Background technology
Starch is a kind of reproducible agriculture primary processed items, and steady sources is abundant, and superiority of effectiveness is obvious, and as natural polysaccharide polymer, starch is widely used as industrial raw materials.In actual production, adopt means such as heat, acid, alkali, oxidation, zymin that starch polymer is carried out modification, to obtain more excellent product performance, the starch conversion product is widely used in fields such as food, medicine, papermaking, weaving.
Organic phosphate starch is a kind of of starch conversion product, belongs to anionic, and is water insoluble or be slightly soluble in water, sticks with paste liquid and then has characteristics such as transparent, that viscosity stability good (acidproof, heat-resisting, anti-shearing), retrogradation weak, nontoxic nothing is smelt, fragrance is clear.In foodstuffs industry, be used as thickening material and emulsifying agent; Be used in the medicine industry bonding, water down, excipient, filling etc.; In the textile industry as auxiliary material of warp sizing agent, dyeing and printing adhesive agent and finished machined etc.; Starch is mainly used in top sizing, internal additives, coating, cardboard tackiness agent in the paper industry, or the like.
The production of organic phosphate starch is carried out in industrial common employing " dry method ", " wet method " or " semidrying " technology.In existing these production technique, finish the phosphating reaction of starch, all need high temperature solid state reaction process through 140~180 ℃, this process exists that temperature is too high, process control is had relatively high expectations, unfavorable factors such as product quality fluctuation.For example in the disclosed technical literature that can retrieve at present, and be CN1781948 at nearest disclosed publication number, name is called the patent application of " a kind of new dry process production low viscosity phosphate ester starch production technique ", with publication number be CN1781949, name is called in the production technique of disclosed phosphate ester starch in the patent application of " a kind of production technique of dry production high viscosity phosphate ester starch ", its esterification reaction process of finishing starch has all passed through 140~180 ℃, 3~8 hours solid phase high-temperature reaction process.There is the shortcoming that consumes energy greatly and be difficult to carry out technology controlling and process in this high temperature solid state reaction.In addition, general " wet method " is lower although technology has temperature of reaction, the process gentleness, and the advantage of uniform in quality, because esterification efficient is low, the product bound phosphorus is very low, is subjected to great restriction in practicality.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have esterification efficient height, product bound phosphorus height, temperature of reaction is lower, power consumption is little and and carries out the method that advantages such as technology controlling and process prepare organic phosphate starch easily.The preparation method of organic phosphate starch of the present invention may further comprise the steps:
(1) in the starch quality percentage composition is 35%~42% starch milk, 1.5%~16% the promotor stearic polyoxyethylene ether that adds 8%~50% phosphoric acid salt mixed thing of starch quality and starch quality, and reactant is mixed, be 5.0~6.5 in 30~60 ℃ of temperature, pH value, under the stirring condition, reacted 3~10 hours;
(2) with the reaction product centrifugation of step (1) gained, dry then getting final product.
In order to realize the present invention better:
Preparation method of the present invention, the mixture that the phosphoric acid salt mixed thing in the described step (1) preferably is made up of the phosphoric acid salt of following mass parts: 0~30 part of sodium phosphate, 10~60 parts of SODIUM PHOSPHATE, MONOBASIC, 0~25 part of Sodium phosphate dibasic;
Starch quality percentage composition preferred 38%~41% in the described starch milk of described step (1);
The quality optimization that adds the phosphoric acid salt mixed thing in the described step (1) is 10%~15% of a starch quality;
The quality optimization that adds the promotor stearic polyoxyethylene ether in the described step (1) is 8%~12% of a starch quality;
Preparation method of the present invention, in the step (1), the pH value of conditioned reaction thing is preferably and is adjusted to 5.5;
Preparation method of the present invention, in the step (1), temperature of reaction is preferably 55 ℃, and the reaction times is preferably 5~10 hours;
Starch milk can directly adopt the undried starch slurry of starch factory, also can commodity starch water furnishing mass concentration is 35%~42% starch milk.
Sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic and stearic polyoxyethylene ether can be selected corresponding purity grade according to the purposes of esterification starch, if the industrial raw material of then selecting technical grade for use, if produce the raw material that food is then selected food grade for use.
The present invention compared with prior art has following beneficial effect:
Therefore (1) preparation method of the present invention, its phosphating reaction is finished at low temperatures, need not pass through common high temperature solid state reaction process, can significantly cut down the consumption of energy, and easier technology be controlled.
(2) preparation method of the present invention, esterification efficient is significantly improved, and compares with traditional phosphoric acid by wet process esterification reaction tech, and the bound phosphorus of the organic phosphate starch behind the purifying has improved more than 2.5 times than the Wet Method Reaction that does not adopt promotor.
Embodiment
Below enumerate preferred implementations more of the present invention, understand the present invention to help further, but practical range of the present invention is not limited thereto.
Sodium phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, stearic polyoxyethylene ether used in following examples are food grade materials.
Embodiment 1
In reactor, add 100Kg water, 80Kg W-Gum furnishing starch milk, add the 2.0Kg sodium phosphate then, 1.6Kg SODIUM PHOSPHATE, MONOBASIC, 2.8Kg Sodium phosphate dibasic, the stearic polyoxyethylene ether of 2Kg, the stirring velocity that keeps per minute 45 to change is warming up to 30 ℃, regulates pH value 6.5, isothermal reaction finished reaction in 3 hours, obtain organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.04%, and whiteness is 90%.
Embodiment 2
In reactor, add 110Kg water, 80Kg W-Gum furnishing starch milk, add the 5.8Kg SODIUM PHOSPHATE, MONOBASIC then, 1.4Kg Sodium phosphate dibasic, 1.8Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 60 to change, be warming up to 60 ℃, regulate pH value 5.0, isothermal reaction finished reaction in 10 hours, obtained organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.15%, and whiteness is 91%.
Embodiment 3
In reactor, add 100Kg water, 80Kg W-Gum furnishing starch milk, add the 9.6Kg SODIUM PHOSPHATE, MONOBASIC then, 1.2Kg Sodium phosphate dibasic, 2.5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 40 to change, be warming up to 58 ℃, regulate pH value 5.0, isothermal reaction finished reaction in 8 hours, obtained organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.19%, and whiteness is 93%.
Embodiment 4
In reactor, add 120Kg water, 80Kg W-Gum furnishing starch milk, add the 2.8Kg sodium phosphate then, 14.5Kg SODIUM PHOSPHATE, MONOBASIC, 1.2Kg Sodium phosphate dibasic, the 5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 80 to change is warming up to 53 ℃, regulates pH value 5.5, isothermal reaction finished reaction in 10 hours, obtain organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.27%, and whiteness is 91%.
Embodiment 5
In reactor, add 92Kg water, 80Kg W-Gum furnishing starch milk, add the 18Kg SODIUM PHOSPHATE, MONOBASIC then, 0.8Kg Sodium phosphate dibasic, 5.5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 80 to change, be warming up to 50 ℃, regulate pH value 5.2, isothermal reaction finished reaction in 10 hours, obtained organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.28%, and whiteness is 92%.
Embodiment 6
In reactor, add 92Kg water, 80Kg W-Gum furnishing starch milk, add the 26Kg SODIUM PHOSPHATE, MONOBASIC then, 0.8Kg Sodium phosphate dibasic, 8.5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 45 to change, be warming up to 55 ℃, regulate pH value 5.2, isothermal reaction finished reaction in 8 hours, obtained organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.32%, and whiteness is 92%.
Embodiment 7
In reactor, add 92Kg water, 80Kg W-Gum furnishing starch milk, add the 38Kg SODIUM PHOSPHATE, MONOBASIC then, 0.5Kg Sodium phosphate dibasic, 2.1Kg sodium phosphate, the 10Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 45 to change is warming up to 53 ℃, regulates pH value 5.4, isothermal reaction finished reaction in 8 hours, obtain organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.31%, and whiteness is 90%.
Embodiment 8
In reactor, add 92Kg water, 80Kg W-Gum furnishing starch milk, add the 37Kg SODIUM PHOSPHATE, MONOBASIC then, 1.5Kg Sodium phosphate dibasic, 0.8Kg sodium phosphate, 12.5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 45 to change is warming up to 55 ℃, regulates pH value 5.2, isothermal reaction finished reaction in 10 hours, obtain organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.36%, and whiteness is 90%.
Embodiment 9
In reactor, add 92Kg water, 80Kg W-Gum furnishing starch milk, add the 38Kg SODIUM PHOSPHATE, MONOBASIC then, 5.5Kg stearic polyoxyethylene ether, the stirring velocity that keeps per minute 80 to change is warming up to 50 ℃, regulates pH value 5.2, isothermal reaction finished reaction in 10 hours, obtain organic phosphate starch through centrifugation and air stream drying, its bound phosphorus is 0.21%, and whiteness is 91%.