | 2012-10-29 | 2013-09-30 | Kontinuierliches verfahren zur herstellung von neopentylglykol |
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DE102012021280A1 (de) | 2012-10-29 | 2014-04-30 | Oxea Gmbh | Verfahren zur Herstellung von Neopentylglykol |
KR101757053B1 (ko) * | 2014-09-25 | 2017-07-12 | 주식회사 엘지화학 | 고효율의 네오펜틸 글리콜의 제조방법 및 이의 제조장치 |
KR101952690B1 (ko) | 2015-09-07 | 2019-02-27 | 주식회사 엘지화학 | 글리콜의 제조장치 및 제조방법 |
CN105061170A (zh) * | 2015-09-08 | 2015-11-18 | 上海华谊(集团)公司 | 制备羟基新戊醛的方法 |
CN105061167A (zh) * | 2015-09-08 | 2015-11-18 | 上海华谊(集团)公司 | 甲醛与异丁醛缩合制备羟基新戊醛的方法 |
CN109320397A (zh) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | 一种新戊二醇的制备方法 |
CN109678642A (zh) * | 2019-01-17 | 2019-04-26 | 中国科学院长春应用化学研究所 | 一种基于醛酮缩合反应合成二烯烃类化合物的方法 |
EP3747855B1 (de) | 2019-06-04 | 2024-01-10 | OQ Chemicals GmbH | Verfahren zur kontinuierlichen herstellung von diolen aus aldehyden mittels raney-cobalt katalyse |
CN112028758A (zh) * | 2020-05-25 | 2020-12-04 | 广安摩珈生物科技有限公司 | 羟基醛的制备方法以及使用电渗析技术拆分光学异构体的方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250337A (en) * | 1978-06-24 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Two stage hydrogenation to make neopentyl glycol |
US4855515A (en) * | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
CN101863738A (zh) * | 2010-07-19 | 2010-10-20 | 淄博明新化工有限公司 | 一种新戊二醇的制备方法 |
GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3340312A (en) | 1964-10-21 | 1967-09-05 | Eastman Kodak Co | Manufacture of neopentyl glycol and isobutanol |
DE2054601C3 (de) | 1970-11-06 | 1980-02-14 | Ruhrchemie Ag, 4200 Oberhausen- Holten | Verfahren zur Herstellung von zweiwertigen Alkoholen |
JPS5118928A (ja) * | 1974-08-08 | 1976-02-14 | Aikoh Co | Uwatsugizokaiyoyumenhifukuban |
US4094014A (en) | 1976-10-29 | 1978-06-13 | Schroeder Charles W | Workman's glove |
CA1137519A (en) | 1978-08-29 | 1982-12-14 | Chao-Chyan Pai | Heterogeneous vapor phase process for the catalytic hydrogenation of aldehydes to alcohols |
DE3644675A1 (de) | 1986-12-30 | 1988-07-14 | Ruhrchemie Ag | Verfahren zur herstellung von 2,2-dimethylpropandiol-(1,3) |
DE3706658A1 (de) * | 1987-03-02 | 1988-09-15 | Henkel Kgaa | Saeureresistenter katalysator fuer die fettsaeuredirekthydrierung zu fettalkoholen |
JP2639462B2 (ja) * | 1989-03-08 | 1997-08-13 | 東燃株式会社 | 1,4―ブタンジオールおよびテトラヒドロフランの製造法 |
JP2595358B2 (ja) * | 1989-12-07 | 1997-04-02 | 東燃株式会社 | 1,4―ブタンジオールおよびテトラヒドロフランの製造方法 |
JP2964621B2 (ja) | 1990-11-06 | 1999-10-18 | 三菱瓦斯化学株式会社 | ネオペンチルグリコールの製造方法 |
US5146012A (en) * | 1991-04-26 | 1992-09-08 | Aristech Chemical Corporation | Manufacture of neopentyl glycol (III) |
JPH05117187A (ja) * | 1991-04-26 | 1993-05-14 | Aristech Chem Corp | ネオペンチルグリコールの製造方法 |
US5134108A (en) * | 1991-05-22 | 1992-07-28 | Engelhard Corporation | Process for preparing catalyst with copper or zinc and with chromium, molybdenum, tungsten, or vanadium, and product thereof |
JPH05201898A (ja) | 1991-06-28 | 1993-08-10 | Aristech Chem Corp | ネオペンチルグリコールの製造方法 |
DE4215559A1 (de) * | 1992-05-12 | 1993-11-18 | Henkel Kgaa | Verfahren zur Herstellung von N-Alkylalkanolaminen |
DE4239247A1 (de) * | 1992-11-21 | 1994-05-26 | Huels Chemische Werke Ag | Katalysator für ein Verfahren zur Herstellung von 4-Hydroxy-2.2.6.6-tetramethylpiperidin |
FI102474B (fi) | 1996-12-30 | 1998-12-15 | Neste Oy | Menetelmä moniarvoisten alkoholien valmistamiseksi |
JP2000178216A (ja) * | 1998-12-16 | 2000-06-27 | Mitsubishi Gas Chem Co Inc | イソブチレングリコールの製造方法 |
DE10024542A1 (de) * | 2000-05-18 | 2001-11-22 | Basf Ag | Verfahren zur Herstellung von gesättigten C3-C20-Alkoholen |
US6479677B1 (en) * | 2000-10-26 | 2002-11-12 | Pure Energy Corporation | Processes for the preparation of 2-methylfuran and 2-methyltetrahydrofuran |
JP4151829B2 (ja) * | 2001-05-30 | 2008-09-17 | ダイセル化学工業株式会社 | 脂環式不飽和アルコールの製造方法 |
DE10317545A1 (de) | 2003-04-16 | 2004-11-04 | Basf Ag | Verfahren zur Herstellung von Neopentylglykol und Hydroxypivalinsäureneopentylglykolester |
DE102008031338B4 (de) * | 2008-07-02 | 2012-09-13 | Oxea Gmbh | Verfahren zur Herstellung von Neopentylglykol |
DE102008033163B4 (de) | 2008-07-15 | 2012-06-14 | Oxea Gmbh | Verfahren zur Gewinnung von Neopentylglykol durch Spaltung von im Herstellverfahren anfallenden Hochsiedern |
DE102012021280A1 (de) * | 2012-10-29 | 2014-04-30 | Oxea Gmbh | Verfahren zur Herstellung von Neopentylglykol |
-
2012
- 2012-10-29 DE DE102012021276.3A patent/DE102012021276A1/de not_active Ceased
-
2013
- 2013-09-30 US US14/432,628 patent/US9133083B2/en not_active Expired - Fee Related
- 2013-09-30 EP EP13773606.2A patent/EP2912001B1/de active Active
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- 2013-09-30 WO PCT/EP2013/002930 patent/WO2014067602A1/de active Application Filing
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- 2013-09-30 KR KR1020157010971A patent/KR102110115B1/ko active IP Right Grant
- 2013-10-28 TW TW102138826A patent/TWI468377B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4250337A (en) * | 1978-06-24 | 1981-02-10 | Chemische Werke Huls Aktiengesellschaft | Two stage hydrogenation to make neopentyl glycol |
US4855515A (en) * | 1987-08-12 | 1989-08-08 | Eastman Kodak Company | Process for the production of neopentyl glycol |
CN101863738A (zh) * | 2010-07-19 | 2010-10-20 | 淄博明新化工有限公司 | 一种新戊二醇的制备方法 |
GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
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US9133083B2 (en) | 2015-09-15 |
EP2912001A1 (de) | 2015-09-02 |
TWI468377B (zh) | 2015-01-11 |
CN104684878A (zh) | 2015-06-03 |
WO2014067602A1 (de) | 2014-05-08 |
TW201416342A (zh) | 2014-05-01 |
US20150225319A1 (en) | 2015-08-13 |
EP2912001B1 (de) | 2018-11-14 |
DE102012021276A1 (de) | 2014-04-30 |
JP6195622B2 (ja) | 2017-09-13 |
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