CN111518224A - Preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content - Google Patents

Preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content Download PDF

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CN111518224A
CN111518224A CN202010549773.0A CN202010549773A CN111518224A CN 111518224 A CN111518224 A CN 111518224A CN 202010549773 A CN202010549773 A CN 202010549773A CN 111518224 A CN111518224 A CN 111518224A
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starch
distarch phosphate
chloropropanol
hydroxypropyl distarch
hydroxypropyl
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别平平
暨伟文
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Foshan Guonong Starch Co ltd
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Foshan Guonong Starch Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00Preparation of derivatives of starch
    • C08B31/16Ether-esters

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention relates to a preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content, which is characterized by comprising the following steps: firstly, preparing starch milk according to a solid-to-liquid ratio of 1: 1.5-1: 2, carrying out early treatment by using amylase, treating for 1-3 hours by using 0.20-3.30 IU of enzyme per gram of starch, and adding Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding propylene oxide to perform a hydroxypropyl reaction, then adding phosphorus oxychloride to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain the finished product of hydroxypropyl distarch phosphate. The preparation method of the hydroxypropyl distarch phosphate for reducing the content of the chloropropanol byproduct pretreats the starch, can change the molecular structure of the starch, and is more beneficial to the subsequent reaction.

Description

Preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content
Technical Field
The invention relates to the technical field of edible modified starch preparation, in particular to a preparation method of hydroxypropyl distarch phosphate for reducing the content of chloropropanol by-products.
Background
Hydroxypropyl distarch phosphate is an additive which is allowed to be widely applied to various fields of food, raw starch is treated by propylene oxide and a cross-linking agent (such as phosphorus oxychloride), and the hydroxypropylation and cross-linking treatment can effectively improve the natural properties of the starch, so that the starch is more suitable for application requirements of certain characteristics, such as pudding, fruit pie filling, seasoning, meat quality and the like, and can provide viscosity and freeze-thaw stability and further improve the texture, viscosity and processing and storage stability of the product.
However, hydroxypropyl distarch phosphate produces chloropropanol as a by-product during its manufacture, and the chloropropanol content of the destructured starch product must be less than 1ppm, according to the regulations of the national food additive board. When the content of chloropropanol produced by a modified starch factory in the conventional method for producing hydroxypropyl distarch phosphate exceeds the limit, the modified starch product needs to be additionally washed to remove byproducts, but the large amount of washing causes starch loss, so that the product yield is low, and the waste water discharge amount is increased. Therefore, a simple and effective method for removing chloropropanol residues in products is needed.
At present, many relevant scholars at home and abroad are dedicated to researching a method for reducing chloropropanol byproduct residue under the condition of ensuring that the substitution degree of a hydroxypropyl distarch phosphate product is not influenced. Leusner et al describe in "preparation of hydroxypropyl starch" (Leusner, S.J., Katcher J.H. etc., Process for hydroxypropyl stability [ P ]. U.S. patent 4431800), aeration of the starch slurry at high pH values for 0.25-24 h to expel propylene oxide after completion of the hydroxypropyl reaction, however long evacuation becomes impractical due to the need for actual production. Adeosun et al describe in "method of reducing chloropropanol content in the hydroxypropyl reaction" (Adeosun J., Borkar A., Wei Q. etc., Process for reducing propylene chloride in hydroxypropyl products [ P ] U.S. Patent20180319902) that residual propylene oxide is removed by dehydrating an alkaline slurry or by washing the starch under alkaline conditions, but this method requires two washes of the destructured starch product, increases the operating procedures and costs, and also produces more wastewater discharge. In addition, if the whole modified starch reaction system is kept for too long time under the condition of high pH value, the stripping phenomenon of the cross-linking chemical bonds in the obtained product can occur, so that the cross-linking degree is reduced, and the quality of the final product is influenced. Thus, there is a need for a process for preparing hydroxypropyl distarch phosphate that produces less chloropropanol by-product without increasing waste water discharge and without affecting the degree of product crosslinking.
Disclosure of Invention
The invention aims to provide a preparation method of hydroxypropyl distarch phosphate for reducing the content of chloropropanol by-product, which aims to solve the problems of overcoming the potential safety hazard caused by chemically modified starch, activating the original starch and increasing the sensibility of the starch to the hydroxypropylation and crosslinking reaction in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content is characterized in that: firstly, preparing starch milk according to a solid-to-liquid ratio of 1: 1.5-1: 2, carrying out early treatment by using amylase, treating for 1-3 hours by using 0.20-3.30 IU of enzyme per gram of starch, and adding Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding propylene oxide to perform a hydroxypropyl reaction, then adding phosphorus oxychloride to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain the finished product of hydroxypropyl distarch phosphate.
Preferably, the amylase is alpha-amylase, beta-amylase, glucoamylase.
Preferably, the solid-to-liquid ratio of the starch emulsion is 1: 1.5-1: 2.
Preferably, the use amount of the enzyme is 0.20-3.3 IU/g of starch.
Preferably, the enzyme treatment time is 1 to 3 hours.
Preferably, the starch is one of waxy corn starch, tapioca starch, potato starch, corn starch, glutinous rice starch, wheat starch or their combination.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the hydroxypropyl distarch phosphate for reducing the content of the chloropropanol byproduct pretreats the starch, can change the molecular structure of the starch, and is more beneficial to the subsequent reaction. The method effectively increases the sensitivity of the starch to the hydroxypropylation and crosslinking processes, reduces the consumption of propylene oxide in the hydroxypropylation process and the consumption of phosphorus oxychloride in the crosslinking process, improves the reaction efficiency, and further reduces the residue of chloropropanol as a byproduct by degrading one or more glucosyl bonds in starch molecules through amylase and cutting branch points in the molecular structure of the starch. In addition, the invention combines the amylase pretreatment and the conventional hydroxypropyl crosslinking treatment for the first time, obviously improves the reaction efficiency, reduces the use amount of propylene oxide and phosphorus oxychloride, reduces the chloropropanol residue as a byproduct and ensures that the chloropropanol content in the hydroxypropyl distarch phosphate product is lower while ensuring that the prepared substitution degree meets the application requirement. 1 ppm; according to the method for reducing chloropropanol residues in the hydroxypropyl distarch phosphate product, the existing workshop wet process production line is not required to be modified, the waste water discharge is not increased, and the qualified product is obtained under the condition of little adjustment on the existing procedures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content is characterized in that: firstly, preparing starch milk according to a solid-to-liquid ratio of 1: 1.5-1: 2, carrying out early treatment by using amylase, treating for 1-3 hours by using 0.20-3.30 IU of enzyme per gram of starch, and adding Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding propylene oxide to perform a hydroxypropyl reaction, then adding phosphorus oxychloride to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain the finished product of hydroxypropyl distarch phosphate.
Furthermore, the amylase is alpha-amylase, beta-amylase or glucoamylase.
Further, the solid-to-liquid ratio of the starch emulsion is 1: 1.5-1: 2.
Furthermore, the enzyme is used in an amount of 0.20-3.3 IU/g starch.
Further, the time for the enzyme treatment is 1 to 3 hours.
Furthermore, the starch is one or the combination of waxy corn starch, cassava starch, potato starch, corn starch, sticky rice starch and wheat starch.
The present invention will be described in further detail with reference to examples, but the embodiments are not limited thereto.
Example 1
Preparing starch milk from 500g waxy corn starch (absolute dry basis) at a solid-to-liquid ratio of 1:1.5, performing pretreatment with α -amylase at an amount of 0.20IU enzyme per gram of starch for 1 hr, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.30ppm by GC/MS.
Example 2
Preparing starch milk from 500g waxy corn starch (calculated by absolute dryness) at a solid-to-liquid ratio of 1:2, performing pretreatment with α -amylase, treating with 2.00IU enzyme per gram starch for 3h, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.25ppm by GC/MS.
Example 3
Preparing starch milk from 500g waxy corn starch (absolute dry basis) according to a solid-to-liquid ratio of 1:2, performing pretreatment with α -amylase, treating for 3h with 3.30IU enzyme per gram starch, and adding 90g Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% propylene oxide of a dry starch basis to perform a hydroxypropyl reaction, then adding 0.05% phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting chlorine in the product by GC/MS (gas chromatography/Mass spectrometer)The propanol content was 0.18 ppm.
Example 4
Preparing starch milk from 500g waxy corn starch (absolute dry basis) at a solid-to-liquid ratio of 1:1.5, performing pretreatment with β -amylase at an amount of 0.20IU enzyme per gram of starch for 1 hr, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting that the chloropropanol content in the product is 0.47ppm by GC/MS.
Example 5
Preparing starch milk from 500g waxy corn starch (oven dry basis) at a solid-to-liquid ratio of 1:2, performing pretreatment with β -amylase at an amount of 2.00IU per gram of starch for 2h, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.36ppm by GC/MS.
Example 6
Preparing starch milk from 500g waxy corn starch (absolute dry basis) according to a solid-to-liquid ratio of 1:2, performing pretreatment with β -amylase, treating for 3h with 3.30IU enzyme per gram starch, and adding 90g Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.31ppm by GC/MS.
Example 7
Preparing starch milk from 500g waxy corn starch (absolute dry basis) at solid-to-liquid ratio of 1:1.5, and performing pretreatment with glucoamylase at a dosage per gram of starchPulverizing into 0.20IU enzyme, treating for 1 hr, adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.52ppm by GC/MS.
Example 8
Preparing starch milk from 500g waxy corn starch (oven dry basis) at solid-to-liquid ratio of 1:2, treating with glucoamylase for 2 hr at an amount of 2.00IU per gram of starch, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.41ppm by GC/MS.
Example 9
Preparing starch milk from 500g waxy corn starch (oven dry basis) at solid-to-liquid ratio of 1:2, treating with glucoamylase for 3 hr at an amount of 3.30IU per gram of starch, and adding 90g Na2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.35ppm by GC/MS.
Example 10
Preparing 500g cassava starch (calculated by absolute dryness) into starch milk according to a solid-to-liquid ratio of 1:1.5, carrying out early-stage treatment by using α -amylase, wherein the using amount is 0.20IU enzyme per gram of starch, treating for 1h, and adding 90g Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding propylene oxide accounting for 10% of the dry basis of the starch for carrying out hydroxypropyl reaction, then adding phosphorus oxychloride accounting for 0.05% of the dry basis of the starch for carrying out crosslinking, and carrying out reverse reactionAfter the reaction is finished, neutralizing until the pH value is about 5.5, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.61ppm by GC/MS.
Example 11
Preparing 500g cassava starch (calculated by absolute dryness) into starch milk according to a solid-to-liquid ratio of 1:2, carrying out pretreatment by using α -amylase, treating for 3h according to 2.00IU enzyme per gram of starch, and adding 90g Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.50ppm by GC/MS.
Example 12
Preparing 500g cassava starch (calculated by absolute dryness) into starch milk according to a solid-to-liquid ratio of 1:2, carrying out prophase treatment by using α -amylase, treating for 3h by using 3.30IU of enzyme per gram of starch, and adding 90g Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding 10% of propylene oxide of a dry starch basis to perform hydroxypropyl reaction, then adding 0.05% of phosphorus oxychloride of the dry starch basis to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain a finished product, and detecting the chloropropanol content in the product to be 0.43ppm by GC/MS.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.

Claims (6)

1. A preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content is characterized in that: firstly, preparing starch milk according to a solid-to-liquid ratio of 1: 1.5-1: 2, and performing early-stage treatment by using amylase, wherein the using amount is 0.20-3 per gram of starch.Treating for 1-3 h by using 30IU enzyme, and adding Na after the treatment is finished2SO4Gelatinizing an inhibitor, adjusting the pH value to 11.0-11.5, adding propylene oxide to perform a hydroxypropyl reaction, then adding phosphorus oxychloride to perform crosslinking, neutralizing until the pH value is about 5.5 after the reaction is finished, washing with water, filtering, drying, crushing and sieving to obtain the finished product of hydroxypropyl distarch phosphate.
2. The method for preparing hydroxypropyl distarch phosphate with reduced chloropropanol by-product content according to claim 1, wherein the hydroxypropyl distarch phosphate is prepared by the following steps: the amylase is alpha-amylase, beta-amylase or glucoamylase.
3. The method for preparing hydroxypropyl distarch phosphate with reduced chloropropanol by-product content according to claim 1, wherein the hydroxypropyl distarch phosphate is prepared by the following steps: the solid-to-liquid ratio of the starch emulsion is 1: 1.5-1: 2.
4. The method for preparing hydroxypropyl distarch phosphate with reduced chloropropanol by-product content according to claim 1, wherein the hydroxypropyl distarch phosphate is prepared by the following steps: the using amount of the enzyme is 0.20-3.3 IU/g starch.
5. The method for preparing hydroxypropyl distarch phosphate with reduced chloropropanol by-product content according to claim 1, wherein the hydroxypropyl distarch phosphate is prepared by the following steps: the enzyme treatment time is 1-3 hours.
6. The method for preparing hydroxypropyl distarch phosphate with reduced chloropropanol by-product content according to claim 1, wherein the hydroxypropyl distarch phosphate is prepared by the following steps: the starch is one or the combination of waxy corn starch, cassava starch, potato starch, corn starch, glutinous rice starch and wheat starch.
CN202010549773.0A 2020-06-16 2020-06-16 Preparation method of hydroxypropyl distarch phosphate for reducing chloropropanol byproduct content Pending CN111518224A (en)

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CN101768224A (en) * 2010-01-22 2010-07-07 鲁郑全 Preparation method of hydroxypropyl starch
CN101979638A (en) * 2010-09-28 2011-02-23 南宁创新科技医药技术有限公司 Method for preparing crosslinked porous cassavastarch
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