CN103382227A - Preparation method of environment-friendly oxidized modified starch - Google Patents
Preparation method of environment-friendly oxidized modified starch Download PDFInfo
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- CN103382227A CN103382227A CN2013102755482A CN201310275548A CN103382227A CN 103382227 A CN103382227 A CN 103382227A CN 2013102755482 A CN2013102755482 A CN 2013102755482A CN 201310275548 A CN201310275548 A CN 201310275548A CN 103382227 A CN103382227 A CN 103382227A
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Abstract
The invention belongs to the field of chemical technology, and more specifically relates to a preparation method of an environment-friendly oxidized modified starch. Equipment investment is not increased; hydrogen peroxide is used as an oxidizing agent; and an appropriate catalyst is added; so that part of the reducing chain ends of the starch are oxidized to carboxyl, glucose units based on 10 are removed because of the oxidation of each reducing chain end, and new reducing chain ends are induced until the oxidation is completed. Products with high purity and excellent effects are prepared by oxidation of starch with hydrogen peroxide, and excess hydrogen peroxide is decomposed into water. Hydrogen peroxide is an ideal green and environment-friendly oxidizing agent, and is capable of reducing sewage processing cost significantly.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method of environmentally friendly modified modified starch.
Background technology
Starch is that green plants passes through a kind of natural macromolecule carbohydrate that is comprised of a plurality of hydroxyl glucose units that photosynthesis generates.Starch and derivative resource thereof are very abundant, have that toxicity is low, readily biodegradable, can be degradable at occurring in nature, very friendly to environment, be widely used in a plurality of industrial circles such as food, weaving, papermaking, oil, building and medicine.Yet along with the development of industrial production technology, also more and more harsher to the requirement of starch property, ative starch has had a strong impact on its practical application effect because of the defective on its structure and performance.Therefore, developed the sex change technology of starch according to the formation and physic-chemical property of starch, Sumstar 190 is one of Some Important Modified Starches of early stage research, use.
Starch is Sumstar 190 with oxygenant effect products obtained therefrom in acid, alkali, neutral medium.Oxidizing reaction can not only make glycosidic link fracture, and also limitedly carbonylate and carboxyl on starch molecular chain drop to the retrogradation effect of amylose starch minimum, have greatly improved stability, film-forming properties, binding property and the transparency of sticking with paste liquid.Because Sumstar 190 has advantages of above-mentionedly, technique is simple, cheap in addition, therefore has a wide range of applications in the industry such as papermaking and weaving.
Adopt different oxidizing process, oxygenant and ative starch can make the different Sumstar 190 of performance, wherein the most frequently used, economical effectiveness again good oxygenant be mainly clorox and potassium permanganate.Use hypochlorite oxidation starch, cheap, though oxidation effectiveness is good, clorox is unstable, easily decomposites chlorine, and operator often feel dizzy due to the pollution of chlorine, has also increased requirement and the cost of sewage disposal aspect simultaneously; Use Potassium Permanganate as Oxidant, all be brown after under low pH value or high pH value condition, oxidized starch is being deposited for some time, had a strong impact on outward appearance and the result of use of product.So be badly in need of now a kind of oxygenant of effective, environmental protection.
Summary of the invention
The object of the invention is to, overcome the deficiencies in the prior art, a kind of preparation method of environmentally friendly modified modified starch is provided.Hydrogen peroxide is cheap, oxidisability is strong, usage quantity is less, can save production cost greatly.The more important thing is, adopt hydrogen peroxide oxidation starch not only can obtain the product of high purity, effect excellence, excessive hydrogen peroxide finally is decomposed into water, is a kind of comparatively desirable environmental protection oxygenant, greatly reduces the sewage disposal expense.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of environmentally friendly modified modified starch, and concrete steps are as follows:
(1) mix: at first prepare the starch emulsion that mass concentration is 30 ~ 38 %, add in mixing tank, start agitator, 0.1 ~ 20 % hydrogen peroxide oxidant that accounts for the catalytic reagent of 0.01 of starch oven dry weight ~ 0.5 ‰ and account for the starch oven dry weight is added in mixing tank and starch mixing 10-20 min;
(2) reaction of degeneration: after well-mixed material, conditioned reaction pH 3 ~ 11,30 ~ 55 ℃ of temperature of reaction, reaction times 1 ~ 5 h;
(3) neutralization reaction: after reaction 3 ~ 8 h, add reductive agent to stop oxidizing reaction; In adding and conditioning agent, make the pH value to 7.0 of final starch system ± 1.0;
(4) screening, weighing, packing: through the product of above-mentioned preparation, weighing and bagging gets final product after bolting.
Starch of the present invention is that one or more of corn, cassava, potato, wheat ative starch are arbitrarily than mixture.
Catalyzer in step of the present invention (1) is that one or more of copper sulfate, ferric sulfate, zinc sulfate are arbitrarily than mixture.
In step of the present invention (1), the mass concentration of hydrogen peroxide is 5 ~ 40 %.
In step of the present invention (2), one or more of regulating pH acid used when acid and be rare conditioning agent and be hydrochloric acid, sulfuric acid, phosphoric acid are arbitrarily than mixture, and mass concentration is 2 ~ 20 %; When regulating pH for alkalescence alkali used be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate solution arbitrarily than mixture, mass concentration is 2 ~ 20 %.
In step of the present invention (3), reductive agent be one or more of Sodium Pyrosulfite, sodium bisulfite, S-WAT, Sulfothiorine arbitrarily than mixture, consumption is 0.05 of starch oven dry weight ~ 0.3 ‰.
In step of the present invention (3), in and conditioning agent be one or more of sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid and phosphoric acid arbitrarily than mixture, mass concentration is 1 ~ 30 %.
The invention has the beneficial effects as follows: the present invention is not in the situation that increase facility investment, take hydrogen peroxide as oxygenant, add suitable catalyzer, just can make that in starch, the part reductibility end of the chain is oxidized to carboxyl, and the glucose unit of counting in 10 is just taken off in each reductibility end of the chain oxidation, simultaneously the new reductibility end of the chain appears again, until oxidation finishes.As long as suitably control the Sumstar 190 that oxidation depth just can obtain to suit the requirements.Preparation technology's advantages of simple of the present invention, low sticking, the high solid that make common ative starch have Sumstar 190 disperse the fundamental characteristics such as property and minimum gelification.In addition, also have several lower some advantage: (1) is compared with conventional hypochlorite oxidation starch, and the oxygenant consumption is few, and thermostability is strong, price is low, less investment; (2) the reaction decomposes product is water and oxygen, and environmental protection is conducive to further reduce cost of sewage disposal; (3) add catalyzer after, obvious Reaction time shorten, production efficiency is high, steady quality and energy consumption reduce greatly.
Embodiment
The below is further elaborated with reference to embodiment, but the present invention is not limited to these embodiment and using method.Experiment material used in following embodiment if no special instructions, all can be bought in routine biochemistry reagent shop; % in embodiment if no special instructions, is the quality percentage composition, and umber is mass parts.
Embodiment 1
Maize oxidized starch:
With 1000 parts of ative starchs and 1600 parts of water furnishing starch milks, add mixing tank, start mixing pump; Add the zinc sulfate of 0.01 % as catalyzer, the oxidant hydrogen peroxide (concentration is 20 %) that slowly adds 2 % that are equivalent to the ative starch over dry, regulate pH to 8.0 with the sodium hydroxide solution of 2 % again, begin to be warming up to 50 ℃, in the whole process of oxidizing reaction, keep pH between 8.0-8.5 always.When the starch emulsion temperature reaches 50 ℃, beginning timing oxidizing reaction 4 h.After reaction finishes, add the Sodium Pyrosulfite of 0.003 % of starch over dry with termination reaction, be neutralized to pH 7 left and right with 8 % hydrochloric acid.In oxidation reaction process, every 1 h sampling, detect viscosity, transmittance and thermostability, to control the various performances of product, reach and satisfy the user to the various service requirementss of Sumstar 190, sieve at last and pack to get the present invention's product.
Thermal stability data (take oxidation 2 h as example): first hour viscosity is as 11.3cp, and second hour viscosity is 10.9cp, and viscosity was 10.2cp in the 3rd hour; Thermostability=10.2 ÷ 11.3 * 100 %=90.26 %.
Embodiment 2
Cassava oxidized starch:
With 1000 parts of cassava ative starchs and 1600 parts of water furnishing starch milks, add mixing tank, start mixing pump; Add the ferric sulfate of 0.03 % as catalyzer, the oxidant hydrogen peroxide (concentration is 26 %) that slowly adds 0.5 % that is equivalent to the ative starch over dry, regulate pH to 4.0 with the hydrochloric acid soln of 6 % again, begin to be warming up to 35 ℃, in the whole process of oxidizing reaction, keep pH between 4.0-4.5 always.When the starch emulsion temperature reaches 35 ℃, beginning timing oxidizing reaction 5 h.After reaction finishes, add the S-WAT of 0.02 % of starch over dry with termination reaction, be neutralized to pH 7 left and right with 10 % sodium hydroxide.In oxidation reaction process, every 1 h sampling, detect viscosity, transmittance and thermostability etc., to control the various performances of product, reach and satisfy the user to the various service requirementss of Sumstar 190, sieve at last and pack to get the present invention's product.
Thermal stability data (take oxidation 3 h as example): viscosity was 21.8 cp in first hour, and second hour viscosity is 20.9 cp, and viscosity was 20.2 cp in the 3rd hour; Thermostability=20.2 ÷ 21.8 * 100 %=92.66 %.
Embodiment 3
Corn and potato mixed oxidization starch:
With 400 parts of native cornstarchs, 600 parts of potato ative starchs and 1600 parts of water furnishing starch milks, add mixing tank, start mixing pump; Add the copper sulfate of 0.01 % as catalyzer, slowly add 3% the oxidant hydrogen peroxide (concentration is 20 %) that is equivalent to the ative starch over dry, regulate pH to 8.0 with 4% sodium hydroxide solution again, begin to be warming up to 50 ℃, in the whole process of oxidizing reaction, keep pH between 7.0-7.5 always.When the starch emulsion temperature reaches 50 ℃, beginning timing oxidizing reaction 3h.After reaction finishes, add the Sodium Pyrosulfite of 0.002 % of starch over dry with termination reaction, be neutralized to pH 7 left and right with 15 % hydrochloric acid.In oxidation reaction process, every 1 h sampling, detect viscosity, transmittance and thermostability, to control the various performances of product, reach and satisfy the user to the various service requirementss of Sumstar 190, sieve at last and pack to get the present invention's product.
Thermal stability data (take oxidation 3 h as example): first hour viscosity is as 20.2cp, and second hour viscosity is 18.6 cp, and viscosity was 16.2cp in the 3rd hour; Thermostability=16.2 ÷ 20.2 * 100 %=80.20 %.
Claims (7)
1. the preparation method of an environmentally friendly modified modified starch, it is characterized in that: concrete steps are as follows:
Mix: at first prepare the starch emulsion that mass concentration is 30 ~ 38 %, add in mixing tank, start agitator, 0.1 ~ 20 % hydrogen peroxide oxidant that accounts for the catalytic reagent of 0.01 of starch oven dry weight ~ 0.5 ‰ and account for the starch oven dry weight is added in mixing tank and starch mixing 10-20 min;
Reaction of degeneration: after well-mixed material, conditioned reaction pH 3 ~ 11,30 ~ 55 ℃ of temperature of reaction, reaction times 1 ~ 5 h;
Neutralization reaction: after reaction 3 ~ 8 h, add reductive agent to stop oxidizing reaction; In adding and conditioning agent, make the pH value to 7.0 of final starch system ± 1.0;
Screening, weighing, packing: through the product of above-mentioned preparation, weighing and bagging gets final product after bolting.
2. a kind of preparation method of environmentally friendly modified modified starch according to claim 1, it is characterized in that: described starch is one or more mixtures of corn, cassava, potato, wheat ative starch.
3. a kind of preparation method of environmentally friendly modified modified starch as according to claim 1, it is characterized in that: the catalyzer in described step (1) is one or more mixtures of copper sulfate, ferric sulfate, zinc sulfate.
4. a kind of preparation method of environmentally friendly modified modified starch according to claim 1, it is characterized in that: in described step (1), the mass concentration of hydrogen peroxide is 5 ~ 40 %.
5. a kind of preparation method of environmentally friendly modified modified starch according to claim 1, it is characterized in that: in described step (2), when regulating pH for acidity, acid used is that rare conditioning agent is one or more mixtures of hydrochloric acid, sulfuric acid, phosphoric acid, and mass concentration is 2 ~ 20 %; When regulating pH for alkalescence, alkali used is one or more mixtures of sodium hydroxide, potassium hydroxide, sodium carbonate solution, and mass concentration is 2 ~ 20 %.
6. a kind of preparation method of environmentally friendly modified modified starch according to claim 1, it is characterized in that: in described step (3), reductive agent is one or more mixtures of Sodium Pyrosulfite, sodium bisulfite, S-WAT, Sulfothiorine, and consumption is 0.05 of starch oven dry weight ~ 0.3 ‰.
7. a kind of preparation method of environmentally friendly modified modified starch according to claim 1, it is characterized in that: in described step (3), in and conditioning agent be one or more mixing in sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid and phosphoric acid, mass concentration is 1 ~ 30 %.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833862A (en) * | 2014-02-27 | 2014-06-04 | 华南理工大学 | Oxidized glutinous rice starch as well as preparation method and application thereof |
| CN104525135A (en) * | 2015-01-20 | 2015-04-22 | 四川大学 | Dual-gel adsorbent and production method thereof |
| CN105441022A (en) * | 2015-12-28 | 2016-03-30 | 常熟市宏宇钙化物有限公司 | Method for preparing calcium hydroxide adhesive |
| CN106146737A (en) * | 2015-05-20 | 2016-11-23 | 内蒙古大学 | The method preparing super absorbent resin with high potassium content for raw material one kettle way with carboxymethyl potato starch and hydrogen peroxide |
| CN106543292A (en) * | 2016-09-28 | 2017-03-29 | 南通宏慈药业有限公司 | A kind of processing technology of oxidation hydroxypropyl starch |
| CN109280193A (en) * | 2018-09-20 | 2019-01-29 | 黄旭东 | A kind of preparation method of starch degradation material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030699A (en) * | 2011-10-08 | 2013-04-10 | 王晓珍 | Preparation method of canna edulis ker oxidized starch |
-
2013
- 2013-07-03 CN CN2013102755482A patent/CN103382227A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030699A (en) * | 2011-10-08 | 2013-04-10 | 王晓珍 | Preparation method of canna edulis ker oxidized starch |
Non-Patent Citations (4)
| Title |
|---|
| 王彦斌: "《淀粉精细化学品合成及其应用》", 1 July 2004, 民族出版社 * |
| 王春艳 等: "双氧水氧化玉米淀粉的制备及其性质研究", 《粮食与饲料工业》 * |
| 陈佑宁 等: "氧化淀粉合成工艺研究", 《中国胶粘剂》 * |
| 陈彦逍 等: "催化氧化制备氧化淀粉", 《中国粮油学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833862A (en) * | 2014-02-27 | 2014-06-04 | 华南理工大学 | Oxidized glutinous rice starch as well as preparation method and application thereof |
| CN103833862B (en) * | 2014-02-27 | 2016-07-06 | 华南理工大学 | A kind of oxidation glutinous rice starch and preparation method thereof and application |
| CN104525135A (en) * | 2015-01-20 | 2015-04-22 | 四川大学 | Dual-gel adsorbent and production method thereof |
| CN106146737A (en) * | 2015-05-20 | 2016-11-23 | 内蒙古大学 | The method preparing super absorbent resin with high potassium content for raw material one kettle way with carboxymethyl potato starch and hydrogen peroxide |
| CN105441022A (en) * | 2015-12-28 | 2016-03-30 | 常熟市宏宇钙化物有限公司 | Method for preparing calcium hydroxide adhesive |
| CN106543292A (en) * | 2016-09-28 | 2017-03-29 | 南通宏慈药业有限公司 | A kind of processing technology of oxidation hydroxypropyl starch |
| CN109280193A (en) * | 2018-09-20 | 2019-01-29 | 黄旭东 | A kind of preparation method of starch degradation material |
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Owner name: SHOUGUANG JINYUANDONG MODIFIED STARCH CO., LTD. Free format text: FORMER OWNER: JUNENG GOLDEN CORN DEVELOPMENT CO., LTD., SHOUGUANG, SHANDONG Effective date: 20131211 |
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Effective date of registration: 20131211 Address after: 262700 Shouguang City, Shandong Province Development Zone Applicant after: Shouguang golden Far East Starch Co. Ltd. Address before: 262700 Shandong city in Weifang Province, Shouguang City emerging Street No. 150 Applicant before: Shandong Shouguang Juneng Group Golden Corn Co., Ltd. |
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Application publication date: 20131106 |