WO1997031951A1 - Process for oxidising starch - Google Patents
Process for oxidising starch Download PDFInfo
- Publication number
- WO1997031951A1 WO1997031951A1 PCT/NL1997/000098 NL9700098W WO9731951A1 WO 1997031951 A1 WO1997031951 A1 WO 1997031951A1 NL 9700098 W NL9700098 W NL 9700098W WO 9731951 A1 WO9731951 A1 WO 9731951A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acylated
- starch
- polysaccharidc
- process according
- polysacchande
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline 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
- C08B31/18—Oxidised starch
Definitions
- the present invention relates to a process for reducing the viscosity of polysaccharides, especially starch, by oxidativc degradation without metal catalysts.
- Starch is economically relevant both as a foodstuff and for non-food applications. Worldwide the annual starch production is about 26 million tons.
- One of the largest non-food users of starch derivatives is the paper industry. In this field starch solutions with high starch content (25 wt.%) and low viscosities are much desired.
- Important features of starch derivatives arc an improved initial wet strength of the paper sheet, a better printability, a better retention of cationic additives and applicability as glue. The demand for these starch derivatives is several million tons a year.
- Starch has to be subjected to a viscosity-reducing treatment, before it can be used on an industrial scale.
- the starch is generally treated oxidatively in an alkaline medium at increased temperature (40-60°C). This treatment takes 4-15 hours at about 60°C, for example in case hypochlorite is used as an oxidising agent together with sulphuric acid or phosphoric acid.
- Disadvantages of this method are the amount of salt produced in addition to chlorine-containing derivatives, and a high proportion of short chain starch molecules. These disadvantages are becoming more and more important as there is an increasing demand for chlorine-free product.
- hydrogen peroxide is used together with a transition metal as a catalyst.
- a transition metal as a catalyst.
- Another disadvantage is the discoloration of the product.
- US-A-5,362,868 discloses a process wherein the viscosity of (hydroxycthyl) starch is reduced by oxidation using a pcracid at pH's ranging from 1 to 6 and at 40- 50°C.
- a pcracid at pH's ranging from 1 to 6 and at 40- 50°C.
- pcroxysulphuric acid H 2 SO 5
- pcracetic acid are used as peracid.
- the peroxysulphuric acid has to be prepared in situ from hydrogen peroxide and sulphuric acid, or else a salt of the acid has to be used, which has the disadvantage of generating salts as byproducts.
- the reactivity of pcracetic acid is lower and results in longer reaction times.
- cellulosic materials such as cotton can be bleached by treating the materials with pciacctic acid without actu ators, and simultaneously subiccting them to an ultrasonic ticatment (35 kHz).
- An object of the invention is to proxide a piocess for reducing the viscosity of starch and other polysaccharides with simple means, without the use of heavy metals and salt-producing agents, and without oiganic by -product It is also an object to provide a viscosity-ieducmg pioccss which allows the starch granule to remain intact, for easier working, drying and handling of the product .
- any wholh of partially water -soluble polysaccharide can be used.
- These comprise firstly starch (e.g. potato, corn. waxy maize, tapioca, wheat, rice and other starches) and fractions and derivatives thereof. such as amylose, floe gels, ethoxylated starch and carboxymethyl starch.
- starch e.g. potato, corn. waxy maize, tapioca, wheat, rice and other starches
- fractions and derivatives thereof such as amylose, floe gels, ethoxylated starch and carboxymethyl starch.
- solubility of cellulose derivatives and inulm and derivatives thereof and pentosans such as xylans can be improved or their viscosity can be reduced with the process of the invention .
- Carbohydrate derivatives such as N-acylated, carboxylatcd, carbow methylated, alkvlatcd, hydroxyalkylated, hydrogenated and dehydrogenated derivative
- the acylated carbohydiate used as a catalyst can be any oligo- or polysacchande which is wholh or partially acvlated It was found that only a small amount of acylated carbohy drate is necessary to cnsure an efficient reaction It is often sufficient if for each 700 anln diogkicosc (or other monosaccharide) units, one acylated monosaccharide unit is present.
- At least one and especially at least four monoacylatcd monosaccharide units are present for each 100 units
- an average of 0 06-0 2 acvlatcd monosacchandc units is present in the total of non-acylated and acylated polysaccharidc.
- acylated comprises alkanoylatcd (formylated, acetylatcd, propionylatcd, etc.), benzoylated, sulphatated, phosphory latcd etc.
- the acylated carbohydrate can simply be obtained by treatment of a carbo- hydrate with an acylating agent such as acetic anhydride using standard methods.
- acylated carbohydrates are commcrciallv available, such as acetyl starch having a DS of about 2.5% or 8%.
- An advantage of the use of an acylated carbohydrate is that the oxidation reaction proceeds smoothly and no undesired by-products arc formed; the acylated polysaccharidc or its oxidation product can be part of the treated polysaccharidc product without any inconvenience.
- the acylated carbohydrate can advantageously be a derivative of the same carbohydrate to be treated.
- the treatment of starch can suitable be performed using acetylated starch as the activator.
- the acvlatcd carbohydrate can be prepared in situ, e.g. by acylation with the corresponding carboxylic anhydride at pH 8-9.5 in a concentrated solution or suspension of the carbohydrate. The acylation may then be followed by the oxidation, but oxidation may also be started during acylation.
- the amount of hydrogen peroxide to be used is entirely dependent on the desired degree of oxidation.
- An amount of 1 wt.% is sufficient in general for achieving an effective viscosity degree.
- hydrogen peroxide 20 wt.% of hydrogen peroxide is used, with reference to the total of polysacchande and acylated carbohydrate.
- the hydrogen peroxide can be added at once, but it has been found that better products arc obtained when the hydrogen peroxide is added gradually or in portions, for example over a period from 5 minutes to 3 hours.
- the reaction can be performed at room temperature, but preferably at increased temperature, generally from 20 to 90°C. in particular from 40°C to 5°C below the pasting temperature, which pasting temperature is at about 65°C for most starch types. This results in a viscosity-reduced product still having a granular structure.
- the reaction time is from several minutes to several hours at that temperature, depending on the particular polysaccharidc and the desired degree of viscosity reduction.
- the polysaccharidc is preferably treated at a relatively high concentration. such as 10-55 wt.%, in particular 33-50 % by weight.
- the treatment is carried out under neutral to alkaline conditions, i.e. at a pH between 5 and 12, especially between 8 and 1 1, in particular between 9 and 1 1 .
- the treatment can advantageously be carried out in two or more stages, i.e. addition of peroxide at neutral pH (5-8.5) and subsequent reaction at alkaline pH (8.5- 1 1 ).
- the acylation can be performed under slightly alkaline conditions (pH 7.5-9.5), during or after acylation peroxide is added with some pH decrease (e.g. pH 6-8.5) and oxidation is completed at higher pH (8.5-1 1 ).
- the product obtained by the process of the invention is essentially free of chlorine (as salt or covalcntly bound), i.e. not above natural abundance ( ⁇ 20 ppm) and of transition metals.
- the carboxyl content is preferably between 0.2 and 5, especially between 0.5 and 3 wt.%.
- the viscosity is preferably below 4000 Brabender units (at 25 w.t% dry substance and at 40°C) and in particular below 1000 Brabender units.
- Viskograph E The results arc given below in Brabender units at 40°C; V 5 means viscosity at 5 wt.%.
- Table 1 summarises the results of the product after 3 hours and after 6 hours. The result of the treatment using only hydrogen peroxide after 3 hours is also given for comparison.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
- Paper (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU22354/97A AU723782B2 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
NZ331585A NZ331585A (en) | 1996-02-29 | 1997-02-28 | Process for reducing the viscosity of a polysaccharide with hydrogen peroxide and an acylated polysaccharide as activator |
BR9707771-2A BR9707771A (en) | 1996-02-29 | 1997-02-28 | Process to reduce the viscosity of a polysaccharide |
PL97328613A PL328613A1 (en) | 1996-02-29 | 1997-02-28 | Starch oxidation process |
JP9530836A JP2000506197A (en) | 1996-02-29 | 1997-02-28 | Preparation method of oxidized starch |
SK1190-98A SK119098A3 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
EP97905500A EP0883630A1 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
EA199800778A EA000896B1 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising polysaccharides |
IL12594297A IL125942A0 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
BG102731A BG102731A (en) | 1996-02-29 | 1998-08-28 | Method for starch oxidation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1002494 | 1996-02-29 | ||
NL1002494A NL1002494C2 (en) | 1996-02-29 | 1996-02-29 | Method for oxidizing starch. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997031951A1 true WO1997031951A1 (en) | 1997-09-04 |
Family
ID=19762420
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1997/000098 WO1997031951A1 (en) | 1996-02-29 | 1997-02-28 | Process for oxidising starch |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0883630A1 (en) |
JP (1) | JP2000506197A (en) |
KR (1) | KR19990087307A (en) |
CN (1) | CN1212708A (en) |
AU (1) | AU723782B2 (en) |
BG (1) | BG102731A (en) |
BR (1) | BR9707771A (en) |
CA (1) | CA2247109A1 (en) |
CZ (1) | CZ266998A3 (en) |
EA (1) | EA000896B1 (en) |
HU (1) | HUP9901784A3 (en) |
IL (1) | IL125942A0 (en) |
NL (1) | NL1002494C2 (en) |
NZ (1) | NZ331585A (en) |
PL (1) | PL328613A1 (en) |
SK (1) | SK119098A3 (en) |
TR (1) | TR199801653T2 (en) |
WO (1) | WO1997031951A1 (en) |
YU (1) | YU37298A (en) |
ZA (1) | ZA971785B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1007085C2 (en) * | 1997-09-19 | 1999-03-22 | Inst Voor Agrotech Onderzoek | Carbohydrate oxidation with hydrogen peroxide |
NL1010660C2 (en) * | 1998-11-26 | 2000-05-30 | Inst Voor Agrotech Onderzoek | Method for oxidizing starch. |
US6635755B1 (en) | 1999-11-08 | 2003-10-21 | Sca Hygiene Products Gmbh | Oxidized polymeric carbohydrates and products made thereof |
DE10241040B4 (en) * | 2001-09-04 | 2004-11-18 | Heppe Gmbh Biotechnologische Systeme Und Materialien | Modified polysaccharide materials and process for their manufacture |
US10759727B2 (en) | 2016-02-19 | 2020-09-01 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100371866B1 (en) * | 2000-06-24 | 2003-02-11 | 주식회사 삼양제넥스 | Modified starch useful for paper surface sizing and a method thereof |
CN101177459B (en) * | 2007-11-30 | 2010-05-19 | 四川大学 | High carbonyl content oxidation starch and method for making same |
US8641863B2 (en) * | 2011-09-30 | 2014-02-04 | Weyerhaeuser Nr Company | Catalytic carboxylation of cellulose fibers in a continuous process with multiple additions of catalyst, secondary oxidant and base to a moving slurry of cellulose fibers |
KR101409213B1 (en) * | 2012-12-20 | 2014-06-19 | 대상 주식회사 | Method for decreasing sulfurous acid included in by-products of corn wet-milling |
EP3205673B1 (en) * | 2016-02-12 | 2018-05-23 | Coöperatie Avebe U.A. | Oxidation of starch |
CN114751994B (en) * | 2022-03-18 | 2023-02-17 | 西南林业大学 | Acetylated oxidized starch and preparation method thereof, modified urea-formaldehyde resin adhesive and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR878146A (en) * | 1940-07-01 | 1943-01-12 | Degussa | Starch separation process |
US2955905A (en) * | 1955-07-27 | 1960-10-11 | Lever Brothers Ltd | Peroxide-ester bleaching process and compositions |
US5342542A (en) * | 1990-12-28 | 1994-08-30 | Ausimont S.P.A. | Process for increasing the bleaching efficiency of persalts by using a partially acetylated sucrose as a bleach activator |
US5362868A (en) * | 1993-06-18 | 1994-11-08 | Degussa Aktiengesellshaft | Thinning of granular starch |
-
1996
- 1996-02-29 NL NL1002494A patent/NL1002494C2/en not_active IP Right Cessation
-
1997
- 1997-02-28 KR KR1019980706715A patent/KR19990087307A/en not_active Application Discontinuation
- 1997-02-28 CA CA002247109A patent/CA2247109A1/en not_active Abandoned
- 1997-02-28 ZA ZA9701785A patent/ZA971785B/en unknown
- 1997-02-28 HU HU9901784A patent/HUP9901784A3/en unknown
- 1997-02-28 CZ CZ982669A patent/CZ266998A3/en unknown
- 1997-02-28 BR BR9707771-2A patent/BR9707771A/en not_active Application Discontinuation
- 1997-02-28 CN CN97192664A patent/CN1212708A/en active Pending
- 1997-02-28 SK SK1190-98A patent/SK119098A3/en unknown
- 1997-02-28 TR TR1998/01653T patent/TR199801653T2/en unknown
- 1997-02-28 PL PL97328613A patent/PL328613A1/en unknown
- 1997-02-28 IL IL12594297A patent/IL125942A0/en unknown
- 1997-02-28 EP EP97905500A patent/EP0883630A1/en not_active Ceased
- 1997-02-28 JP JP9530836A patent/JP2000506197A/en active Pending
- 1997-02-28 NZ NZ331585A patent/NZ331585A/en unknown
- 1997-02-28 AU AU22354/97A patent/AU723782B2/en not_active Ceased
- 1997-02-28 EA EA199800778A patent/EA000896B1/en not_active IP Right Cessation
- 1997-02-28 WO PCT/NL1997/000098 patent/WO1997031951A1/en not_active Application Discontinuation
- 1997-02-28 YU YU37298A patent/YU37298A/en unknown
-
1998
- 1998-08-28 BG BG102731A patent/BG102731A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR878146A (en) * | 1940-07-01 | 1943-01-12 | Degussa | Starch separation process |
US2955905A (en) * | 1955-07-27 | 1960-10-11 | Lever Brothers Ltd | Peroxide-ester bleaching process and compositions |
US5342542A (en) * | 1990-12-28 | 1994-08-30 | Ausimont S.P.A. | Process for increasing the bleaching efficiency of persalts by using a partially acetylated sucrose as a bleach activator |
US5362868A (en) * | 1993-06-18 | 1994-11-08 | Degussa Aktiengesellshaft | Thinning of granular starch |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL1007085C2 (en) * | 1997-09-19 | 1999-03-22 | Inst Voor Agrotech Onderzoek | Carbohydrate oxidation with hydrogen peroxide |
NL1010660C2 (en) * | 1998-11-26 | 2000-05-30 | Inst Voor Agrotech Onderzoek | Method for oxidizing starch. |
WO2000031145A1 (en) * | 1998-11-26 | 2000-06-02 | Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) | Process for oxidising starch |
US6635755B1 (en) | 1999-11-08 | 2003-10-21 | Sca Hygiene Products Gmbh | Oxidized polymeric carbohydrates and products made thereof |
US6987181B2 (en) | 1999-11-08 | 2006-01-17 | Sca Hygiene Products Gmbh | Oxidized polymeric carbohydrates and products made thereof |
DE10241040B4 (en) * | 2001-09-04 | 2004-11-18 | Heppe Gmbh Biotechnologische Systeme Und Materialien | Modified polysaccharide materials and process for their manufacture |
US10759727B2 (en) | 2016-02-19 | 2020-09-01 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
US11840500B2 (en) | 2016-02-19 | 2023-12-12 | Intercontinental Great Brands Llc | Processes to create multiple value streams from biomass sources |
Also Published As
Publication number | Publication date |
---|---|
ZA971785B (en) | 1997-09-29 |
IL125942A0 (en) | 1999-04-11 |
BG102731A (en) | 1999-07-30 |
NZ331585A (en) | 2000-03-27 |
EP0883630A1 (en) | 1998-12-16 |
PL328613A1 (en) | 1999-02-01 |
BR9707771A (en) | 2000-01-04 |
HUP9901784A2 (en) | 1999-10-28 |
EA199800778A1 (en) | 1999-02-25 |
KR19990087307A (en) | 1999-12-27 |
EA000896B1 (en) | 2000-06-26 |
TR199801653T2 (en) | 1998-12-21 |
HUP9901784A3 (en) | 1999-11-29 |
YU37298A (en) | 1999-09-27 |
AU723782B2 (en) | 2000-09-07 |
JP2000506197A (en) | 2000-05-23 |
CZ266998A3 (en) | 1999-03-17 |
NL1002494C2 (en) | 1997-09-01 |
CN1212708A (en) | 1999-03-31 |
AU2235497A (en) | 1997-09-16 |
CA2247109A1 (en) | 1997-09-04 |
SK119098A3 (en) | 1999-06-11 |
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