CN104530245B - A kind of method that the concentrated sulfuric acid and toluenesulfonic acid catalysis prepares high substituted degree rice starch acetate - Google Patents
A kind of method that the concentrated sulfuric acid and toluenesulfonic acid catalysis prepares high substituted degree rice starch acetate Download PDFInfo
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- CN104530245B CN104530245B CN201410843656.XA CN201410843656A CN104530245B CN 104530245 B CN104530245 B CN 104530245B CN 201410843656 A CN201410843656 A CN 201410843656A CN 104530245 B CN104530245 B CN 104530245B
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Abstract
The present invention relates to a kind of method that concentrated sulfuric acid and toluenesulfonic acid catalysis prepare high substituted degree rice starch acetate.The present invention is to add a certain amount of rice starch and glacial acetic acid at room temperature, after stirring and being heated to specified for temperature ranges, after being slowly added to acetic anhydride, it is slow added into the glacial acetic acid reaction a period of time for being mixed with the concentrated sulfuric acid and toluenesulfonic acid, scrubbed, suction filtration, drying, crushing, screening obtain starch acetate product, and substitution value is up to more than 2.5.The product processes are simply applicable, and reaction efficiency is high, and yield is high, and substitution value is high, largely reduces the degraded of starch in course of reaction, alleviates the corrosion of equipment, and reduces environmental.
Description
Technical field
The present invention relates to a kind of side that high substituted degree rice starch is prepared using the concentrated sulfuric acid and toluenesulfonic acid mixed catalyst
Method, belong to starch field of deep.
Background technology
The esterification of starch significantly improves many performances of starch, such as the property of anticoagulant, transparency and other side
Ative starch product can be better than, be widely used in the industrial departments such as food, papermaking, weaving, adhesive.Starch acetate is
The most common and most heavy one kind of esterification starch, has certain thermoplastic.The Starch Acetates with High Degree of Substitution of function admirable
It can be molded by the methods of hot pressing, molding, obtain corresponding sheet material and the moulded products of other forms, and this starch is
Degradable, its catabolite is also environment-friendly.The acetate starch for preparing high substituted degree in retribution for sins road was with jade in recent years
Rice starch is in the majority, and rice starch is not seen for raw material.
As the improvement of people's living standards, people are to Rice producing required precision also more and more higher, with grading
The progressively reinforcement arranged, rice are cracked rice also more and more caused by finishing.It is limited to existing husk rice technology, it is processed
10%~15% is inevitably produced in journey to crack rice, although chemically from composition, is cracked rice with whole rice too not big
Difference, but its price is only the 30%~50% of rice starch.The caused general accessory substance that is only used as of cracking rice is handled, economic valency
Value is very low, causes huge waste.
The technique of existing rank medium well production high substituted degree acetate, typically all uses liquid acid (such as sulfuric acid) or organic acid (toluene
Sulfonic acid) prepared as catalyst, but this 2 kinds of methods all Shortcomings.Though liquid acid catalytic effect is good, liquid corrosion
By force, and a certain amount of starch degradation can be caused, yield is relatively low.The obtained product substitution value of organic acid catalysis is relatively low, tends not to reach
To the requirement of some purposes, and toluenesulfonic acid is poisonous, and directly discharge can cause Heavy environmental pollution.In recent years, though there is research table
Bright, the method for acetate starch is prepared using high sub- liquid as solvent can reach the requirement that yield is high and substitution value is good, but
It is limited to ionic liquid this expensive price, this method is unsuitable for factory's use.Therefore, product yield can be improved, reduce by seeking one kind
Equipment corrosion, noxious material density and gross volume of such pollutants to be discharged, the new method of high substituted degree are reduced with regard to imperative.
The content of the invention
In order to make up the deficiency of existing process, the rate of side effects of course of reaction is reduced, reduces equipment corrosion degree, again
Catalyst cost can be reduced, improves high substituted degree, the invention provides a kind of economical and practical, yield height, substitution value height, product symbol
Close and require, it is small to equipment corrosion, the Starch Acetates with High Degree of Substitution of discharge of poisonous waste total amount mitigation environmental pollution can be reduced
Preparation method, this method are suitable for factory's use.
The technical scheme is that：
A kind of method that the concentrated sulfuric acid and toluenesulfonic acid catalysis prepares high substituted degree rice starch acetate, including following step
Suddenly：
(1) glacial acetic acid starch milk is prepared：Take a certain amount of rice starch to be mixed with glacial acetic acid, and be stirred at room temperature certain
Time；
(2) preparation of mixed catalyst glacial acetic acid liquid：A certain amount of concentrated sulfuric acid and toluenesulfonic acid are added in glacial acetic acid,
It is sufficiently mixed；
(3) esterification：The glacial acetic acid starch milk prepared is heated up, after adding a certain amount of acetic anhydride, will be prepared
Mixed catalytic liquid be added in glacial acetic acid starch milk, react certain time；
(4) wash：Filtered after fully being washed with distilled water；
(5) dry：Be dried in vacuo under filter cake, crush, sieve after obtain product.
Preferably, in the step (1), 100 parts of rice starch and 100~150 parts of glacial acetic acid are taken to mix.
Preferably, in the step (1), mixing time 10min.
Preferably, in the step (2), 2~3 parts of the concentrated sulfuric acid and 15~30 parts of toluenesulfonic acid are added to 100~
In 150 parts of glacial acetic acid.
Preferably, in the step (3), the glacial acetic acid starch milk prepared is warming up to 70~80 DEG C, is slowly added to 250
~300 parts of acetic anhydride.
Preferably, in the step (3), the mixed catalytic liquid prepared is added to glacial acetic acid starch milk in 15min
In, react 2~3h.
Preferably, in the step (5), filter cake is dried in vacuo 24h at 50 DEG C.
A kind of rice starch acetate, is prepared by above-mentioned method, and its substitution value is higher than 2.5.
Preferably, the substitution value of described rice starch acetate is 2.5-2.8.
Beneficial effects of the present invention：Although the inventive method also using sulfuric acid and toluenesulfonic acid as catalyst, still
It is different when one of which material makees catalyst with being used alone, because sulfuric acid is to be reentered after being diluted with glacial acetic acid in reaction system
, simultaneously because the concerted catalysis effect of toluenesulfonic acid, makes the usage amount of the concentrated sulfuric acid and toluenesulfonic acid while reduces, reacting
Obvious degradation does not occur for starch in journey, and the product substitution value prepared is higher than single use toluenesulfonic acid as catalyst
Obtained product.In summary, the preparation method has yield height, and small to equipment corrosion, substitution value is higher than 2.5 (in 2.5-2.8
In the range of), the characteristics of discharge of poisonous waste total amount reduces, and with use ionic liquid as the method for solvent with ten clearly demarcated
Aobvious price advantage.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
The technology contents and effect of the present invention are further illustrated below by example.
Embodiment 1
Take 100 parts of glacial acetic acid to pour into 100 parts of rice starch, 75 DEG C are warming up to after being sufficiently stirred, add 250 parts of acetic acid
Acid anhydride, 2 parts of concentrated sulfuric acids and 15 parts of toluenesulfonic acids are added in 100 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 2.5h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, crushes, substitution value is obtained after screening as 2.54
Rice starch acetate.
Embodiment 2
Take 100 parts of glacial acetic acid to pour into 100 parts of rice starch, 75 DEG C are warming up to after being sufficiently stirred, add 250 parts of acetic acid
Acid anhydride, 3 parts of concentrated sulfuric acids and 15 parts of toluenesulfonic acids are added in 150 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 2.5h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, crushes, substitution value is obtained after screening as 2.61
Rice starch acetate.
Embodiment 3
Take 150 parts of glacial acetic acid to pour into 100 parts of rice starch, 80 DEG C are warming up to after being sufficiently stirred, add 250 parts of acetic acid
Acid anhydride, 2 parts of concentrated sulfuric acids and 20 parts of toluenesulfonic acids are added in 140 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 2.5h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, crushes, substitution value is obtained after screening as 2.60
Rice starch acetate.
Embodiment 4
Take 130 parts of glacial acetic acid to pour into 100 parts of rice starch, 70 DEG C are warming up to after being sufficiently stirred, add 300 parts of acetic acid
Acid anhydride, 3 parts of concentrated sulfuric acids, 320 parts of toluenesulfonic acids are added in 150 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 3h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, it is 2.73 to crush, substitution value is obtained after screening
Rice starch acetate.
Embodiment 5
Take 150 parts of glacial acetic acid to pour into 100 parts of rice starch, 80 DEG C are warming up to after being sufficiently stirred, add 300 parts of acetic acid
Acid anhydride, 2 parts of concentrated sulfuric acids and 30 parts of toluenesulfonic acids are added in 130 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 2h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, it is 2.54 to crush, substitution value is obtained after screening
Rice starch acetate.
Embodiment 6
Take 150 parts of glacial acetic acid to pour into 100 parts of rice starch, 80 DEG C are warming up to after being sufficiently stirred, add 250 parts of acetic acid
Acid anhydride, 2 parts of concentrated sulfuric acids and 20 parts of toluenesulfonic acids are added in 150 parts of glacial acetic acid, then by mixed liquor in being added drop-wise to reaction in 15min
In system, after reacting 2.5h, scrubbed, suction filtration, 24h is dried in vacuo at 50 DEG C, crushes, substitution value is obtained after screening as 2.76
Rice starch acetate.
Claims (1)
1. a kind of method that concentrated sulfuric acid and toluenesulfonic acid catalysis prepare high substituted degree rice starch acetate, it is characterised in that bag
Include following steps：
(1) glacial acetic acid starch milk is prepared：Take 100 parts of rice starch and 100~150 parts of glacial acetic acid to mix, and be stirred at room temperature
10min；
(2) preparation of mixed catalyst glacial acetic acid liquid：2~3 parts of the concentrated sulfuric acid and 15~30 parts of toluenesulfonic acid are added to 100
In~150 parts of glacial acetic acid, it is sufficiently mixed；
(3) esterification：The glacial acetic acid starch milk prepared is warming up to 70~80 DEG C, is slowly added to 250~300 parts of acetic acid
Acid anhydride, the mixed catalytic liquid prepared is added in 15min in glacial acetic acid starch milk, reacts 2~3h；
(4) wash：Filtered after fully being washed with distilled water；
(5) dry：Filter cake is dried in vacuo 24h at 50 DEG C, crushes, the product that substitution value is 2.5-2.8 is obtained after screening.
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| CN107372744A (en) * | 2017-07-15 | 2017-11-24 | 诸城市东方食品有限公司 | A kind of vegetable biscuit and its processing technology |
| CN110420599A (en) * | 2019-08-31 | 2019-11-08 | 齐鲁工业大学 | A kind of synthetic method of dodecyl benzene sulfonic acid cornstarch ester surfactant |
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| US5710269A (en) * | 1996-01-16 | 1998-01-20 | Hoechst Celanese Corp. | Method of making starch acetate using an acid catalyst |
| CN1583797A (en) * | 2004-05-29 | 2005-02-23 | 中山市南方新元食品生物工程有限公司 | Preparation of high-substituted acetylizing starch (acetic acid starch) |
| CN101362804B (en) * | 2008-09-28 | 2010-09-08 | 东北林业大学 | Acetyl starch with high degree of substitution and preparation method thereof |
| CN101863994A (en) * | 2010-06-18 | 2010-10-20 | 罗代洪 | Method for preparing esterified starch by microwave |
| CN104031153B (en) * | 2014-06-20 | 2016-06-08 | 湘潭大学 | A kind of catalyzed with solid supported heteropolyacid prepares the method for Starch rice acetic ester |
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