CN104479032A - Method for preparing rice starch acetate with high substitution degree through catalysis of phosphotungstic acid and toluenesulfonic acid - Google Patents
Method for preparing rice starch acetate with high substitution degree through catalysis of phosphotungstic acid and toluenesulfonic acid Download PDFInfo
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- CN104479032A CN104479032A CN201410849340.1A CN201410849340A CN104479032A CN 104479032 A CN104479032 A CN 104479032A CN 201410849340 A CN201410849340 A CN 201410849340A CN 104479032 A CN104479032 A CN 104479032A
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Abstract
The invention belongs to the field of starch deep processing, and relates to a method for preparing rice starch acetate with a high substitution degree through catalysis of phosphotungstic acid and toluenesulfonic acid. The method is characterized in that rice starch serves as a raw material, glacial acetic acid serves as a solvent, and acetic oxide serves as an esterifying agent; the reaction is carried out for 2 to 3 hours at a temperature of 70 to 80 DEG C through catalysis of the phosphotungstic acid and the toluenesulfonic acid; a reaction product is sufficiently washed with plenty of distilled water; the rice starch acetate with a substitution degree of above 2.5 is obtained after vacuum drying. The method has the characteristics of high yield, high substitution degree, short reaction time, little corrosion of equipment, etc.
Description
Technical field
The present invention relates to a kind of method that high substitution value Starch rice acetic ester is prepared in phospho-wolframic acid and toluenesulphonic acids catalysis, belong to starch field of deep.
Background technology
China's rice has its advantageous superiority, at home and abroad market share consequence, and along with growth in the living standard, people require more and more higher to rice mouthfeel.Due to traditional husk rice technology, and the circulation in the course of processing can produce 10% ~ 15% crack rice, these crack rice general as feed use, but the protein in cracking rice, the nutritive substances such as starch are close with rice, and price only has 30% ~ 50% of rice, if insufficient utilization, rice can be caused to provide former very large waste, therefore research and develop product of cracking rice and just seem more and more urgent.Due to the starch content up to 70% in rice, the raw material that can be used as and produce modified starch of cracking rice.
In recent years, the research of the acetate starch with high substitution value reported is a lot, but not seeing of utilizing Starch rice to prepare.The preparation of high substituted starch acetic ester generally adopts the vitriol oil to make catalyzer, although liquid acid is inexpensive, catalytic activity is high, and obtained starch substitution value can reach requirement, but side reaction is many, equipment corrosion is serious, productive rate is low.People study novel process always, although ionic liquid preparation environmental protection, obtained product also meets the requirements, and due to the selling at exorbitant prices of height liquid, industrial production cannot realize.With organic acid (as toluenesulphonic acids etc.) as catalyzer, although output is high, the substitution value of product is slightly on the low side, and between 2.0 ~ 2.5, and toluenesulphonic acids is poisonous, and in boiling water, discharge can cause environmental pollution.
Phospho-wolframic acid is catalyzer conventional in organic reaction, mainly replaces liquid acids at home and abroad, as sulfuric acid, hydrofluoric acid, aluminum chloride etc.But with the research not report of phospho-wolframic acid as catalyst preparing starch acetate.Under the environment in laboratory, carry out, with the research of phospho-wolframic acid as catalyst preparing Starch rice acetic ester, finding that the catalytic effect of phospho-wolframic acid is better than liquid acid and toluene.But because phospho-wolframic acid price is higher, promote and have certain difficulty.Therefore, the break technique of production Starch Acetates with High Degree of Substitution of existing rank haves much room for improvement.
Summary of the invention
The present invention is in order to make up the deficiency of existing technique, reduce the rate of side effects of reaction process, reduce equipment corrosion degree, catalyzer cost can be reduced again, keep high substitution value, provide a kind of economical and practical, output is high, substitution value is high, and product meets the requirements, to the preparation method of the little Starch Acetates with High Degree of Substitution of equipment corrosion.
Technical scheme of the present invention is:
A method for high substitution value Starch rice acetic ester is prepared in phospho-wolframic acid and toluenesulphonic acids catalysis, comprises the following steps:
(1) Starch rice is mixed with Glacial acetic acid, obtain the starch milk of certain mass mark, and at room temperature fully stir;
(2) starch milk is heated up, add a certain amount of phospho-wolframic acid, toluenesulphonic acids and acetic anhydride successively;
(3), after reacting certain hour, use distilled water fully to wash, suction filtration, vacuum-drying, obtains Starch rice acetic ester.
Preferably, in described step (1), Starch rice is mixed with Glacial acetic acid, obtain the starch milk of massfraction 25% ~ 33%.
Preferably, in described step (1), churning time is 10 ~ 20min.
Preferably, in described step (2), starch milk is warmed up to 70 ~ 80 DEG C.
Preferably, in described step (2), the mass ratio of starch, Glacial acetic acid, phospho-wolframic acid, toluenesulphonic acids and acetic anhydride is 10:(20 ~ 30): (0.5 ~ 1): (2 ~ 3): (20 ~ 30).
Preferably, in described step (3), the reaction times is 2 ~ 3h.
Preferably, in described step (3), by filter cake vacuum-drying 24h at 50 DEG C.
A kind of Starch rice acetic ester, be prepared from by above-mentioned method, its substitution value is higher than 2.5.
Preferably, the substitution value of described Starch rice acetic ester is 2.5-2.7.
Preferably, described Starch rice acetic ester is faint yellow.
Beneficial effect of the present invention: the present invention, with Starch rice raw material, adopts mixed catalyst to prepare high substitution value Starch rice acetic ester.The method overcome liquid acid low as productive rate during catalyzer, equipment corrosion seriously waits shortcomings, and the product substitution value obtained is high, and the product that more simple organic acid catalysis obtains has obvious advantage.Importantly, although phospho-wolframic acid is on the high side, under the synergy of toluenesulphonic acids, phospho-wolframic acid consumption is less, excellent catalytic effect, and prepare starch acetate relative to the ionic liquid of costliness as solvent, price advantage is obvious.Therefore, the production technique of this invention is specially adapted to factory's use.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Technology contents of the present invention and effect is further illustrated below by example.
Embodiment 1
Get 20 parts of Starch rices, at room temperature stir 15min with 50 parts of Glacial acetic acid and fully mix, be warming up to 75 DEG C, add 1 part of phospho-wolframic acid, toluenesulphonic acids 5 parts, then add 55 parts of acetic anhydride, reaction 2.5h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.53.
Embodiment 2
Get 20 parts of Starch rices, at room temperature stir 15min with 50 parts of Glacial acetic acid and fully mix, be warming up to 80 DEG C, add 2 parts of phospho-wolframic acids, toluenesulphonic acids 4 parts, then add 54 parts of acetic anhydride, reaction 3h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.62.
Embodiment 3
Get 20 parts of Starch rices, at room temperature stir 15min with 60 parts of Glacial acetic acid and fully mix, be warming up to 70 DEG C, add phospho-wolframic acid 1 part, toluenesulphonic acids 6 parts, then add 40 parts of acetic anhydride, reaction 2.5h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.52.
Embodiment 4
Get 20 points of Starch rices, at room temperature stir 20min with 40 parts of Glacial acetic acid and fully mix, be warming up to 80 DEG C, add phospho-wolframic acid 2 parts, toluenesulphonic acids 5 parts, then add 50 parts of acetic anhydride, reaction 2h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.60.
Embodiment 5
Get 20 parts of Starch rices, at room temperature stir 20min with 40 parts of Glacial acetic acid and fully mix, be warming up to 70 DEG C, add phospho-wolframic acid 1 part, toluenesulphonic acids 4 parts, then add 40 parts of acetic anhydride, reaction 2h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.50.
Embodiment 6
Get 20 parts of Starch rices, at room temperature stir 10min with 55 parts of glacialacetic acids and fully mix, be warming up to 75 DEG C, add 1 part of phospho-wolframic acid, 5 parts, toluene acid iodide, then add 55 parts of acetic anhydride, reaction 2.5h.After having reacted, fully wash with a large amount of distilled water, vacuum-drying 24h at 50 DEG C, obtain the Starch rice acetic ester that substitution value is 2.58.
Claims (10)
1. a method for high substitution value Starch rice acetic ester is prepared in phospho-wolframic acid and toluenesulphonic acids catalysis, it is characterized in that, comprises the following steps:
(1) Starch rice is mixed with Glacial acetic acid, obtain the starch milk of certain mass mark, and at room temperature fully stir;
(2) starch milk is heated up, add a certain amount of phospho-wolframic acid, toluenesulphonic acids and acetic anhydride successively;
(3), after reacting certain hour, use distilled water fully to wash, suction filtration, vacuum-drying, obtains Starch rice acetic ester.
2. method according to claim 1, is characterized in that, in described step (1), is mixed by Starch rice with Glacial acetic acid, obtains the starch milk of massfraction 25% ~ 33%.
3. method according to claim 1, is characterized in that, in described step (1), churning time is 10 ~ 20min.
4. method according to claim 1, is characterized in that, in described step (2), starch milk is warmed up to 70 ~ 80 DEG C.
5. method according to claim 1, it is characterized in that, in described step (2), the mass ratio of starch, Glacial acetic acid, phospho-wolframic acid, toluenesulphonic acids and acetic anhydride is 10:(20 ~ 30): (0.5 ~ 1): (2 ~ 3): (20 ~ 30).
6. method according to claim 1, is characterized in that, in described step (3), the reaction times is 2 ~ 3h.
7. method according to claim 1, is characterized in that, in described step (3), by filter cake vacuum-drying 24h at 50 DEG C.
8. Starch rice acetic ester prepared by the method according to any one of claim 1-7, it is characterized in that, substitution value is higher than 2.5.
9. Starch rice acetic ester according to claim 8, is characterized in that, described substitution value is 2.5-2.7.
10. Starch rice acetic ester according to claim 8, is characterized in that, described Starch rice acetic ester is faint yellow.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410849340.1A CN104479032A (en) | 2014-12-30 | 2014-12-30 | Method for preparing rice starch acetate with high substitution degree through catalysis of phosphotungstic acid and toluenesulfonic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316103A (en) * | 1996-05-28 | 1997-12-09 | Mitsubishi Gas Chem Co Inc | Manufacture of polycarboxylic acid type polysaccharide |
| CN102604127A (en) * | 2012-03-21 | 2012-07-25 | 东北师范大学 | Method for preparing water insoluble polysaccharide nano particles by catalyzing and hydrolyzing of solid heteropolyacid |
| CN104031153A (en) * | 2014-06-20 | 2014-09-10 | 湘潭大学 | Method for preparing rice starch acetate through supported heteropoly acid catalyst |
-
2014
- 2014-12-30 CN CN201410849340.1A patent/CN104479032A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316103A (en) * | 1996-05-28 | 1997-12-09 | Mitsubishi Gas Chem Co Inc | Manufacture of polycarboxylic acid type polysaccharide |
| CN102604127A (en) * | 2012-03-21 | 2012-07-25 | 东北师范大学 | Method for preparing water insoluble polysaccharide nano particles by catalyzing and hydrolyzing of solid heteropolyacid |
| CN104031153A (en) * | 2014-06-20 | 2014-09-10 | 湘潭大学 | Method for preparing rice starch acetate through supported heteropoly acid catalyst |
Non-Patent Citations (3)
| Title |
|---|
| O.B.沃兹堡主编: "《变性淀粉的性能与应用（第1版）》", 31 December 1989, 纺织工业出版社 * |
| 华坚主编: "《环境污染控制工程材料（第1版）》", 30 September 2009, 化学工业出版社 * |
| 罗玉梅等: "磷钨酸催化合成苹果酯", 《化学与生物工程》 * |
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Application publication date: 20150401 |