CN103275233B - Method for preparing oxidized starch with chlorine dioxide ultrasonic semi-dry method - Google Patents
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Abstract
The invention discloses a method for preparing oxidized starch with a chlorine dioxide ultrasonic semi-dry method. The method comprises the steps as follows: (1) a 0.1-0.2 mol/L chlorine dioxide solution is sprayed and added into native starch in a stirring state, and the ratio of the added chlorine dioxide solution volume to the starch mass is (1-4) mL:1g; (2) the mixture reacts for 35-55 min under 150 W-300 W ultrasonic wave; (3) 0.1 mol/L sodium sulfite solution is added to reduce unreacted oxidizing agent chlorine dioxide; (4) the mixture is rinsed repeatedly with distilled water and placed into a drying oven for drying until the moisture content is 10%-12%, and the ratio of the distilled water use volume to the starch mass is (10-20) mL:1g; and (5) the mixture is ground, subjected to 40-100-mesh sieve, packaged to obtain an oxidized starch finished product. The method has the advantages of low cost, small energy consumption and little pollution, production water is reduced by 40%-50%, energy consumption is reduced by 35%-45%, waste water discharge capacity is reduced by 30%-40%, and later-period wastewater treatment cost is reduced correspondingly. Various integrated economic and technical norms of the oxidized starch product prepared through the method meet the national standard of industrial oxidized starch products (HG/T3933-2007).
Description
Technical field
The present invention relates to the preparation method of the Sumstar 190 that a kind of physics combines with chemical process, specifically a kind of chlorine dioxide ultrasonic semi-dry method prepares the method for Sumstar 190.
Technical background
Sumstar 190 is a kind of modified starch that purposes is the widest, is widely used in the industry such as papermaking, weaving, food.Sumstar 190 is used for paper industry, as sizing agent and tackiness agent, the slipperiness of paper can be improved, surface strength of paper, as bursting strength, folding endurance etc., improve paper smoothness while reducing paper dry linting, make paper finer and smoother, and the printability of paper can be improved, make printed matter bright in luster happy.As slurry in textile industry, starching is carried out to yarn and good coating is provided.Mainly be used as additive, the low sticky thickening material of varieties of food items in the food industry, Arabic number glue, agar can be replaced to manufacture jelly and soft sweets based food, application Sumstar 190 manufactures soft sweets, and depot stable, production cost reduces, than good with denaturated starch by acid.The market demand of Sumstar 190 is very large, needs deep research, prepares the product that cost is low, product are of fine quality, performance is good.
Oxidant species for starch oxidation sex change is more, but industrially produces oxygenant used mainly clorox, potassium permanganate, hydrogen peroxide etc. in enormous quantities, and wherein clorox is most widely used oxygenant.Use hypochlorite oxidation starch, it is many that this technique produces waste water, and environmental pollution is very large, do not meet environmental requirement, and the gel-strength of starch is low.Use potassium permanganate oxidation starch, time in neutrality or acidic medium, manganese atom reduces to positive 4 valencys by positive 7 valencys, produces the insoluble Manganse Dioxide particle of brownish black, makes the hurried increase of starch spot number, and whiteness value declines.Hydrogen peroxide is more stable under slightly acidic or neutrallty condition, is activated in the basic conditions, has stronger oxidisability.So hydrogen peroxide oxidation carries out all in the basic conditions, but the suspension of Sumstar 190 easily turns yellow in the basic conditions, affects the whiteness of starch.Dioxide peroxide (ClO
2) be a kind of water-soluble oxidizers, have widely applicable, using dosage is few, speed of response is fast and reaction product is nontoxic, to the advantage such as human body is non-stimulated, is classified as A1 level security high effect disinfectants by the World Health Organization.ClO
2as oxygenant, its toxicological test result is nontoxic level.ClO
2oxidation capacity is strong, by available oxygen, and ClO
2the oxidation capacity had in theory is 2.63 times of chlorine, is 2.8 times of clorox.With ClO
2for industrial sex change Sumstar 190 prepared by oxygenant, ensure that the stability of Sumstar 190 for the security of food, high efficiency and quality product, and due to reaction efficiency high, ClO
2consumption reduces relatively, at the end of reaction, and the ClO in reaction solution
2residual quantity is low, has saved bath water amount, has reduced production cost, and reduces pollutant emission and Pollutant Treatment expense, is conducive to environment protection.Therefore, research adopts Chlorine Dioxide Oxidation starch, is the technological innovation that existing clorox process system cannot realize.
Usual indication ultrasonic wave, range of frequency is 2 × 10
4~ 10
9hz, compared with common sound wave, ultrasonic wave has beam because its wavelength is short, frequency is high strong and easy in focusing on the feature concentrating energy.When it is propagated in media as well, mechanical effect, cavatition, heat effect and chemical effect can be produced with medium interaction.In recent years, ultrasonic technology is also applied to starch field gradually, and ultrasonic technology has short, the advantage such as degraded nonrandomness, easy to control and energy consumption simple to operate are lower action time, is therefore identified as a kind of Novel physical method of starch conversion.Studies have found that, ultrasonic energy changes the supramolecular structure of starch granules and crystallizing field, and can reduce starch crystals district, thus improve the chemical reactivity of starch, increase Product yields, optimized product performance, improve raw material availability, show good prospects for commercial application.
The production method mainly wet processing of conventional oxidation starch, adds after water is adjusted to certain density starch milk by ative starch and carries out oxidizing reaction at a certain temperature.Wet processing can keep graininess, is easy to filter, wash after having reacted, and obtains the product that purity is high, but there is the shortcomings such as water of productive use amount is large, complex procedures, energy consumption are high, environmental pollution is serious.Dry process refers to that ative starch disperses under dry state or after drying in conversion unit, adds the oxygenant configured simultaneously, carries out the technique of oxidizing reaction at a certain temperature.Dry and wet way is compared, and reaction reagent adds few, and can avoid the operation such as filtration, washing, drying polluting environment in producing, and have the advantages such as flow process is short, energy consumption is low, simple equipments, be a kind of energy-conservation, green technique.But dry process reaction requires comparatively strict to ative starch water content, the water yield added greatly reduces, starch granules can not moisten preferably to be opened, and is unfavorable for that chemical reagent enters starch granules inside.The maximum difference of semidrying and dry method is that semidrying does not have pre-drying process, and in reaction, moisture is relatively high, is conducive to chemical reagent and enters starch granules inside.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that chlorine dioxide ultrasonic semi-dry method prepares Sumstar 190, prepare to solve conventional oxidation agent and technology the shortcoming that Sumstar 190 exists, and make that the preparation cost of Sumstar 190 is low, power consumption less, safety, efficient and constant product quality, environmental pollution be few.
The present invention solves the problems of the technologies described above with following technical scheme:
A kind of chlorine dioxide ultrasonic semi-dry method of the present invention prepares the method for Sumstar 190, and its operation steps is as follows:
(1) ative starch is placed in flask, start agitator and stir, spraying adds 0.1 ~ 0.2mol/L ClO 2 solution, and the ClO 2 solution volume added is 1 ~ 4mL ︰ 1g with the ratio of starch quality, is stirred to evenly;
(2) being placed in power is react 35 ~ 55min under 150 ~ 300W ultrasonic wave;
(3) add 0.1mol/L sodium sulfite solution and reduce unreacted oxygenant dioxide peroxide, until the terminal of reaction;
(4) with the rinsing repeatedly of enough distilled water, distilled water uses volume and ative starch mass ratio to be 10 ~ 20mL ︰ 1g, and then putting into drying in oven to moisture content is 10% ~ 12%;
(5) pulverize, cross 40 ~ 100 mesh sieves, packaging, namely obtain Sumstar 190 finished product.
Ative starch used in step (1) is tapioca (flour), W-Gum, yam starch or wheat starch.
In step (1), the stir speed (S.S.) of agitator is 50 ~ 65r/min.
In step (2), hyperacoustic temperature of reaction is 40 ~ 70 DEG C.
Oven temperature in step (4) is 40 ~ 55 DEG C.
Starch potassium iodide paper is adopted to judge terminal, stopped reaction after starch potassium iodide paper is become colorless by blueness in step (3).
The inventive method adopts dioxide peroxide combining ultrasonic ripple semidrying to prepare Sumstar 190, be characterized in solving tradition with clorox for oxygenant wet processing produces the problems such as the water of productive use amount that Sumstar 190 brings is large, complex procedures, energy consumption are high, environmental pollution is serious, solve again dry process starch granules can not to moisten preferably, be unfavorable for that chemical reagent enters the shortcoming of starch granules inside.
The inventive method is compared with traditional technique, and water of productive use amount reduces 40-50%, and energy consumption reduces 35-45%, and the quantity discharged of waste water decreases 30-40%, the corresponding reduction of later stage wastewater treatment expense.And the Sumstar 190 product every mixed economy technical indicator adopting the inventive method to prepare meets the national standard (HG/T3933-2007) of industrial oxidation starch product.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
The present invention is further described below in conjunction with specific embodiment.
Embodiment 1
100g cassava ative starch is placed in 250mL beaker, start agitator, stir speed (S.S.) controls at 60r/min, spraying adds the ClO 2 solution 300mL of 0.1mol/L, stir and be placed in ultrasound reactor, controlling its power is 150W, temperature of reaction is 60 DEG C, 0.1mol/L sodium sulfite solution is sprayed into gradually after reaction 45min, judge terminal with starch potassium iodide paper simultaneously, until starch potassium iodide paper become colorless by blueness after stopped reaction, moisture 4 times rinsing starch is repeatedly distilled with 1000mL, be placed in watch-glass, to put into temperature be 40 DEG C of drying in oven to moisture content is 10%, pulverize, cross 40 mesh sieves, packaging, namely described cassava oxidized starch is obtained.Product every mixed economy technical indicator meets the national standard (HG/T3933-2007) of industrial oxidation starch product.
Embodiment 2
20g native cornstarch is placed in 250ml beaker, start agitator, stir speed (S.S.) controls at 50r/min, spraying adds the ClO 2 solution 80mL of 0.15mol/L, stir and be placed in ultrasound reactor, controlling its power is 200W, temperature of reaction is 50 DEG C, 0.1mol/L sodium sulfite solution is sprayed into gradually after reaction 35min, judge terminal with starch potassium iodide paper simultaneously, until starch potassium iodide paper become colorless by blueness after stopped reaction, moisture 4 times rinsing starch is repeatedly distilled with 400mL, be placed in watch-glass, to put into temperature be 45 DEG C of drying in oven to moisture content is 11%, pulverize, cross 60 mesh sieves, packaging, namely described maize oxidized starch is obtained.Product every mixed economy technical indicator meets the national standard (HG/T3933-2007) of industrial oxidation starch product.
Embodiment 3
50g potato ative starch is placed in 250mL beaker, start agitator, stir speed (S.S.) controls at 65r/min, spraying adds the ClO 2 solution 100mL of 0.2mol/L, stir and be placed in ultrasound reactor, controlling its power is 250W, temperature of reaction is 40 DEG C, until spray into 0.1mol/L sodium sulfite solution after reaction 50min, judge terminal with starch potassium iodide paper simultaneously, until starch potassium iodide paper become colorless by blueness after stopped reaction, moisture 4 times rinsing starch is repeatedly distilled with 800mL, be placed in watch-glass, putting into temperature is 55 DEG C of baking ovens, interior oven dry to moisture content is 12%, pulverize, cross 80 mesh sieves, packaging, namely described potato oxidized starch is obtained.Product every mixed economy technical indicator meets the national standard (HG/T3933-2007) of industrial oxidation starch product.
Embodiment 4
20g wheat ative starch is placed in 250ml beaker, start agitator, stir speed (S.S.) controls at 50r/min, spraying adds the ClO 2 solution 20mL of 0.2mol/L, stir and be placed in ultrasound reactor, controlling its power is 300W, temperature of reaction is 70 DEG C, 0.1mol/L sodium sulfite solution is sprayed into gradually after reaction 40min, judge terminal with starch potassium iodide paper simultaneously, until starch potassium iodide paper become colorless by blueness after stopped reaction, moisture 4 times rinsing starch is repeatedly distilled with 300mL, be placed in watch-glass, to put into temperature be 50 DEG C of drying in oven to moisture content is 10%, pulverize, cross 100 mesh sieves, packaging, namely described wheat Sumstar 190 is obtained.Product every mixed economy technical indicator meets the national standard (HG/T3933-2007) of industrial oxidation starch product.
Claims (6)
1. chlorine dioxide ultrasonic semi-dry method prepares a method for Sumstar 190, it is characterized in that, its operation steps is as follows:
(1) ative starch is placed in flask, start agitator and stir, spraying adds 0.1 ~ 0.2mol/L ClO 2 solution, and the ClO 2 solution volume added is 1 ~ 4mL ︰ 1g with the ratio of starch quality, is stirred to evenly;
(2) being placed in power is react 35 ~ 55min under 150 ~ 300W ultrasonic wave;
(3) add 0.1mol/L sodium sulfite solution and reduce unreacted oxygenant dioxide peroxide, until the terminal of reaction;
(4) with the rinsing repeatedly of enough distilled water, distilled water uses volume and ative starch mass ratio to be 10 ~ 20mL ︰ 1g, and then putting into drying in oven to moisture content is 10% ~ 12%;
(5) pulverize, cross 40 ~ 100 mesh sieves, packaging, namely obtain Sumstar 190 finished product.
2. prepare the method for Sumstar 190 according to chlorine dioxide ultrasonic semi-dry method described in claim 1, it is characterized in that, ative starch used in step (1) is tapioca (flour), W-Gum, yam starch or wheat starch.
3. prepare the method for Sumstar 190 according to chlorine dioxide ultrasonic semi-dry method described in claim 1, it is characterized in that, in step (1), the stir speed (S.S.) of agitator is 50 ~ 65r/min.
4. prepare the method for Sumstar 190 according to chlorine dioxide ultrasonic semi-dry method described in claim 1, it is characterized in that, in step (2), hyperacoustic temperature of reaction is 40 ~ 70 DEG C.
5. prepare the method for Sumstar 190 according to chlorine dioxide ultrasonic semi-dry method described in claim 1, it is characterized in that, the oven temperature in step (4) is 40 ~ 55 DEG C.
6. prepare the method for Sumstar 190 according to chlorine dioxide ultrasonic semi-dry method described in claim 1, it is characterized in that, adopt starch potassium iodide paper to judge terminal, stopped reaction after starch potassium iodide paper is become colorless by blueness in step (3).
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| CN103694362A (en) * | 2013-12-19 | 2014-04-02 | 青岛农业大学 | Method for synthesizing oxidized corn starch by assisting composite oxidant through ultrasonic waves and synthesized substance |
| CN108824078A (en) * | 2018-07-01 | 2018-11-16 | 王琪宇 | A kind of preparation method of corrugated paper top sizing new material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1613875A (en) * | 2003-11-06 | 2005-05-11 | 广州泰成消毒洗涤用品有限公司 | Production for modified chlorinated starch |
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| CN1613875A (en) * | 2003-11-06 | 2005-05-11 | 广州泰成消毒洗涤用品有限公司 | Production for modified chlorinated starch |
Non-Patent Citations (2)
| Title |
|---|
| 新型氧化剂微波干法制备氧化淀粉及其性能研究;彭佳莹;《中国粮油学报》;20121231;第27卷(第5期);30页 * |
| 超声波辅助复合氧化法合成氧化玉米淀粉;李玉秀;《化学与生物工程》;20121231;61页 * |
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Inventor after: Huang Lijie Inventor after: Cai Yuanyuan Inventor after: Wang Shuangfei Inventor after: Su Dehua Inventor after: Yang Ying Inventor before: Huang Lijie Inventor before: Wang Shuangfei Inventor before: Su Dehua Inventor before: Yang Ying |
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Free format text: CORRECT: INVENTOR; FROM: HUANG LIJIE WANG SHUANGFEI SU DEHUA YANG YING TO: HUANG LIJIE CAI YUANYUANWANG SHUANGFEI SU DEHUA YANG YING |