CN103739723A - Method for preparing octenyl succinate starch ester - Google Patents
Method for preparing octenyl succinate starch ester Download PDFInfo
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- CN103739723A CN103739723A CN201310708191.2A CN201310708191A CN103739723A CN 103739723 A CN103739723 A CN 103739723A CN 201310708191 A CN201310708191 A CN 201310708191A CN 103739723 A CN103739723 A CN 103739723A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a method for preparing octenyl succinate starch ester. The method is characterized in that the octenyl succinate starch ester is prepared by using starch as a raw material, using hydrogen peroxide or sodium hypochlorite as oxidant and using octenyl succinic anhydride as esterifying agent according to the following reaction process: A. respectively adding the starch, the oxidant and the esterifying agent into a supercritical reaction kettle, adding CO2 by using a high-pressure pump, and then, heating up to a supercritical temperature of 40-60 DEG C, wherein the supercritical pressure is 8.0-25 Mpa and the reaction time is 1-6 hours; B. carrying out an oxidation and esterification one-step synthesis reaction under the supercritical reaction conditions and a stirring condition; and C. after the oxidation and esterification one-step synthesis reaction, supercritical extracting the reactants to obtain powdery octenyl succinate starch ester.
Description
Technical field
The invention belongs to foodstuff additive preparing technical field, specifically a kind of method of preparing starch octenyl succinate anhydride.
Background technology
Starch octenyl succinate anhydride (OSAS) is to be a kind ofly widely used in that the fields such as food, medicine, makeup, biological products are eco-friendly, the modified starch of green safety.At present, the method for making starch octenyl succinate anhydride (OSAS) both at home and abroad has multiple, and mainly adopting water method is main wet processing, also has part to adopt solvent method technique and the dry process of organic solvent.And take at present both at home and abroad mainly the wet processing that water is medium, prepare OSAS as main.
Making aspect starch octenyl succinate anhydride (OSAS), we have retrieved following open source literatures, but all corresponding existence some use limitation.For example:
1. patent documentation CN1431285 has introduced a kind of production method of starch octenyl succinate anhydride, comprises the following steps: 1) yam starch and water are blended into emulsion under the effect of constant temperature blender with magnetic force; 2) adopt pH value to 7.5～8.0 of the sodium hydroxide adjusting above-mentioned emulsion that weight concentration is 3%; 3) adopt dehydrated alcohol dilution octenyl succinic acid anhydride; 4) by step 3) octenyl succinic acid anhydride and step 2 after the dilution of gained) the emulsion mixed reaction system that forms mutually of gained; The NaoH solution that interpolation weight concentration is 3% maintains pH value to 7.5～8.0 of reaction system, and the reaction times is 2～4 hours; 5) first with the hydrochloric acid soln of 2mol/L, be adjusted to step 4) pH value to 6.4～6.6 of products therefrom; Each washing of the ethanol that water, weight concentration are 70% respectively more once; Then be dried successively and pulverize.
2. patent documentation CN101407552 has introduced a kind of technique of producing low viscosity octenylsuccinate starch by oxidation process ester, in reaction vessel, Waxy Rice Starch and water are made into starch milk, then be warming up to 34-38 ℃, add sodium hydroxide solution to adjust pH value between 9.3-9.7; Add clorox to carry out oxidizing reaction, and keep above-mentioned pH value and temperature of reaction; Then add Sodium Pyrosulfite to carry out reduction reaction, in reaction process, add the pH value of hydrochloric acid soln adjustment starch milk between 8.5-9.0, and be cooled to 28-31 ℃, then slowly add the octenyl succinic acid anhydride of over dry starch total mass 2-3% to carry out esterification, after esterification finishes, add hydrochloric acid soln that starch milk is neutralized to pH value between 5.5-6.5, the starch milk after neutralization is made to finished product through washing, being dried.
Yet, above-mentionedly take wet processing that water is medium and have the following problem that solves of cannot evading and be difficult to: (1) alkenyl succinic anhydride is the material of indissoluble water, the rate of mass transfer that needs to accelerate by increasing mass transfer interface alkenyl succinic anhydride, could effectively add fast response; (2) can there is hydrolysis reaction in alkenyl succinic anhydride under acidity, neutrality or alkaline environment, and its hydrolysis reaction degree is to reaction efficiency important; (3) in order to facilitate aftertreatment, temperature of reaction must be controlled at below starch gelatinization temperature, and starch keeps particulate form (solid-state), and reaction system is liquid-liquid-solid three-phase heterogeneous reaction system, control requirement to reaction conditions is quite strict, is also difficult to improve the esterification efficiency of esterification; (4) although water method can effectively be removed the impurity such as unreacting reagent, but need to make respectively the repeatedly reacted product of repetitive scrubbing of water and Virahol, acetone equal solvent, the complexity that has improved aftertreatment technology, has extended life cycle of the product, has also greatly increased product preparation cost.
Summary of the invention
The object of this invention is to provide a kind of method of preparing starch octenyl succinate anhydride, high to overcome above-mentioned preparation method's foreign matter content, the shortcoming that reaction efficiency is low.
In order to solve the problems of the technologies described above, the invention provides a kind of method of preparing starch octenyl succinate anhydride, comprise the following steps:
A, starch, oxygenant and esterifying agent are added respectively in supercritical reaction still, and add CO by high-pressure pump
2, then temperature is risen to 40～60 ℃ of supercritical temperatures, supercritical pressure 8.0～25Mpa, the reaction times is 1～6 hour;
B, in above-mentioned supercritical reaction conditions, and under agitation condition, oxidation and esterification one-step synthesis are reacted;
C, carry out after mixed precipitation, temperature is remained on to 30～35 ℃; This step can be so that the purity of starch alkenyl succinate ester improves more than 5%.
D, after oxidation and esterification one-step synthesis reaction, reactant is carried out to supercritical extraction, obtain pulverous starch octenyl succinate anhydride.
Above-described starch material is tapioca (flour), W-Gum or yam starch.
In above-described A step, starch quality concentration is 65%～86%, and oxygenant is 0.25%～0.32%, and esterifying agent is 0.43%～11.8%, and water is 12%～19.7%.
In above-described A step, can be added into basic catalyst fast reaction speed.
The range of viscosities of the starch octenyl succinate anhydride being prepared from according to above step is: 5～25mPas(6%, 95 ℃), substitution value is 0.005～0.12.
The present invention uses the harmless supercritical CO of low toxicity
2for reaction medium, recycling supercritical CO
2the byproduct generating in fluid extraction unreacting reagent and reaction process, product starch octenyl succinate anhydride is without Harmful chemicals and dissolvent residual, guaranteed product edible safety, make chemical reagent quick permeation in starch granules, reaction evenly, esterification efficiency is high, has effectively solved the problems of preparing starch octenyl succinate anhydride in water medium, is a kind of friendly process of efficient synthesizing octene base succinic acid starch ester.
Embodiment
Embodiment 1
The novel method of preparing starch octenyl succinate anhydride under a kind of super critical condition.Its operational path is: in supercritical reaction still, add 100 grams of W-Gums, and 2.5 grams of oxygenants, 5 grams of esterifying agents, 2.0 grams of sodium hydroxide, 25 grams of water, with supercritical CO
2for reaction medium, 45 ℃ of supercritical temperatures, supercritical pressure 16MPa carries out starch oxidation and esterification modification reaction subsequently simultaneously under stirring state, and in 2 hours reaction times, reaction is complete remains on 30 ℃ by temperature, at 40 ℃ of supercritical temperatures, pressure 22MPa, CO
2flow is 15 L/h supercritical extraction purified products, obtains pulverous starch octenyl succinate anhydride product.
The product substitution value that the present embodiment obtains is 0.021, and viscosity is 10 ~ 12 mPas(6%, 92 ℃).
Embodiment 2
The novel method of preparing starch octenyl succinate anhydride under a kind of super critical condition.Its operational path is: in supercritical reaction still, add 100 grams of tapioca (flour)s, and 1.5 grams, oxygenant, 10 grams of esterifying agents, 30 grams, water, with supercritical CO
2for reaction medium, 60 ℃ of supercritical temperatures, supercritical pressure 12MPa, remains on 30 ℃ by temperature, carries out starch oxidation and esterification modification reaction under stirring state simultaneously, and in 4 hours reaction times, reaction is finished, at 45 ℃ of supercritical temperatures, pressure 26MPa, CO
2flow is 20 L/h supercritical extraction purified products, obtains pulverous starch octenyl succinate anhydride product.
The product substitution value that the present embodiment obtains is 0.061, and viscosity is 16 ~ 21 mPas(6%, 93 ℃).
Claims (4)
1. a method of preparing starch octenyl succinate anhydride, is characterized in that: using starch as raw material, hydrogen peroxide or clorox are as oxygenant, and octenyl succinic acid anhydride, as esterifying agent, is made through following reaction process:
A, starch, oxygenant and esterifying agent are added respectively in supercritical reaction still, and add reaction medium CO by high-pressure pump
2, then temperature is risen to 40～60 ℃ of supercritical temperatures, supercritical pressure 8.0～25Mpa, the reaction times is 1～6 hour;
B, in above-mentioned supercritical reaction conditions, and under agitation condition, oxidation and esterification one-step synthesis are reacted;
C, carry out after mixed precipitation, temperature is remained on to 30～35 ℃;
E, after oxidation and esterification one-step synthesis reaction, reactant is carried out to supercritical extraction, obtain pulverous starch octenyl succinate anhydride.
2. the method for preparing starch octenyl succinate anhydride according to claim 1, is characterized in that: described starch material is tapioca (flour), W-Gum or yam starch.
3. the method for preparing starch octenyl succinate anhydride according to claim 1, is characterized in that: in described A step, starch quality concentration is 65%～86%, and oxygenant is 0.25%～0.32%, and esterifying agent is 0.43%～11.8%, and water is 12%～19.7%.
4. the method for preparing starch octenyl succinate anhydride according to claim 1, is characterized in that: in described A step, be added into basic catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310708191.2A CN103739723A (en) | 2013-12-20 | 2013-12-20 | Method for preparing octenyl succinate starch ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310708191.2A CN103739723A (en) | 2013-12-20 | 2013-12-20 | Method for preparing octenyl succinate starch ester |
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| CN103739723A true CN103739723A (en) | 2014-04-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519051A (en) * | 2016-10-19 | 2017-03-22 | 广西大学 | Method for preparing starch high carbonate ester under supercritical condition |
| CN108290963A (en) * | 2015-11-26 | 2018-07-17 | 卡吉尔公司 | Stabilize starch |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0893451A2 (en) * | 1997-07-25 | 1999-01-27 | National Starch and Chemical Investment Holding Corporation | Polysaccharide modification in densified fluid |
| CN101139401A (en) * | 2007-10-25 | 2008-03-12 | 重庆泰威生物工程股份有限公司 | Starch ester and preparation method and use thereof |
| CN101503476A (en) * | 2009-03-16 | 2009-08-12 | 天津大学 | Method for synthesizing starch ester of ocentyl succinic |
| CN102367280A (en) * | 2011-11-16 | 2012-03-07 | 广西大学 | Preparation method of starch octenyl succiniade under supercritical condition |
-
2013
- 2013-12-20 CN CN201310708191.2A patent/CN103739723A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0893451A2 (en) * | 1997-07-25 | 1999-01-27 | National Starch and Chemical Investment Holding Corporation | Polysaccharide modification in densified fluid |
| CN101139401A (en) * | 2007-10-25 | 2008-03-12 | 重庆泰威生物工程股份有限公司 | Starch ester and preparation method and use thereof |
| CN101503476A (en) * | 2009-03-16 | 2009-08-12 | 天津大学 | Method for synthesizing starch ester of ocentyl succinic |
| CN102367280A (en) * | 2011-11-16 | 2012-03-07 | 广西大学 | Preparation method of starch octenyl succiniade under supercritical condition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290963A (en) * | 2015-11-26 | 2018-07-17 | 卡吉尔公司 | Stabilize starch |
| CN108290963B (en) * | 2015-11-26 | 2021-09-21 | 卡吉尔公司 | Stabilized starch |
| CN106519051A (en) * | 2016-10-19 | 2017-03-22 | 广西大学 | Method for preparing starch high carbonate ester under supercritical condition |
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Application publication date: 20140423 |