CN101024492A - High-purity chlorine dioxide gas generating method and apparatus - Google Patents
High-purity chlorine dioxide gas generating method and apparatus Download PDFInfo
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- CN101024492A CN101024492A CN 200710061513 CN200710061513A CN101024492A CN 101024492 A CN101024492 A CN 101024492A CN 200710061513 CN200710061513 CN 200710061513 CN 200710061513 A CN200710061513 A CN 200710061513A CN 101024492 A CN101024492 A CN 101024492A
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Abstract
The invention relates to a producing method for high purity chlorine dioxide gas and the device to realize the method. It uses sodium chlorate solution and hydrochloric acid as raw material, and taking reaction. The mixture gas of chlorine and chlorine dioxide would pass through gas washing device of CPVC material filled with sodium chlorite solid and transfer chlorine to chlorine dioxide to gain high purity chlorine dioxide gas. The gas washing device is multilevel structure that installs detonation separating board between gas washing device and reactor. The invention has high yield of chlorine dioxide, and the purity could reach 98%, yield could reach 95%. The high purity chlorine dioxide could be used for sterilization.
Description
Technical field
The present invention relates to a kind of method for generation of chlorine dioxide with high purity gas, specifically relate to a kind of method that obtains chlorine dioxide with high purity gas behind sodium chlorate and hydrochloric acid reaction, the Textone gas washing of utilizing.The invention still further relates to a kind of generating unit that is used to realize this method.Method for generation of the present invention and generating unit are suitable for the sterilization and disinfection of space environments such as vegetables, fruit, grain reserve bank and supermarket.
Background technology
Dioxide peroxide is a kind of wide spectrum, efficient, nontoxic disinfection sanitizer, have the sterilization wide spectrum, effective concentration is low, speed of action is fast, colourless, odorless, advantage such as nontoxic, safe in utilization, extensively be applied to the fields such as sterilization fresh-keeping of water treatment, association with pulp bleaching, food-processing, medical treatment, purifying air, vegetable and fruit as disinfection sanitizer, deodorization mould inhibitor, food preservative, water quality cleansing agent, the social demand amount increases day by day.The World Health Organization thinks that dioxide peroxide does not have carcinogenic, teratogenecity fully, and it is come the first place of safe disinfection agent, be described as the 4th generation disinfectant.
Because dioxide peroxide character instability, therefore volatile, easy decomposition, explosive are difficult for preserving, and can only produce preparation nearby in the scene, use as early as possible.
Different according to reaction raw materials and technology have many different dioxide peroxide preparation methods, comprise electrochemical process, chemical synthesis and their combination.Ma Dixun the earliest (Mathieson) method is to produce chlorine dioxide with the sulphur dioxide reduction sodium chlorate.Thereafter having developed a series of is raw material with the sodium chlorate, makes the chlorine dioxide production method of reductive agent respectively with Manganse Dioxide, hydrochloric acid, sodium-chlor and sulfuric acid etc.Wherein the R2 method is reductive agent with sodium-chlor, generates hydrogenchloride with sulfuric acid reaction, and the sodium chlorate of further reducing again obtains dioxide peroxide.This method produces the waste liquid that contains sulfuric acid and sodium sulfate in a large number, the recycling trouble.The Solvey method is a raw material with sodium chlorate, sulfuric acid and methyl alcohol, and wherein methyl alcohol is reductive agent, and the dioxide peroxide yield of this method is 85～90%.The R8 method is raw materials used identical with the Solvey method, adopts U.S. Albright company to develop improved methyl alcohol method, owing to adopted the unitary reactor of reaction-evaporate-crystallization, has improved throughput, and transformation efficiency is increased to more than 95%.The technological operation of R8 method is simple, production efficiency is high, be used widely abroad at present, but this technology needs transpiring moisture, and it is bigger to consume quantity of steam.Direct method adopts the electrolytic process technology of Canadian Chemeties company exploitation, adopt sodium-chlor to make electrolytic solution, drop into and carry out electrolysis in the septate electrolyzer, produce the mixed gas of dioxide peroxide, chlorine, ozone and hydrogen peroxide, by-product is sodium hydroxide and hydrogen.The deficiency of this method is that investment is big, raw material consumption is big, power consumption is high, and barrier film needs often to clean and change, dioxide peroxide proportion less than 30%, and output is limited.
The production method investment cost height of above dioxide peroxide, equipment volume is huge, and auxiliary facility is many, and only suitable large-scale industry purposes is not suitable for commercialization, small serial production.
At present, the dioxide peroxide that uses for commercial on-site preparation mainly utilizes the chemical process preparation by small-sized chlorine dioxide generating device, is mainly used in fields such as drinking water disinfection, Hospital Sewage Treatment, industrial circulating water sterilization algae removal.Wherein, be that the method for feedstock production dioxide peroxide roughly has following several with the Textone:
2NaClO
2+Cl
2＝2ClO
2+2NaCl (1)
5NaClO
2+4HCl＝4ClO
2+5NaCl+2H
2O (2)
2NaClO
2+NaOCl+2HCl＝2ClO
2+3NaCl+H
2O (3)
The dioxide peroxide yield of reaction (1) is higher, but that device needs the chlorination system is supporting, and using value is little.
The titanium dioxide rate yield of reaction (2) only is 80% (wherein 20% being converted into sodium-chlor) of Textone transformation efficiency, and the hydrochloric acid input amount is 3 times of theoretical reacting weight, can produce a large amount of chlorions and residual hydrochloric acid, causes certain influence in actual applications.
Reaction (3) needs three kinds of materials to participate in reaction simultaneously, and needs to divide the two-stage to carry out, and promptly generates chlorine by clorox and hydrochloric acid reaction earlier, generates dioxide peroxide by chlorine and Textone reaction again, and operation is comparatively complicated, seldom adopts at present.
In general, because the price of Textone is equivalent to 3～4 times of the sodium chlorate price, be that the running cost of feedstock production dioxide peroxide is too high with the Textone.
In view of above situation, now numerous small-sized chlorine dioxide generating devices all are to be that raw material is produced the dioxide peroxide that contains a large amount of chlorine with sodium chlorate and hydrochloric acid, are called the compound producer of chemical method chlorine dioxide.Compound chlorine dioxide generating device is raw material generation dioxide peroxide with the oxymuriate, and running cost is lower.But also there is significant disadvantages: the one, the chlorine that produces has accounted for bigger ratio, and dioxide peroxide only accounts for 1/3rd, the purity of dioxide peroxide is lower; The 2nd, the sodium chlorate transformation efficiency is low, and the dioxide peroxide yield is less than 40%, and a large amount of unconverted raw materials, auxiliary material are with discharging of waste liquid, and reaction cost increases; The 3rd, the waste reaction solution that contains a large amount of sodium chlorate and sodium-chlor is rationally handled so far as yet, and the residual concentration of dioxide peroxide is higher in the waste reaction solution, and environment is caused certain pollution.
Therefore, be that the problem that the chlorine dioxide generating device of raw material need solve is to improve the purity of dioxide peroxide with the oxymuriate, improve the transformation efficiency of oxymuriate, reduce the residual quantity of dioxide peroxide in the waste reaction solution.
Summary of the invention
The objective of the invention is to address the above problem, a kind of sodium chlorate transformation efficiency height is provided, reaction safety, chlorine dioxide with high purity gas method for generation completely.
A kind of generating unit that is used to realize chlorine dioxide method for generation of the present invention is provided, and the security that further improves generating unit is another goal of the invention of the present invention.
Chlorine dioxide method for generation of the present invention is that sodium chlorate method and Textone method are organically combined, and utilizes following reaction formula:
2NaClO
3+4HCl→2ClO
2+Cl
2+2NaCl+2H
2O
2NaClO
2+Cl
2→2ClO
2+2NaCl
Produce chlorine dioxide.
Particularly, chlorine dioxide with high purity gas method for generation of the present invention is to be raw material with sodium chlorate solution and hydrochloric acid, under the condition that in reaction system, feeds warm air, react, the chlorine that reaction produces and the mixed gas of dioxide peroxide are by being equipped with Textone solid air-washer, with chlorine conversion wherein is dioxide peroxide, obtains highly purified chlorine dioxide.
In the first step reaction, the mass concentration of choosing the sodium chlorate solution is 35%～50%, and sodium chlorate solution's excessive concentration reacts too violent, and concentration is low excessively, and it is too slow again to react, and further, best sodium chlorate solution's mass concentration of the present invention is 45%.The mass concentration of choosing hydrochloric acid soln is 40%～65%, and concentration of hydrochloric acid is too high, and by product chlorine generation increases, and concentration is low excessively, can produce a large amount of waste liquids, causes waste liquid aftertreatment amount to increase, and further, best hydrochloric acid soln mass concentration of the present invention is 55%.
The present invention also feeds certain temperature in reaction system warm air carries out aeration, and the effect of warm air aeration is for reaction system provides required heat on the one hand, make reaction can be fast, steadily carry out; Then the reaction liquid phase is played the effect of stirring on the other hand, guarantee to react evenly, carry out smoothly; Simultaneously, the chlorine dioxide that reaction can also be produced rapid stripping from liquid phase comes out, and to improve the transformation efficiency of sodium chlorate, makes reaction thoroughly.The hot air temperature that feeds in reaction system should be controlled between 70 ℃～90 ℃, and optimal reaction temperature of the present invention is 75 ℃.
In the second step reaction, the Textone solid that is used to transform chlorine is to load on bulk thread CPVC material earlier, reinstalls in the air-washer, and the packing density of Textone and thread CPVC filler is 0.3～0.5: 1.This filling method and the packing density of Textone can guarantee that the chlorine that produces all is converted into chlorine dioxide, can guarantee that the resistance when gas passes through air-washer is less simultaneously again, are beneficial to gas and pass through smoothly.Select the purpose of CPVC filler to be the corrosion that this kind material is not subjected to chlorine dioxide or chlorine, durable in use.
The invention provides a kind of generating unit that is applicable to above-mentioned chlorine dioxide method for generation, include reactor, air-washer, sodium chlorate solution's storage tank and hydrochloric acid storage tank, sodium chlorate solution's storage tank is connected with reactor with valve by pipeline with the hydrochloric acid storage tank, the control of sodium chlorate solution and hydrochloric acid is entered in the reactor, in reactor, be placed with an air aeration head, and be connected with the air outside pump by aeration tube, air-washer is connected the top of reactor, inside is filled with the bulk thread CPVC material of load Textone solid, and the bottom of reactor is by valve and waste liquid tank of pipe connection.
Air-washer wherein is multistage structure, puts out quick-fried dividing plate all being equipped with between every grade of air-washer and between air-washer and the reactor.Putting out quick-fried dividing plate and utilize safety philosophy design, is to be provided with on the CPVC plate of 4mm to put out quick-fried gap at thickness, and this gap can make gas pass through smoothly, has guaranteed the security of reactor again.
The present invention also is connected with heating unit on aeration tube, so that the air that feeds in the reaction system is heated.Described heating unit can be interchanger, electric heater, oil bath heating, heating tube etc.
The preferred heating unit of the present invention is a stainless heat exchanger, and its inner coil pipe that crawls that adopts is communicated with aeration tube, and the coil pipe that crawls outward and fill high temperature heat conductive oil between the outer cover of heat exchanger and add warm air.
In the chlorine dioxide gas generating apparatus of the present invention, comprise reactor, air-washer, aeration tube, the manufacturing of the first-class whole employing CPVC material of aeration, transmitters such as temperature, pressure are corrosion-resistant.
Chlorine dioxide method for generation of the present invention is the combination of sodium chlorate method and Textone method.In reaction, utilize warm air to carry out aeration, both guaranteed the temperature of reacting required to play the effect of stirring reaction system again, the dioxide peroxide stripping from liquid phase that produces can also be come out simultaneously, make reaction more abundant.In the generating unit of the present invention, the air-washer on reactor top is made up of multilevel hierarchy, add the puffy filler of forming by thread CPVC and solid Textone in every level structure, the chlorine of generation and the mixed gas of dioxide peroxide are risen when passing through, and are chlorine dioxide with chlorine conversion further.Because chlorine dioxide is blast easily under certain condition, between reactor top and air-washer and multi-stage scrubbing device, be provided with and put out quick-fried dividing plate, put out quick-fried dividing plate and utilize the safety philosophy design, on dividing plate, be provided with and put out quick-fried gap, this gap both can make the chlorine of reactor generation and the gas mixture of dioxide peroxide pass through smoothly, had guaranteed the security of reactor system simultaneously again.
Adopt method for generation of the present invention and generating unit, reaction is carried out thoroughly, and the transformation efficiency height of sodium chlorate can reach more than 95%, and the chlorine dioxide purity that obtains reaches more than 98%, and yield is more than 95%.The chlorine dioxide with high purity gas that the present invention produces can be directly used in vegetables, fruit and other sterilization and disinfection that is not suitable for various space environment microorganisms such as liquid sterilization disinfectant such as supermarket, grain reserve bank and use.
Description of drawings
Fig. 1 is the structural representation of chlorine dioxide with high purity gas generating unit of the present invention.
Embodiment
The structure of chlorine dioxide with high purity gas generating unit constitutes agent structure jointly by reactor 7 and the air-washer 5 that communicates with it as shown in Figure 1.Be connected with sodium chlorate solution's storage tank 4 and the hydrochloric acid storage tank 11 that supplies raw material on reactor 7 tops, the sodium chlorate solution enters reactor by valve and under meter, hydrochloric acid is pressed into participation reaction in the reactor by valve and under meter control under the pressurized air effect by pneumatic pump 13 generations and process air cushioning jar 14.Another part air in the air cushioning jar 14 feeds in the aeration tube 10, and after interchanger 12 heating, under valve control, the aeration head 8 of process reactor bottom enters and carries out hot aeration in the reaction soln.Reactor top is provided with the pressure and temperature display unit, with reaction pressure in the Indicator Reaction device and temperature.The chlorine that reactor produces and the mixed gas of dioxide peroxide enter in the air-washer 5 that is connected reactor 7 tops under the stirring of airflow drives.Air-washer 5 is made up of multilevel hierarchy, adds the puffy filler of being made up of thread CPVC and solid Textone in every grade of air-washer, and being used for chlorine conversion is chlorine dioxide.Put out quick-fried dividing plate 6 also being equipped with between every grade of air-washer and between air-washer and the reactor.The high-purity chlorine dioxide gas that produces by air-washer 5 backs enters in the airstream device 3, and the pressurized air that pneumatic pump 2 produces by airstream device 3, is derived chlorine dioxide under air flowmeter control through air cushioning jar 1, is used for sterilization and disinfection.Residual reaction liquid in the reactor 7 imports in the waste liquid tank 9, after separating treatment, and the hydrochloric acid recycling use, sodium chloride solution is discharged, and there is not secondary pollution in whole process.
All materials such as reactor, air-washer, solution storage tank and gas piping all adopt impregnating material CORZAN CPVC to make.
Principle of work of the present invention is as follows: it is 45% solution that certain amount of industrial level sodium chlorate is mixed with concentration, in the sodium chlorate solution's storage tank 4 of packing into, enters reactor 7 through valve and under meter control; Adding concentration is 55% hydrochloric acid soln in the hydrochloric acid storage tank 11, slowly is pressed in the reactor 7 with pressurized air and reacts.Pressurized air is after interchanger 12 heating, carry out hot aeration in the aeration head 8 feeding reaction solns by aeration tube 10 and reactor 7 bottoms, provide reaction required temperature on the one hand, play the effect of stirring on the other hand, and will react and enter air-washer 5 after the chlorine that produces and chlorine dioxide are taken out of.Putting out between the air-washer 5 is provided with on the quick-fried dividing plate 6 puts out quick-fried gap, plays the effect of flame proof on the one hand, on the other hand the filler in the air-washer 5 is had supporting role.After mixed gas enters air-washer 5, chlorine wherein further with filler in Textone reaction be converted into chlorine dioxide.The high-purity chlorine dioxide gas that produces is derived by airstream device 3.
Claims (10)
1, a kind of chlorine dioxide with high purity gas method for generation, be to be raw material with sodium chlorate solution and hydrochloric acid, under the condition that in reaction system, feeds warm air, react, the chlorine that reaction produces and the mixed gas of dioxide peroxide are by being equipped with Textone solid air-washer, with chlorine conversion wherein is dioxide peroxide, obtains highly purified chlorine dioxide.
2, chlorine dioxide with high purity gas method for generation according to claim 1 is characterized in that described Textone solid is to load on the bulk thread CPVC material, reinstalls in the air-washer.
3, chlorine dioxide with high purity gas method for generation according to claim 1, the mass concentration that it is characterized in that described sodium chlorate solution is 35%～50%.
4, chlorine dioxide with high purity gas method for generation according to claim 1, the mass concentration that it is characterized in that described hydrochloric acid soln is 40%～65%.
5, chlorine dioxide with high purity gas method for generation according to claim 1 is characterized in that the temperature of the warm air that feeds in the reaction system is 70 ℃～90 ℃.
6, a kind of chlorine dioxide with high purity gas generating unit, include reactor (7), air-washer (5), sodium chlorate solution's storage tank (4) and hydrochloric acid storage tank (11), sodium chlorate solution's storage tank (4) and hydrochloric acid storage tank (11) pass through pipeline, under meter is connected with reactor (7) with valve, the control of sodium chlorate solution and hydrochloric acid is entered in the reactor (7), in reactor (7), be placed with an air aeration head (8), and be connected with air outside pump (13) by aeration tube (10), air-washer (5) is connected the top of reactor (7), inside is filled with the bulk thread CPVC material of load Textone solid, and the bottom of reactor (7) is by a valve and a waste liquid tank of pipe connection (9).
7, chlorine dioxide with high purity gas generating unit according to claim 6 is characterized in that described air-washer (5) is multistage structure, puts out quick-fried dividing plate (6) being equipped with between every grade of air-washer (5) and between air-washer (5) and the reactor (7).
8, chlorine dioxide with high purity gas generating unit according to claim 6 is characterized in that being connected with heating unit (12) on aeration tube (10).
9, chlorine dioxide with high purity gas generating unit according to claim 8 is characterized in that described heating unit (12) is an interchanger.
10, chlorine dioxide with high purity gas generating unit according to claim 6 is characterized in that described chlorine dioxide generating device adopts the manufacturing of CPVC material.
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| CNB2007100615133A CN100491236C (en) | 2007-02-09 | 2007-02-09 | High-purity chlorine dioxide gas generating method and apparatus |
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| CN100491236C CN100491236C (en) | 2009-05-27 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218152A (en) * | 2011-06-08 | 2011-10-19 | 中北大学 | Gasifying device for air disinfection |
| CN102907489A (en) * | 2012-10-22 | 2013-02-06 | 江南大学 | Method for sterilizing and preserving surface of shell egg by using gaseous chlorine dioxide |
| CN102963871A (en) * | 2012-12-21 | 2013-03-13 | 闫云涛 | Chlorine dioxide generator |
| CN102976272A (en) * | 2012-09-24 | 2013-03-20 | 潍坊海洁环保设备有限公司 | Chlorine dioxide generator |
| CN106348249A (en) * | 2016-10-26 | 2017-01-25 | 吴予奇 | Manufacturing method for chlorine dioxide gas synthesis device |
| CN108100998A (en) * | 2018-01-17 | 2018-06-01 | 济南科林沃德环境科技有限公司 | A kind of pure chlorine dioxide generating means |
| CN111333367A (en) * | 2020-05-18 | 2020-06-26 | 湖南凝英新材料科技有限公司 | Preparation method of polycarboxylate superplasticizer |
| CN111908426A (en) * | 2020-07-06 | 2020-11-10 | 中润(大连)生物科技有限公司 | Chlorine dioxide gas generating device for space disinfection and preparation method |
| CN112741109A (en) * | 2021-02-22 | 2021-05-04 | 卫溯源(北京)生物医药科技有限公司 | Preparation method of chlorine dioxide sterilizing gas |
| CN114684790A (en) * | 2022-03-30 | 2022-07-01 | 中源(大连)生物环保科技有限公司 | Controllable dry method and device for preparing pure chlorine dioxide gas |
| CN116462160A (en) * | 2023-03-29 | 2023-07-21 | 大连交通大学 | By flue gas SO 2 Method and system for preparing steady-state chlorine dioxide for raw materials |
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- 2007-02-09 CN CNB2007100615133A patent/CN100491236C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218152A (en) * | 2011-06-08 | 2011-10-19 | 中北大学 | Gasifying device for air disinfection |
| CN102976272A (en) * | 2012-09-24 | 2013-03-20 | 潍坊海洁环保设备有限公司 | Chlorine dioxide generator |
| CN102976272B (en) * | 2012-09-24 | 2014-10-22 | 潍坊海洁环保设备有限公司 | Chlorine dioxide generator |
| CN102907489A (en) * | 2012-10-22 | 2013-02-06 | 江南大学 | Method for sterilizing and preserving surface of shell egg by using gaseous chlorine dioxide |
| CN102963871A (en) * | 2012-12-21 | 2013-03-13 | 闫云涛 | Chlorine dioxide generator |
| CN106348249A (en) * | 2016-10-26 | 2017-01-25 | 吴予奇 | Manufacturing method for chlorine dioxide gas synthesis device |
| CN108100998A (en) * | 2018-01-17 | 2018-06-01 | 济南科林沃德环境科技有限公司 | A kind of pure chlorine dioxide generating means |
| CN111333367A (en) * | 2020-05-18 | 2020-06-26 | 湖南凝英新材料科技有限公司 | Preparation method of polycarboxylate superplasticizer |
| CN111908426A (en) * | 2020-07-06 | 2020-11-10 | 中润(大连)生物科技有限公司 | Chlorine dioxide gas generating device for space disinfection and preparation method |
| CN111908426B (en) * | 2020-07-06 | 2022-12-06 | 中润(大连)生物科技有限公司 | Chlorine dioxide gas generating device for space disinfection and preparation method |
| CN112741109A (en) * | 2021-02-22 | 2021-05-04 | 卫溯源(北京)生物医药科技有限公司 | Preparation method of chlorine dioxide sterilizing gas |
| CN114684790A (en) * | 2022-03-30 | 2022-07-01 | 中源(大连)生物环保科技有限公司 | Controllable dry method and device for preparing pure chlorine dioxide gas |
| CN114684790B (en) * | 2022-03-30 | 2023-08-29 | 中源(大连)生物环保科技有限公司 | Method and device for preparing pure chlorine dioxide gas in controllable dry mode |
| CN116462160A (en) * | 2023-03-29 | 2023-07-21 | 大连交通大学 | By flue gas SO 2 Method and system for preparing steady-state chlorine dioxide for raw materials |
| CN116462160B (en) * | 2023-03-29 | 2024-05-24 | 大连交通大学 | By flue gas SO2Method and system for preparing steady-state chlorine dioxide for raw materials |
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