EP2310420A1 - Process for continuous catalytic acetylation - Google Patents
Process for continuous catalytic acetylationInfo
- Publication number
- EP2310420A1 EP2310420A1 EP09777447A EP09777447A EP2310420A1 EP 2310420 A1 EP2310420 A1 EP 2310420A1 EP 09777447 A EP09777447 A EP 09777447A EP 09777447 A EP09777447 A EP 09777447A EP 2310420 A1 EP2310420 A1 EP 2310420A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- polysaccharide
- acetic acid
- acetylation
- acetic anhydride
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000021736 acetylation Effects 0.000 title claims abstract description 17
- 238000006640 acetylation reaction Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 title description 2
- 150000004676 glycans Chemical class 0.000 claims abstract description 35
- 239000005017 polysaccharide Substances 0.000 claims abstract description 35
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 68
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000002826 coolant Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 238000007738 vacuum evaporation Methods 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- -1 polysaccharide acetate Chemical class 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B17/00—Apparatus for esterification or etherification of cellulose
- C08B17/02—Apparatus for esterification or etherification of cellulose for making organic esters of cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
Definitions
- the invention relates to a process for the continuous acetylation of polysaccharides.
- the process of acetylation of polysaccharides has long been known.
- the polysaccharide to be reacted is conventionally contacted with a mixture of acetic anhydride and anhydrous acetic acid and other additives in a stirred tank.
- the acetic anhydride reacts with the polysaccharide to polysaccharide (s) acetate and acetic acid.
- the acetic acid is instant
- Polysaccharide is usually fully acetylated, which is a partial acetylation but also possible according to the invention.
- the polysaccharide is inoculated with the aid of a catalyst.
- the catalyst is usually a strong acid.
- Added additives often have the role of the plasticizer of the polysaccharide, these usually react with and the reaction products can then be plasticizer of the polysaccharide (s) acetate.
- the activity of the catalyst increases with the temperature.
- the catalyst alters the polysaccharide and produces shorter molecules.
- the process is therefore characterized by accurate catalyst dosing and temperature control because the reaction is highly exothermic.
- this temperature control can be carried out by gradually adding the supercooled liquid reactants and the catalyst to the polysaccharide mass. Likewise, part of the heat can be dissipated through the cooling jacket of the stirred tank. This process is very slow due to the poor mixing performance of the stirred tank and the boiler must have a very large volume to accommodate the initially very light polysaccharide (low bulk density).
- GB 969 711 shows a process for the continuous acetylation of amylose. there the process is run at a certain temperature and at a certain pressure.
- the object of the invention is to find a continuous process and corresponding devices which make it possible to complete the acetylation with the lowest possible residence time in the reaction space with a high degree of conversion, in order at the same time to keep the production costs of the reactor small and the catalyst exposure time short. so that unwanted side reactions are suppressed.
- the polysaccharide and a portion of the liquid educts are premixed in an upstream unit and fed as a suspension to a continuous reactor, which is for example a mixing kneader, by means of a suitable conveying member in the process space of the reactor in which it is under a set pressure which corresponds to the boiling point of the acetic acid at the desired process temperature.
- a continuous reactor which is for example a mixing kneader
- the acetic acid and partially also the acetic anhydride therefore evaporates in parts, thus depriving the reactor of excess energy from the exotherm and being withdrawn through one or more bridgehead mounted on the reactor, condensed, and the process along with the liquid reactants and catalyst completely or partially recycled.
- This process creates a local dilution of the mixture in the recycle or feed zone, which favors the suspension of the polysaccharide in the feed zone, which in turn accelerates the reaction since the acetic anhydride gets easier access to the polysaccharide.
- the entry member into the process space according to the invention is a lock.
- Process space is metered, but the polysaccharide is previously suspended in sufficient amount of anhydrous acetic acid. Then it is pumped into a continuous sieve centrifuge or granulator operating under the same pressure conditions as in the reactor or the excess
- Acetic acid is separated again.
- the solid-acetic acid suspension is then pumped directly into the reactor or falls into it by gravity.
- Another advantage of this invention relates to the cooling of the condensate. It can be done by tempered cooling water, while the conventional process, the liquids must be overcooled or added as a solid to compensate for the exothermic energy.
- the process according to the invention allows by targeted recycling only parts of the acetic acid or by a downstream flash to adjust the residual content of acetic acid in Polysaccharidazetats.
- the partial stream not returned to the reactor can be reused directly in the premix.
- the process of the invention also allows to adjust the residual content of the polysaccharide acetate to acetic acid as desired. If too much acetic acid is present, a partial stream or the entire stream of the condensate is withdrawn from the recirculation and discharged separately. Since this substream is anhydrous, it can be reused directly or after conversion to acetic anhydride.
- the process according to the invention for the continuous acetylation of polysaccharide begins in a premixer 1, followed by a centrifuge 2. Thereafter, the product passes into a reactor 3, from which in turn the product is transferred via a flash 7 in a Vakuumausdampfer 8, from which then the final product is discharged.
- the starting materials or parts of the educts are continuously metered into the premixer 1 and homogeneously mixed there. Excess acetic acid may be mechanically separated in the case of using a centrifuge or otherwise. However, it is also possible that the suspension from the premixer 1 is pumped directly into the reactor 3 or falls into the reactor 3 via a vacuum lock.
- split metered portion further fractions of the split educts are fed directly to the reactor 3 continuously.
- This may be a catalyst, acetic anhydride or other additives.
- Acetic anhydride which is condensed in a condenser 4 and partly 5 or completely returned to the reactor or discharged at 6.
- the exhaust stream may be connected to a vacuum system, to control the product temperature (evaporation temperature) in the reactor.
- the polysaccharide acetate is introduced via flash 7 into a vacuum steamer 8 in which the residual acetic acid and acetic anhydride are removed. Is discharged polysaccharide.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008035401A DE102008035401B4 (en) | 2008-07-29 | 2008-07-29 | Process for the continuous catalytic acetylation of polysaccharides |
PCT/EP2009/005412 WO2010012430A1 (en) | 2008-07-29 | 2009-07-27 | Process for continuous catalytic acetylation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2310420A1 true EP2310420A1 (en) | 2011-04-20 |
Family
ID=41404017
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09777447A Withdrawn EP2310420A1 (en) | 2008-07-29 | 2009-07-27 | Process for continuous catalytic acetylation |
Country Status (7)
Country | Link |
---|---|
US (1) | US20110213140A1 (en) |
EP (1) | EP2310420A1 (en) |
JP (1) | JP2011529510A (en) |
CN (1) | CN102124033A (en) |
BR (1) | BRPI0916587A2 (en) |
DE (1) | DE102008035401B4 (en) |
WO (1) | WO2010012430A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10982011B2 (en) * | 2014-05-21 | 2021-04-20 | Titan Wood Limited | Process for acetylation of wood in the presence of an acetylation catalyst |
CN115197335A (en) * | 2022-05-12 | 2022-10-18 | 上海应用技术大学 | Yam polysaccharide and extraction method and application thereof |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1560620A (en) * | 1925-01-28 | 1925-11-10 | Eastman Kodak Co | Process of manufacturing cellulose acetate |
GB355382A (en) * | 1929-06-12 | 1931-08-27 | Us Ind Alcohol Co | Manufacture of cellulose derivatives |
US2136030A (en) * | 1936-10-14 | 1938-11-08 | Eastman Kodak Co | Process for preparing cellulose esters |
US2376378A (en) * | 1941-09-20 | 1945-05-22 | John D Murray | Acetylation process and product |
DE1020615B (en) * | 1955-03-25 | 1957-12-12 | Gevaert Photo Prod Nv | Device for the esterification of cellulose fibers while maintaining structure |
GB969711A (en) * | 1961-11-29 | 1964-09-16 | Nat Starch Chem Corp | Improvements in or relating to a process for the continuous acylation of amylose |
US3320022A (en) * | 1964-04-27 | 1967-05-16 | Fmc Corp | Method for the continuous vapor phase acetylation of cellulose fiber |
JPS60139701A (en) * | 1983-12-28 | 1985-07-24 | Daicel Chem Ind Ltd | Production of cellulose acetate |
BR9306539A (en) * | 1992-06-11 | 1998-09-15 | Eastman Chem Co | Process for cellulose activation |
WO1994003497A1 (en) * | 1992-08-07 | 1994-02-17 | Eastman Chemical Company | Process for acetylation of cellulose |
GB9322187D0 (en) * | 1993-10-28 | 1993-12-15 | Bp Chem Int Ltd | Acetylation of lignocellulosic materials |
JPH09157303A (en) * | 1995-12-06 | 1997-06-17 | Bio Polymer Res:Kk | Acetylation of cellulose |
JPH09272701A (en) * | 1996-02-08 | 1997-10-21 | Daicel Chem Ind Ltd | Method for reaction control and apparatus therefor |
US5869646A (en) * | 1996-02-08 | 1999-02-09 | Daicel Chemical Industries, Ltd. | Method and apparatus for acetylating cellulose |
DE19857996A1 (en) * | 1998-12-16 | 2000-06-21 | Buna Sow Leuna Olefinverb Gmbh | Process for the production of thermoplastically processable starch esters |
JP3405981B1 (en) * | 2002-06-26 | 2003-05-12 | 日本財経株式会社 | Method for producing cellulose acetate |
DE102005001802A1 (en) * | 2004-09-30 | 2006-04-06 | List Holding Ag | Process for the continuous performance of polymerization processes |
-
2008
- 2008-07-29 DE DE102008035401A patent/DE102008035401B4/en not_active Expired - Fee Related
-
2009
- 2009-07-27 BR BRPI0916587A patent/BRPI0916587A2/en not_active IP Right Cessation
- 2009-07-27 CN CN2009801319026A patent/CN102124033A/en active Pending
- 2009-07-27 EP EP09777447A patent/EP2310420A1/en not_active Withdrawn
- 2009-07-27 JP JP2011520371A patent/JP2011529510A/en active Pending
- 2009-07-27 US US13/056,326 patent/US20110213140A1/en not_active Abandoned
- 2009-07-27 WO PCT/EP2009/005412 patent/WO2010012430A1/en active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2010012430A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN102124033A (en) | 2011-07-13 |
DE102008035401A1 (en) | 2010-02-11 |
JP2011529510A (en) | 2011-12-08 |
BRPI0916587A2 (en) | 2015-11-10 |
US20110213140A1 (en) | 2011-09-01 |
WO2010012430A1 (en) | 2010-02-04 |
DE102008035401B4 (en) | 2011-04-21 |
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Legal Events
Date | Code | Title | Description |
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Effective date: 20110225 |
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AX | Request for extension of the european patent |
Extension state: AL BA RS |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: DIENER, ANDREAS Inventor name: WITTE, DANIEL |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: DIENER, ANDREAS Inventor name: WITTE, DANIEL |
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DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20140716 |
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GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
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INTG | Intention to grant announced |
Effective date: 20160622 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20161103 |