CN103145101A - Sugar manufacturing process-based high-purity chlorine dioxide preparation method - Google Patents
Sugar manufacturing process-based high-purity chlorine dioxide preparation method Download PDFInfo
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- CN103145101A CN103145101A CN2013100893308A CN201310089330A CN103145101A CN 103145101 A CN103145101 A CN 103145101A CN 2013100893308 A CN2013100893308 A CN 2013100893308A CN 201310089330 A CN201310089330 A CN 201310089330A CN 103145101 A CN103145101 A CN 103145101A
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Abstract
The invention discloses a sugar manufacturing process-based high-purity chlorine dioxide preparation method. The preparation method comprises the steps of: with sodium chlorate as raw material and cane sugar, glucose, as well as sugar juice or syrup in the sugar production process as a reducing agent, preparing high-purity chlorine under the action of phosphoric acid, wherein as a settling agent in sugar production, phosphate produced in reaction is added into sugar juice for reutilization. The purity of the produced chlorine dioxide is more than 96%, the raw material conversion rate is more than 90%, and the sterilization rate of sugar juice is more than 98%. The method has the advantages that raw materials are conveniently prepared and can be obtained from sugar production enterprises or purchased with lower price, the technological operation is simple and convenient, continuous operation can be performed, the purity of the chlorine dioxide is high, the cost is low, no waste slag and waste liquor are discharged, the safety is high, and the preparation method is suitably applied in sugar production technology.
Description
Technical field
The invention belongs to sterilization, sterilant field, specifically a kind of chlorine dioxide with high purity preparation method based on sugar refining technology.
Background technology
Dioxide peroxide is a kind of strong oxidizer and efficient germicide, effect to microorganism is because of dioxide peroxide, cell walls to be had stronger absorption and penetrativity, the oxidation cell includes the enzyme of sulfydryl effectively, suppress fast the synthetic of microprotein, cause the microbial metabolism obstacle and necrocytosis, bacterium, fungi, algae, virus and cell gemma are all had killing effect preferably, but be safe and harmless to humans and animals.The World Health Organization has classified it as A I level wide spectrum, efficient and safe sterilizing agent, is widely used in sterilization, the sterilization of tap water, health care, three industrial wastes, oil production, fowl dirty swine product, aquaculture, food-processing and the aspect such as fresh-keeping.The Bactericidal Mechanism of dioxide peroxide is that oxidizing reaction rather than chlorination have occured, different from chlorine, do not produce chlorinated compound, therefore the good sterilization effect of dioxide peroxide is in chlorine, can not produce haloform etc. strong " three cause " (carcinogenic, teratogenesis, mutagenesis) material, European and American developed countries' widespread use dioxide peroxide substitute chlorine and carry out the sterilization of tap water.
Produce at present dioxide peroxide chlorite method commonly used and chlorate process.Chlorite oxidation style owned by France generates dioxide peroxide with hydrochloric acid, sulfuric acid or chlorine reaction, although the productive rate of dioxide peroxide can be up to more than 95%, and reaction does not need heating, in product, purity of chlorine dioxide is high, but because the Textone raw materials cost is expensive, the suitability for industrialized production difficulty is large.
Oxymuriate reduction method owned by France is widely used because cost of material is lower.Chlorate process prepares dioxide peroxide mainly take sodium chlorate as raw material under reductive agent and acidic conditions.Reductive agent commonly used has methyl alcohol, sulfurous gas, hydrochloric acid, hydrogen peroxide and urea etc., and acidic medium is often hydrochloric acid or sulfuric acid.Take methyl alcohol as reductive agent, by product is many, and purity of chlorine dioxide is low, and speed of response is slow, and methyl alcohol is poisonous inflammable, is not suitable for using in sugar refinery or drinking water treatment; Take urea, sulfurous gas or hydrogen peroxide etc. as reductive agent, all there are the shortcomings such as the technique difficulty is controlled, feed stock conversion is low, production cost is high, purity of chlorine dioxide is low.Take hydrochloric acid as souring agent with during reductive agent, need higher acid concentration, the dioxide peroxide of production approximately 50% the chlorine that can adulterate, not only purity of chlorine dioxide is low and can produce " three cause " material, has potential safety hazard; Take sulfuric acid as souring agent, because sulfuric acid corrosion resistance is strong, high to equipment and operating environment requirement, cost of investment is high.In addition, take hydrochloric acid or sulfuric acid as souring agent, also can produce the by products such as a large amount of sodium-chlor or saltcake, needing in time to discharge the guarantee reaction when producing continuously carries out smoothly, and the by product added value is not high, and recovery processing technique is complicated, and cost is high, particularly the by product such as sodium-chlor or saltcake and excessive souring agent enter Closed Circulation in Sugar Production production unit are caused corrosion and affect quality product, and therefore the method for existing production dioxide peroxide is not suitable for the sterilization of Closed Circulation in Sugar Production.
Carbohydrate can be used as reductive agent, and widely used carbohydrate is mainly sucrose and glucose, and the main component of the syrup in sugar manufacturing process and syrup is also sucrose, so raw material sources are extensive, and is cheap and easy to get.Phosphoric acid is mineral acid, and character is stable than sulfuric acid and hydrochloric acid, and processing safety is high, is the souring agent of desirable preparation dioxide peroxide, but does not have so far take oxymuriate as raw material, sucrose or glucose and phosphoric acid is applied to produce the patent report of dioxide peroxide.
At sugarcane or beet-sugar factory, when entering to press, a large amount of bacteriums can be brought in production process the sugaring raw material, Leuconostoc mesenteroides particularly, not only can consume a large amount of sucrose, produce simultaneously full-bodied dextran, blocking pipeline, and give follow-up clarification, boil the workshop sections such as sugar, purging and cause material impact, quality and the output of product reduced.Report, due to the existence of Leuconostoc mesenteroides, every 10000t sugaring raw material is Direct Loss 7t sucrose approximately.The general applied chemistry sterilant of sugar manufacturing industry is processed the microbiological contamination problem at present, usually the chemical composition that contains food production forbidding in the traditional chemical sterilant, the sterilant that therefore need a kind of efficient, safety, cheapness, environmental protection, meets the foodstuff additive service requirements is applied to sugar manufacturing industry.Dioxide peroxide (GB2760-2007) is listed in foodstuffs industry by China's " foodstuff additive use hygienic standard " and is used list with processing aid, but the technology report of the production dioxide peroxide of desirable suitable sugar manufacturing industry use is not yet arranged so far.
Therefore high in the urgent need to a kind of product purity, production cost is low, technical matters is easy, be fit to the method for the production dioxide peroxide of sugar refining technology.
Summary of the invention
The object of the present invention is to provide a kind of chlorine dioxide with high purity preparation method based on sugar refining technology.The method product purity is high, production cost is low, technical matters is easy and safety and environmental protection.
The technical scheme that the present invention solves the problems of the technologies described above is:
A kind of chlorine dioxide with high purity preparation method based on sugar refining technology is to be that 15～50% sodium chlorate solution, mass percentage concentration are that 10～65% reductive agent and souring agent phosphoric acid add in reactor respectively continuously with mass percentage concentration, the mol ratio of sodium chlorate and reductive agent is 16～53:1, adding souring agent phosphoric acid to make reaction system acidity is 4～12mol/L, be that 50～85 ℃, pressure are to react under 0.01～0.06MPa, reaction times 10～40min condition in temperature, obtain dioxide peroxide.
Described reductant solution is syrup in sucrose, glucose, sugar manufacturing process or the syrup in sugar manufacturing process.
The dioxide peroxide that generates is drawn, and add in the syrup of Closed Circulation in Sugar Production line and carry out sterilising treatment, the phosphoric acid salt that reaction generates need to add in syrup by actual Closed Circulation in Sugar Production and recycles.
Above-mentioned sodium chlorate solution's mass percentage concentration is preferably 20～45%.
The mol ratio of above-mentioned sodium chlorate and reductive agent is preferably 20～48:1.
The above-mentioned souring agent phosphoric acid that adds makes reaction system acidity be preferably 5～10mol/L.
Above-mentioned temperature of reaction is preferably 60～80 ℃, and the reaction times is preferably 15～30min.
Chemical reaction of the present invention is as follows:
1) reaction take sucrose or syrup as reductive agent:
48NaClO
3+C
12H
22O
11+16H
3PO
4→48ClO
2↑+16Na
3PO
4+12CO
2↑+35H
2O
2) reaction take glucose as reductive agent:
24NaClO
3+C
6H
12O
6+8H
3PO
4→24ClO
2↑+8Na
3PO
4+6CO
2↑+18H
2O
Beneficial effect of the present invention is as follows:
1. sucrose is the Closed Circulation in Sugar Production product, glucose is cheap monose, (sucrose quality percentage composition is about (10～65%) and is the Closed Circulation in Sugar Production intermediate for syrup or syrup, and souring agent phosphoric acid is the sugaring processing aid, therefore convenient for the preparation of the raw material sources of dioxide peroxide, all can be in the inner acquisition of sugar enterprise or with under-buy, production and carrying cost have been reduced, and the sucrose that reaction consumes is far smaller than the sucrose loss that is brought by microorganism, and is significant to improving sugar enterprise's economic benefit.
2. the present invention is take phosphoric acid as souring agent, reaction does not produce chlorine, product purity is high, and feed stock conversion is high, and speed of reaction is fast, the phosphoric acid salt that generates can continue to carry out fully recovering in sugar refining technology, discharge without waste residue and liquid, non-environmental-pollution is realized the clean cycle utilization, be suitable for industrialization and produce continuously, be particluarly suitable for sugar manufacturing industry and use.
Embodiment
Below by embodiment, the present invention is described in further detail.Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 20% solution that sodium chlorate is dissolved into mass percentage concentration, it is 10% solution that sucrose dissolved is become mass percentage concentration, continuously two solution in reactor are mixed by sodium chlorate and sucrose mol ratio at 48: 1, keeping temperature of reaction system is 70 ℃, adding continuously phosphoric acid to control reaction system acidity is 8mol/L, the maintenance reactor pressure is 0.06MPa, reaction 30min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 99.2%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, detect purity of chlorine dioxide and sodium chlorate transformation efficiency, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 97.7%, and transformation efficiency is 93.6%.
Embodiment 2
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 30% solution that sodium chlorate is dissolved into mass percentage concentration, it is 30% solution that sucrose dissolved is become mass percentage concentration, continuously two solution in reactor are mixed by sodium chlorate and sucrose mol ratio at 40: 1, keeping temperature of reaction system is 75 ℃, adding continuously phosphoric acid to control reaction system acidity is 5mol/L, the maintenance reactor pressure is 0.05MPa, reaction 40min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 99.0%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, detect purity of chlorine dioxide and sodium chlorate transformation efficiency, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 96.8%, and transformation efficiency is 91.7%.
Embodiment 3
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 15% solution that sodium chlorate is dissolved into mass percentage concentration, it is 25% solution that glucose is dissolved into mass percentage concentration, continuously two solution were mixed in reactor in 20: 1 in molar ratio, keeping temperature of reaction system is 50 ℃, adding continuously phosphoric acid to control reaction system acidity is 12mol/L, the maintenance reactor pressure is 0.02MPa, reaction 10min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 98.4%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 96.5%, and transformation efficiency is 92.8%.
Embodiment 4
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 50% solution that sodium chlorate is dissolved into mass percentage concentration, it is 40% solution that glucose is dissolved into mass percentage concentration, continuously two solution were mixed in reactor in 16: 1 in molar ratio, keeping temperature of reaction system is 60 ℃, adding continuously phosphoric acid to control reaction system acidity is 4mol/L, the maintenance reactor pressure is 0.01MPa, reaction 30min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 98.3%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 96.2%, and transformation efficiency is 90.9%.
Embodiment 5
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 25% solution that sodium chlorate is dissolved into mass percentage concentration, getting mass percentage concentration from the Closed Circulation in Sugar Production line is 65% syrup, continuously two solution in reactor are mixed by sodium chlorate and sucrose mol ratio at 53: 1, keeping temperature of reaction system is 85 ℃, adding continuously phosphoric acid to control reaction system acidity is 7mol/L, the maintenance reactor pressure is 0.02MPa, reaction 25min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 98.8%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 96.5%, and transformation efficiency is 92.9%.
Embodiment 6
Chlorine dioxide with high purity preparation method based on sugar refining technology:
it is 45% solution that sodium chlorate is dissolved into mass percentage concentration, getting mass percentage concentration from the Closed Circulation in Sugar Production line is 15% syrup, continuously two solution in reactor are mixed by sodium chlorate and sucrose mol ratio at 44: 1, keeping temperature of reaction system is 80 ℃, adding continuously phosphoric acid to control reaction system acidity is 10mol/L, the maintenance reactor pressure is 0.03MPa, reaction 15min, the dioxide peroxide that generates is added in the syrup of Closed Circulation in Sugar Production line, total number of bacterial colony in the syrup of sampling and measuring effect front and back after 5min, the dioxide peroxide sterilization rate is 98.5%, the phosphoric acid salt that reaction produces need to add in syrup by actual Closed Circulation in Sugar Production and recycles.Separately react under same materials proportioning and reaction conditions, the chlorine dioxide that produces is absorbed ClO in assaying reaction liquid and absorption liquid with frozen water
2, ClO
3 -And Cl
2Content, ClO
2Purity is 97.1%, and transformation efficiency is 93.3%.
Claims (5)
1. chlorine dioxide with high purity preparation method based on sugar refining technology, it is characterized in that: be that 15～50% sodium chlorate solution, mass percentage concentration are that 10～65% reductive agent and souring agent phosphoric acid add in reactor respectively continuously with mass percentage concentration, the mol ratio of sodium chlorate and reductive agent is 16～53: 1, adding souring agent phosphoric acid to make reaction system acidity is 4～12mol/L, be that 50～85 ℃, pressure are to react under 0.01～0.06MPa, reaction times 10～40min condition in temperature, obtain dioxide peroxide;
Described reductant solution is syrup in sucrose, glucose, sugar manufacturing process or the syrup in sugar manufacturing process;
The dioxide peroxide that generates is drawn, and add in the syrup of Closed Circulation in Sugar Production line and carry out sterilising treatment, the phosphoric acid salt that reaction generates need to add in syrup by actual Closed Circulation in Sugar Production and recycles.
2. a kind of chlorine dioxide with high purity preparation method based on sugar refining technology according to claim 1, it is characterized in that: described sodium chlorate solution's mass percentage concentration is 20～45%.
3. a kind of chlorine dioxide with high purity preparation method based on sugar refining technology according to claim 1, it is characterized in that: the mol ratio of described sodium chlorate and reductive agent is 20～48:1.
4. a kind of chlorine dioxide with high purity preparation method based on sugar refining technology according to claim 1 is characterized in that: described to add souring agent phosphoric acid to make reaction system acidity be 5～10mol/L.
5. a kind of chlorine dioxide with high purity preparation method based on sugar refining technology according to claim 1, it is characterized in that: described temperature of reaction is 60～80 ℃, the reaction times is 15～30min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278108A (en) * | 2014-10-22 | 2015-01-14 | 广西科技大学 | Oxidative decolorization method for remelt syrup of brown granulated sugar by using lime clarification method combined with chlorine dioxide |
| CN115215296A (en) * | 2022-06-09 | 2022-10-21 | 广西国宏智鸿环保科技集团股份有限公司 | Method for preparing chlorine dioxide solution in situ |
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| CN1353083A (en) * | 2000-11-14 | 2002-06-12 | 董为毅 | Process for preparing ClO2 |
| CN1506319A (en) * | 2002-12-12 | 2004-06-23 | 天津华特环保技术开发有限公司 | Composite ClO2 generating process |
| US20060006361A1 (en) * | 2004-07-08 | 2006-01-12 | Joseph Callerame | Clathrate of chlorine dioxide |
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2013
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Patent Citations (4)
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| CN1353083A (en) * | 2000-11-14 | 2002-06-12 | 董为毅 | Process for preparing ClO2 |
| CN1247448C (en) * | 2002-10-21 | 2006-03-29 | 绵阳高新区鑫天科技有限公司 | Process for preparing ClO2 and coproducing organic salts and(or) compound fertilizer simultaneously |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278108A (en) * | 2014-10-22 | 2015-01-14 | 广西科技大学 | Oxidative decolorization method for remelt syrup of brown granulated sugar by using lime clarification method combined with chlorine dioxide |
| CN115215296A (en) * | 2022-06-09 | 2022-10-21 | 广西国宏智鸿环保科技集团股份有限公司 | Method for preparing chlorine dioxide solution in situ |
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