CA2329040A1 - Method for producing hexanediol - Google Patents
Method for producing hexanediol Download PDFInfo
- Publication number
- CA2329040A1 CA2329040A1 CA002329040A CA2329040A CA2329040A1 CA 2329040 A1 CA2329040 A1 CA 2329040A1 CA 002329040 A CA002329040 A CA 002329040A CA 2329040 A CA2329040 A CA 2329040A CA 2329040 A1 CA2329040 A1 CA 2329040A1
- Authority
- CA
- Canada
- Prior art keywords
- copper
- surface area
- cuo
- porosity
- calculated
- 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
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 title claims abstract 3
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract 19
- 229910052802 copper Inorganic materials 0.000 claims abstract 19
- 239000010949 copper Substances 0.000 claims abstract 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract 13
- 238000000034 method Methods 0.000 claims abstract 11
- 239000003054 catalyst Substances 0.000 claims abstract 10
- 150000002148 esters Chemical class 0.000 claims abstract 9
- 239000000203 mixture Substances 0.000 claims abstract 8
- 235000011037 adipic acid Nutrition 0.000 claims abstract 5
- 239000001361 adipic acid Substances 0.000 claims abstract 5
- 239000012535 impurity Substances 0.000 claims abstract 5
- 150000002896 organic halogen compounds Chemical class 0.000 claims abstract 4
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract 2
- 229910052736 halogen Inorganic materials 0.000 claims 3
- 150000002367 halogens Chemical class 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 3
- 239000007791 liquid phase Substances 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical class OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 claims 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000003809 water extraction Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 1
Classifications
-
- 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
- B01J23/72—Copper
-
- 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
-
- 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
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for producing hexanediol by hydrogenating adipic acid dialkyl esters or mixtures containing adipic acid dialkyl esters as an essential constituent and organic halogen compounds as impurities. According to said method, the adipic acid dialkyl esters or the mixtures containing adipic acid dialkyl esters are guided over copper catalysts at a temperature of 50 to 250 ~C and at a pressure of 1 to 100 bar before hydrogenation in order to remove the organic halogen compounds. Said copper catalysts contain 0.5 to 80 wt. % copper calculated as CuO and have a surface of 5 to 1500 m2/g, 0.05 to 1.5 cm3/g porosity and a copper surface of 0.1 to 20 m2/g.
Claims (10)
1. A process for the preparation of hexanediol by hydrogenating dialkyl adipates or mixtures which contain a dialkyl adipate as the essential component and organic compounds as impurities, wherein, before the hydrogenation, the dialkyl adipates or the mixtures containing dialkyl adipates are passed at from 50 to 250°C and from 1 to 100 bar over copper catalysts which have a copper content, calculated as CuO, of from 0.5 to 80% by weight, a surface area of from 5 to 1500 m2/g, a porosity of from 0.05 to 1.5 cm3/g and a copper surface area of from 0.1 to 20 m2/g, in order to remove the organic halogen compounds.
2. A process as claimed in claim 1, wherein copper catalysts which have a copper content, calculated as CuO, of from 2 to 60% by weight, a surface area of from 10 to 1000 m2/g, a porosity of from 0.1 to 0.8 cm3/g and a specific copper surface area of from 0.5 to 10.0 m2/g are used.
3. A process as claimed in claim 1, wherein TiO2-containing unsupported copper catalysts which have a copper content, calculated as CuO, of from 20 to 60% by weight, a surface area of from 10 to 150 m2/g, a porosity of from 0.1 to 0.5 cm3/g and a specific copper surface area of from 0.5 to 3.0 m2/g are used.
4. A process as claimed in claim 1 wherein ZrO2-supported copper catalysts which have a copper content, calculated as CuO, of from 2 to 8% by weight, a surface area of from 50 to 150 m2/g, a porosity of from 0.2 to 0.4 cm3/g and a specific copper surface area of from 1.0 to 3.0 m2/g are used.
5. A process as claimed in claim 1, wherein active carbon-supported copper catalysts which have a copper content, calculated as CuO, of from 2 to 8% by weight, a surface area of from 500 to 1000 m2/g, a porosity of from 0.5 to 0.8 cm3/g and a specific copper surface area of from 1.0 to 5.0 m2/g are used.
6. A process as claimed in claim 1, wherein the halogen-containing impurities are removed in the liquid phase in continuous operation with a liquid space velocity of 0.05 - 50 kg of ester mixture per 1 of catalyst per hour at 50 - 250°C and at 1 - 100 bar.
7. A process as claimed in claim 1, wherein the halogen-containing impurities are removed in the liquid phase in continuous operation with a liquid space velocity of 0.1 - 10 kg of ester mixture per 1 of catalyst per hour at 100 - 200°C and at 1 - 10 bar.
8. A process as claimed in claim 1, wherein the halogen-containing impurities are removed in the liquid phase in continuous operation with a liquid space velocity of 0.2 - 1.0 kg of ester mixture per 1 of catalyst per hour at 150 - 180°C and at 1 - 5 bar.
9. A process as claimed in claim 1, wherein the starting material used is an ester fraction as obtained (a) by esterification of an aqueous dicarboxylic acid mixture, which contains adipic acid, 6-hydroxycaproic acid and small amounts of 1,4-cyclohexanediols and which is obtained as a byproduct in the oxidation of cyclohexane to cyclohexanone/cyclohexanol with oxygen or oxygen-containing gases and by water extraction of the reaction mixture, with a low molecular weight alcohol, (b) removal of the excess alcohol and of the low boilers in a first distillation stage and (c) separation of the bottom product in a second distillation into a fraction containing at least the major part of the cyclohexanediols and an ester fraction which is essentially free of 1,4-cyclohexanediols and is to be hydrogenated.
10. A process as claimed in claim 1, wherein the content of organic halogen compounds is reduced to less than 0.1 ppm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998118096 DE19818096A1 (en) | 1998-04-23 | 1998-04-23 | Hexandiol production by hydrogenation of dialkyl adipate |
| DE19818096.9 | 1998-04-23 | ||
| PCT/EP1999/002448 WO1999055653A1 (en) | 1998-04-23 | 1999-04-12 | Method for producing hexanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2329040A1 true CA2329040A1 (en) | 1999-11-04 |
| CA2329040C CA2329040C (en) | 2009-11-10 |
Family
ID=7865515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002329040A Expired - Fee Related CA2329040C (en) | 1998-04-23 | 1999-04-12 | Method for producing hexanediol |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6313358B1 (en) |
| EP (1) | EP1082282B1 (en) |
| JP (1) | JP2002512992A (en) |
| KR (1) | KR100543496B1 (en) |
| CA (1) | CA2329040C (en) |
| DE (2) | DE19818096A1 (en) |
| ES (1) | ES2203112T3 (en) |
| TW (1) | TW505625B (en) |
| WO (1) | WO1999055653A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007080946A1 (en) * | 2006-01-13 | 2007-07-19 | Ube Industries, Ltd. | Process for production of 1,6-hexanediol |
| JP2008120116A (en) * | 2006-11-08 | 2008-05-29 | Hitachi Constr Mach Co Ltd | Bending construction vehicle |
| JP4805118B2 (en) * | 2006-12-13 | 2011-11-02 | 日立建機株式会社 | Power steering device |
| JP5052147B2 (en) * | 2007-01-25 | 2012-10-17 | 日立建機株式会社 | Steering device for construction vehicles |
| WO2010071761A1 (en) * | 2008-12-18 | 2010-06-24 | Invista Technologies S.A.R.L. | Cyclohexane oxidation process byproduct stream derivatives and methods for using the same |
| GB201205764D0 (en) * | 2012-03-30 | 2012-05-16 | Johnson Matthey Plc | Catalyst and method of manufacture |
| DE102014113197A1 (en) * | 2014-09-12 | 2016-03-17 | L’AIR LIQUIDE Société Anonyme pour l’Etude et l’Exploitation des Procédés Georges Claude | Process and plant for the production of fatty alcohols |
| WO2020207874A1 (en) * | 2019-04-12 | 2020-10-15 | Basf Se | Catalyst system for producing aromatic amines |
| CN113683483B (en) * | 2021-06-07 | 2022-05-13 | 浙江博聚新材料有限公司 | Production method and device of high-purity 1, 6-hexanediol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW208050B (en) | 1991-07-05 | 1993-06-21 | Kitamura Youzi | |
| DE4141199A1 (en) | 1991-12-13 | 1993-06-17 | Sued Chemie Ag | CHROME-FREE CATALYST FOR HYDRATING ORGANIC COMPOUNDS CONTAINING THE CARBONYL FUNCTIONS |
| US5614644A (en) | 1995-09-01 | 1997-03-25 | Eastman Chemical Company | Process for the removal of organic chlorides from furan and hydrogenated furans |
| EP0883590B1 (en) * | 1996-03-01 | 2001-05-02 | Basf Aktiengesellschaft | Process for preparing 1,6 hexane diol with a level of purity over 99 % |
-
1998
- 1998-04-23 DE DE1998118096 patent/DE19818096A1/en not_active Withdrawn
-
1999
- 1999-04-06 TW TW88105438A patent/TW505625B/en active
- 1999-04-12 CA CA002329040A patent/CA2329040C/en not_active Expired - Fee Related
- 1999-04-12 ES ES99915756T patent/ES2203112T3/en not_active Expired - Lifetime
- 1999-04-12 DE DE59906012T patent/DE59906012D1/en not_active Expired - Fee Related
- 1999-04-12 KR KR1020007011722A patent/KR100543496B1/en not_active Expired - Fee Related
- 1999-04-12 WO PCT/EP1999/002448 patent/WO1999055653A1/en not_active Ceased
- 1999-04-12 US US09/673,125 patent/US6313358B1/en not_active Expired - Fee Related
- 1999-04-12 EP EP99915756A patent/EP1082282B1/en not_active Expired - Lifetime
- 1999-04-12 JP JP2000545814A patent/JP2002512992A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP1082282B1 (en) | 2003-06-18 |
| ES2203112T3 (en) | 2004-04-01 |
| EP1082282A1 (en) | 2001-03-14 |
| JP2002512992A (en) | 2002-05-08 |
| KR20010042913A (en) | 2001-05-25 |
| DE19818096A1 (en) | 1999-10-28 |
| WO1999055653A1 (en) | 1999-11-04 |
| CA2329040C (en) | 2009-11-10 |
| TW505625B (en) | 2002-10-11 |
| KR100543496B1 (en) | 2006-01-20 |
| US6313358B1 (en) | 2001-11-06 |
| DE59906012D1 (en) | 2003-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |