EP0778850A1 - Method of modifying starch - Google Patents
Method of modifying starchInfo
- Publication number
- EP0778850A1 EP0778850A1 EP95928638A EP95928638A EP0778850A1 EP 0778850 A1 EP0778850 A1 EP 0778850A1 EP 95928638 A EP95928638 A EP 95928638A EP 95928638 A EP95928638 A EP 95928638A EP 0778850 A1 EP0778850 A1 EP 0778850A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- slurry
- reagent
- lye
- temperature
- starch
- 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- Withdrawn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
- 229920002472 Starch Polymers 0.000 title claims abstract description 26
- 235000019698 starch Nutrition 0.000 title claims abstract description 26
- 239000008107 starch Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 230000003068 static effect Effects 0.000 claims abstract description 10
- 230000005670 electromagnetic radiation Effects 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000008187 granular material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 43
- 239000000047 product Substances 0.000 description 12
- 229920000881 Modified starch Polymers 0.000 description 6
- 239000004368 Modified starch Substances 0.000 description 5
- 235000019426 modified starch Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
- C08B30/16—Apparatus therefor
-
- 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
-
- 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
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
Definitions
- modified starch products such as starch ethers and starch esters
- starch ethers and starch esters are often used as additive in the food and paper industry.
- applications of inter alia hydroxypropyl starch are the use as additive in textile printing and as size for corrugated board.
- the production of modified starch with a low molar substitution is done on an industrial scale by reaction of a suitable reagent, for instance ethylene oxide, propylene oxide or vinyl acetate, in an aqueous slurry of starch.
- the invention contemplates providing a solution to one o more of these problems and is partly based on the insight th the problem of poor reproducibility and homogeneity of the product can be obviated at least partly by distributing the added lye homogeneously in the slurry.
- the invention accordingly relates to a method for continuously modifying starch, wherein a suspension of starc granules (slurry) in an aqueous liquid is heated to a temperature at which still no gelatinization occurs, then ly and reagent are continuously fed to the suspension, with the lye and optionally also the reagent being distributed homogeneously in the slurry, whereafter by means of electromagnetic radiation the mixture is further heated to temperature desired for complete gelatinization and the modification and the mixture is fed to a reactor section provided with static mixing elements.
- the invention is based on the surprising insight that b special combination of measures the objects of the inventio can be realized. Of importance in this combination is first the preheating of the suspension of starch particles to a temperature at which still no gelatinization occurs. Preferably, this preheating is effected to a temperature which is not more than 15, preferably not more than 10 and more particularly not more than 5°C below the temperature at which gelatinization will occur.
- a second aspect of the invention is concerned with the homogeneous feed of lye, which means that the lye is uniformly distributed throughout the entire slurry in a shortest possible period of time, while in the liquid substantially no concentration gradient of the supplied component over the cross section of the space arises.
- the modifying reagent often an alkene oxide or vinyl acetate, preferably ethylene oxide and/or propylene oxide, is added simultaneously with the lye or prior thereto.
- this addition is also effected homogeneously, although this seems to be less critical.
- a third aspect of the invention is concerned with the homogeneous heating of the continuously gelatinizing mixture by means of electromagnetic radiation, in short, with a magnetron.
- Heating the continuously gelatinizing mixture with a magnetron leads to a highly uniform rise in temperature, so that the viscosity of the mixture over a cross section of the reactor remains the same. This prevents any substantial spread in the residence time due to differences in viscosity.
- Other methods of heating entail the problem that the non-uniform distribution of the heat, for instance due to a gradient over the cross section of the reactor, gives rise to large viscosity differences, as a consequence of which parts of t reactor content "shoot through" while other parts linger fo long time. The result is a marked difference in product quality in the reactor output.
- modified starch which satisfies the conditions in the introduction. More particularly, a homogeneous and reproducible product of a low sodium hydroxide (lye) conten is obtained.
- the various process conditions can be chosen by the skilled person, depending on the final products actually desired.
- the nature of the substitution and the degree of substitution partly determine the process conditions, such as the amount of lye, the preheat temperature, and so forth.
- these variables also depend on the amount of starch in the suspension, which may for instance be between 10 and 45% by weight.
- the lye solution preferably with a concentration of from 0.05 to 5 molar, is to be adde homogeneously, it being sufficient to use a concentration o maximally 300 mol/m 3 slurry.
- This can be effected with advantage by feeding the lye and optionally also the alkene oxide to the slurry in a tubular reactor segment using one or more supply tubes which are arranged axially in the tubular reaction segment, and which supply tubes are provided with radial outlet openings.
- Heating of the mixture is effected to a temperature which will be dependent on the degree of substitution and on the nature of the substituent, as well as on the amount of lye. It is noted that the supplied lye not only (partly) effects the gelatinization, but can also catalyze the modification reaction, for instance the etherification or the esterification reaction. Preferably, heating is effected to a temperature between 60 and 120°C, whereafter the heated mixture reacts further in the section of static mixing elements.
- a reactor is depicted which is suitable for the practise of the method according to the invention.
- the reactor 1. is provided with a supply for the starch slurry 2, which slurry is mixed in mixing chamber 3 with reagent and lye. These are supplied via feed lines 4 and 5. It is of great importance in this connection that the feed of lye via line 5 takes place uniformly throughout the liquid. According to the invention, this can be achieved by providing the feed line 5 at the end thereof with radial openings, indicated by arrow 6. After passing the mixing chamber, the gelatinizing slurry enters reactor section 7, which is provided with static mixing elements 8, for instance SMX ® elements.
- the slurry is further heated to the temperature desired for the complete gelatinization and modification, by means of electromagnetic radiation generated with microwave unit 9.
- the reaction can be continued further in react segments (not shown) provided with static mixing elements, whereafter finally the modified starch can be discharged fr the reactor and be processed further into a form that is suitable for sale and/or be stored.
- a slurry consisting of 34.8% by weight of starch granul in water was fed at a flow rate of 3.07xl0" 3 kg/s to a reac as depicted in the drawing.
- This slurry had been heated in preheating unit (not shown in the drawing) to a temperature 57°C.
- preheating unit not shown in the drawing
- 0.21 g/s propylene oxide and 0. g/s of a 4 molar lye solution were continuously added to th slurry.
- the resultant highly viscous liquid was then heated a temperature of 90°C in the mixing section 8 by means of t microwave unit 9. After a residence time of 300 s in the reactor section of the reactor, which was also maintained a
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)
- Crystallography & Structural Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL9401412A NL9401412A (nl) | 1994-08-31 | 1994-08-31 | Werkwijze voor het modificeren van zetmeel. |
NL9401412 | 1994-08-31 | ||
PCT/NL1995/000283 WO1996006866A1 (en) | 1994-08-31 | 1995-08-25 | Method of modifying starch |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0778850A1 true EP0778850A1 (en) | 1997-06-18 |
Family
ID=19864592
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95928638A Withdrawn EP0778850A1 (en) | 1994-08-31 | 1995-08-25 | Method of modifying starch |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0778850A1 (nl) |
AU (1) | AU3231995A (nl) |
NL (1) | NL9401412A (nl) |
WO (1) | WO1996006866A1 (nl) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101747445B (zh) * | 2008-12-15 | 2012-12-12 | 天津科技大学 | 一种经超声和微波协同作用制备羟丙基淀粉的方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2074596B (en) * | 1980-04-25 | 1983-07-06 | Cpc International Inc | Method of modifying starch |
ZA815023B (en) * | 1980-08-07 | 1982-07-28 | Cpc International Inc | Method of modifying starch |
FR2629684B1 (fr) * | 1988-04-06 | 1991-06-07 | Agronomique Inst Nat Rech | Matiere amylacee et son procede de fabrication |
-
1994
- 1994-08-31 NL NL9401412A patent/NL9401412A/nl not_active Application Discontinuation
-
1995
- 1995-08-25 WO PCT/NL1995/000283 patent/WO1996006866A1/en not_active Application Discontinuation
- 1995-08-25 EP EP95928638A patent/EP0778850A1/en not_active Withdrawn
- 1995-08-25 AU AU32319/95A patent/AU3231995A/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO9606866A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1996006866A1 (en) | 1996-03-07 |
AU3231995A (en) | 1996-03-22 |
NL9401412A (nl) | 1996-04-01 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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17P | Request for examination filed |
Effective date: 19970327 |
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17Q | First examination report despatched |
Effective date: 19970710 |
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GRAH | Despatch of communication of intention to grant a patent |
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STAA | Information on the status of an ep patent application or granted ep patent |
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18D | Application deemed to be withdrawn |
Effective date: 19981204 |