WO2014137619A1 - Process for acid dehydration of sugar alcohols - Google Patents
Process for acid dehydration of sugar alcohols Download PDFInfo
- Publication number
- WO2014137619A1 WO2014137619A1 PCT/US2014/017563 US2014017563W WO2014137619A1 WO 2014137619 A1 WO2014137619 A1 WO 2014137619A1 US 2014017563 W US2014017563 W US 2014017563W WO 2014137619 A1 WO2014137619 A1 WO 2014137619A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dehydration
- process according
- inflate
- catalyst
- sorbitol
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Definitions
- the present Invention is concerned with processes for making dehydration products from sugar alcohols, and more particularly but without limitation : to acid-catalyzed processes for making Isohexides, such as Isosorbide, from hexito!s such as sorbitol or from rnonoanhydrohexitois such as 1.4-sorbitan.
- Isohexides such as Isosorbide
- hexito!s such as sorbitol
- rnonoanhydrohexitois such as 1.4-sorbitan.
- a variety of acid catalysts have been evaluated for use in carrying out the dehydration of sorbitol through certain monoanhvdrohexitoi intermediates (e.g., 1 ,4-sorbitan) to Isosorbide.
- inorganic acids such as H2SO4, H3PO4, and NCI are readily obtained, inexpensive materials but are difficult to regenerate.
- solid resin catalysts have been tried. Unfortunately, In the presence of wafer and at the temperatures required for carrying out the dehydration, very few solid acids can demonstrate the activity and stability needed to begin to contemplate a commercially viable process.
- US Pat. No, 7,772,412 io Holladay et al. describes a process for making isosorbide wherein sorbitol Is fed to a reactor containing a dehydration catalyst and a hydrogenation co-catalyst, with hydrogen being supplied countercurrentiy to the reactor for removing water as it is formed and for "reducing or eliminating ...o!igomeric or polymeric material in the dehydration product " , to which undesirable color formation had been attributed.
- Suitable dehydration catalysts include the mineral acid catalysts, solid acid catalysts such as the heteropolyaeids, mesoporous silicas, acid clays, sulfated zirconia, molecular sieve materials, cation exchange resins and zeolites, and combinations of any of these.
- the hydrogenation catalyst is described as typically being a supported metal or multi-metal catalyst. Palladium in particular is described as especially preferable for the metal, with platinum, nickel, cobalt, ruthenium, rhenium, rhodium, Iridium and iron also being listed.
- the dehydration process is conducted rapidly and with rapid cooling of the dehydration products prior to any separation of the residual sugar alcoho s) from the dehydration products in the overall product mixture, in the manner prescribed for the dehydration of aqueous sugar solutions in WO 2013/106136 to Sanborn et al.
- the present invention in a first aspect concerns a process for the acid-catalyzed dehydration of a sugar alcohol wherein the catalyst comprises a water-tolerant Lewis acid, in particular embodiments, the catalyst comprises a homogeneous water-tolerant Lewis acid, especially a homogeneous Lewis acid selected from the group consisting of bismuth (ill) irifiate, gallium (ill) inflate, scandium (IM) inflate, aluminum inflate, fin (II) inflate and Indium (111) triflate.
- a homogeneous water-tolerant Lewis acid especially a homogeneous Lewis acid selected from the group consisting of bismuth (ill) irifiate, gallium (ill) inflate, scandium (IM) inflate, aluminum inflate, fin (II) inflate and Indium (111) triflate.
- Such catalysts are effective for dehydrating both of sorbitol and the 1 ,4-sorbiian dehydration precursor of Isosorblde, and bismuth (III) triflate particularly is beneficial for dehydrating mannitoi to iso annide , so that in a second, more particular aspect the present invention concerns an improved process for making an isohexide from a corresponding hexltol.
- a preferred process according to the present invention for dehydrating sorbitol involves mixing sorbitol with from 0.005 mo! percent and greater of a water-tolerant Lewis acid, heating to at least 140 degrees Celsius, and carrying out the acid-catalyzed dehydration of sorbitol isotherma!ly for an hour or longer under a reduced pressure to continuously remove water from the reaction.
- the water-tolerant Lewis aoid is preferably one or more of bismuth (III) trifiate, gallium (HI) trifiate, scandium (ill) trifiate, aluminum trifiate, tin (II) trifiate and indium (ill) trifiate, and while yields of isosorbide and the 1 ,4-sorbitan precursor of isosorbide obtained from these catalysts can be seen from the examples below to vary somewhat dependent on the catalyst used, the catalyst loading and reaction conditions of temperature and duration, It Is expected that catalyst loadings of not more than 0 1 mol percent, temperatures of not more than 160 degrees Celsius and reaction times of not more than 3 hours will provide commercially acceptable yields of isosorbide, The crude product mixture may then be purified according to any of the known methods for doing so.
- sugar alcohols generally (where "sugar alcohols" is understood to include partially dehydrated sugar alcohols such as, for example, monoanhydrobexitols from the partial dehydration of hexitols), the extent to which certain benefits or advantages are observed, the pellicular water-tolerant Lewis acid catalysts that prove most effective and the optimum process conditions for carrying out the Lewis aeid-ealaiyzed dehydrations can he expected to vary somewhat from one sugar alcohol to the next. As an example, we found bismuth inflate to be particularly advantageous for catalyzing the dehydration of mannitol to isomannide. Those skilled in the art will be well able, in any event, to determine the optimum features of a process for dehydrating a particular sugar alcohol using a water-tolerant, Lewis acid catalyst as claimed herein by routine experimentation.
- Acid % sor j ol isgsof ide 2 : 5;:Scr it n Accountability inversion .vM ims! f*t %;
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157027290A KR20150123923A (en) | 2013-03-05 | 2014-02-21 | Process for acid dehydration of sugar alcohols |
EP14759625.8A EP2964743B1 (en) | 2013-03-05 | 2014-02-21 | Process for acid dehydration of sugar alcohols |
JP2015561383A JP6267240B2 (en) | 2013-03-05 | 2014-02-21 | Method for acid dehydration of sugar alcohols |
US14/771,825 US9630974B2 (en) | 2013-03-05 | 2014-02-21 | Process for acid dehydration of sugar alcohols |
CN201480010308.2A CN105026542A (en) | 2013-03-05 | 2014-02-21 | Process for acid dehydration of sugar alcohols |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361772642P | 2013-03-05 | 2013-03-05 | |
US61/772,642 | 2013-03-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014137619A1 true WO2014137619A1 (en) | 2014-09-12 |
Family
ID=51491780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/017563 WO2014137619A1 (en) | 2013-03-05 | 2014-02-21 | Process for acid dehydration of sugar alcohols |
Country Status (6)
Country | Link |
---|---|
US (1) | US9630974B2 (en) |
EP (1) | EP2964743B1 (en) |
JP (1) | JP6267240B2 (en) |
KR (1) | KR20150123923A (en) |
CN (1) | CN105026542A (en) |
WO (1) | WO2014137619A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016137833A1 (en) | 2015-02-24 | 2016-09-01 | Archer Daniel Midland Company | Isoidide manufacture and purification |
WO2017030684A1 (en) * | 2015-08-14 | 2017-02-23 | Archer Daniels Midland Company | Dehydrative cyclization of pentitols using water-tolerant lewis acid catalysts under mild conditions and derivatives |
WO2017030685A1 (en) * | 2015-08-14 | 2017-02-23 | Archer Daniels Midland Company | One-pot synthesis of anhydropentitol mono- and diethers |
WO2017100402A1 (en) * | 2015-12-11 | 2017-06-15 | Archer Daniels Midland Company | One-pot synthesis of anhydropentitol esters from pentitols, catalyzed by water-tolerant lewis acids |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6803703B2 (en) | 2016-08-29 | 2020-12-23 | 国立大学法人北海道大学 | A solid catalyst for dehydration of mannitol, and a method for producing 2,5-sorbitan and / or isomannide using this catalyst. |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6849748B2 (en) | 2000-11-01 | 2005-02-01 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US20070173654A1 (en) * | 2006-01-26 | 2007-07-26 | Holladay Johnathan E | Methods for dehydration of sugars |
US20070173653A1 (en) * | 2006-01-26 | 2007-07-26 | Jianli Hu | Method of performing sugar dehydration and catalyst treatment |
US7420067B2 (en) | 2006-03-09 | 2008-09-02 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US7439352B2 (en) | 2000-11-01 | 2008-10-21 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US7982059B2 (en) | 2007-04-06 | 2011-07-19 | Sud-Chemie Inc. | Sorbitol conversion process |
WO2012081785A1 (en) * | 2010-12-15 | 2012-06-21 | Samyang Genex Corporation | Methods for distilling and manufacturing anhydrosugar alcohols |
WO2012121913A2 (en) * | 2011-03-10 | 2012-09-13 | Archer Daniels Midland Company | Improved method for quantitative analysis of sugars, sugar alcohols and related dehydration products |
WO2013106136A1 (en) | 2012-01-10 | 2013-07-18 | Archer Daniels Midland Company | Process for making hmf and hmf derivatives from sugars, with recovery of unreacted sugars suitable for direct fermentation to ethanol |
WO2013138153A1 (en) | 2012-03-12 | 2013-09-19 | Archer Daniels Midland Company | Process for making sugar and/or sugar alcohol dehydration products |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3223734A (en) * | 1961-04-26 | 1965-12-14 | Archer Daniels Midland Co | Process for producing tertiary amines |
PL193289B1 (en) * | 1999-11-12 | 2007-01-31 | Univ Gdanski | Method of obtaining osmotherapeutic mixtures of anhydrohexithioles |
EP1283840B1 (en) * | 2000-05-26 | 2005-02-09 | E.I. Dupont De Nemours And Company | Process for the manufacture of anhydro sugar alcohols |
KR101421514B1 (en) * | 2012-05-22 | 2014-07-30 | 대구가톨릭대학교산학협력단 | Method for preparing isosorbide from sorbitol using water-compatible lewis acid |
-
2014
- 2014-02-21 WO PCT/US2014/017563 patent/WO2014137619A1/en active Application Filing
- 2014-02-21 CN CN201480010308.2A patent/CN105026542A/en active Pending
- 2014-02-21 JP JP2015561383A patent/JP6267240B2/en not_active Expired - Fee Related
- 2014-02-21 US US14/771,825 patent/US9630974B2/en not_active Expired - Fee Related
- 2014-02-21 EP EP14759625.8A patent/EP2964743B1/en not_active Not-in-force
- 2014-02-21 KR KR1020157027290A patent/KR20150123923A/en not_active Application Discontinuation
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6849748B2 (en) | 2000-11-01 | 2005-02-01 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US7439352B2 (en) | 2000-11-01 | 2008-10-21 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US20070173654A1 (en) * | 2006-01-26 | 2007-07-26 | Holladay Johnathan E | Methods for dehydration of sugars |
US20070173653A1 (en) * | 2006-01-26 | 2007-07-26 | Jianli Hu | Method of performing sugar dehydration and catalyst treatment |
US7772412B2 (en) | 2006-01-26 | 2010-08-10 | Battelle Memorial Institute | Methods for dehydration of sugars and sugar alcohols |
US7420067B2 (en) | 2006-03-09 | 2008-09-02 | Archer-Daniels-Midland Company | Process for the production of anhydrosugar alcohols |
US7982059B2 (en) | 2007-04-06 | 2011-07-19 | Sud-Chemie Inc. | Sorbitol conversion process |
WO2012081785A1 (en) * | 2010-12-15 | 2012-06-21 | Samyang Genex Corporation | Methods for distilling and manufacturing anhydrosugar alcohols |
WO2012121913A2 (en) * | 2011-03-10 | 2012-09-13 | Archer Daniels Midland Company | Improved method for quantitative analysis of sugars, sugar alcohols and related dehydration products |
WO2013106136A1 (en) | 2012-01-10 | 2013-07-18 | Archer Daniels Midland Company | Process for making hmf and hmf derivatives from sugars, with recovery of unreacted sugars suitable for direct fermentation to ethanol |
WO2013138153A1 (en) | 2012-03-12 | 2013-09-19 | Archer Daniels Midland Company | Process for making sugar and/or sugar alcohol dehydration products |
Non-Patent Citations (1)
Title |
---|
YAMAGUCHI, ARITOMO ET AL.: "Sorbitol dehydration in high temperature liquid water", GREEN CHEMISTRY, vol. 13, no. 4, 1 January 2011 (2011-01-01), pages 873 - 881, XP055278086, DOI: 10.1039/C0GC00426J * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016137833A1 (en) | 2015-02-24 | 2016-09-01 | Archer Daniel Midland Company | Isoidide manufacture and purification |
WO2017030684A1 (en) * | 2015-08-14 | 2017-02-23 | Archer Daniels Midland Company | Dehydrative cyclization of pentitols using water-tolerant lewis acid catalysts under mild conditions and derivatives |
WO2017030685A1 (en) * | 2015-08-14 | 2017-02-23 | Archer Daniels Midland Company | One-pot synthesis of anhydropentitol mono- and diethers |
WO2017100402A1 (en) * | 2015-12-11 | 2017-06-15 | Archer Daniels Midland Company | One-pot synthesis of anhydropentitol esters from pentitols, catalyzed by water-tolerant lewis acids |
Also Published As
Publication number | Publication date |
---|---|
KR20150123923A (en) | 2015-11-04 |
US9630974B2 (en) | 2017-04-25 |
EP2964743A1 (en) | 2016-01-13 |
EP2964743A4 (en) | 2016-07-13 |
CN105026542A (en) | 2015-11-04 |
EP2964743B1 (en) | 2018-09-05 |
JP2016516014A (en) | 2016-06-02 |
US20160016970A1 (en) | 2016-01-21 |
JP6267240B2 (en) | 2018-01-24 |
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