CN100491237C - A chlorine dioxide gas generating device - Google Patents

A chlorine dioxide gas generating device Download PDF

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Publication number
CN100491237C
CN100491237C CNB2007100615148A CN200710061514A CN100491237C CN 100491237 C CN100491237 C CN 100491237C CN B2007100615148 A CNB2007100615148 A CN B2007100615148A CN 200710061514 A CN200710061514 A CN 200710061514A CN 100491237 C CN100491237 C CN 100491237C
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China
Prior art keywords
reactor
chlorine dioxide
air
gas generating
generating apparatus
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Expired - Fee Related
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CNB2007100615148A
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CN101024493A (en
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胡双启
晋日亚
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North University of China
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North University of China
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Abstract

The invention relates to a chlorine dioxide gas generating device that includes a reactor, gas washing device and air aeration head. Under the condition of passing hot air into reactor through air aeration head, the sodium chlorate solution would take reaction with hydrochloric acid to generate mixture gas of chlorine and chlorine dioxide. CPVC material filled with sodium chlorite solid is installed in gas washing device, which is used to 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

A kind of chlorine dioxide gas generating apparatus
Technical field
The present invention relates to a kind of chlorine dioxide gas generating apparatus, specifically relate to a kind of device that utilizes sodium chlorate and hydrochloric acid reaction, behind the Textone gas washing, obtains chlorine dioxide with high purity gas.Generating unit of the present invention is 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.As 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.The Solvey method is the synthetic dioxide peroxide of raw material with sodium chlorate, sulfuric acid and methyl alcohol, and wherein methyl alcohol is reductive agent.The R8 method is raw materials used identical with the Solvey method, adopts U.S. Albright company to develop the synthetic chlorine dioxide of improved methyl alcohol method.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 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, with the Textone be the device of feedstock production dioxide peroxide mainly based on following several reaction principles:
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)
Chlorine dioxide generating device gas recovery ratio based on reaction (1) is higher, but that device needs the chlorination system is supporting, and using value is little.
Titanium dioxide rate generating unit gas recovery ratio based on reaction (2) only is 80% (wherein 20% being converted into sodium-chlor) of Textone transformation efficiency, the hydrochloric acid input amount is 3 times of theoretical reacting weight, can produce a large amount of chlorions and residual hydrochloric acid, cause certain influence in actual applications.
Chlorine dioxide generating device based on reaction (3) needs three kinds of materials to participate in reaction simultaneously, and need to divide the two-stage to carry out, promptly generate chlorine by clorox and hydrochloric acid reaction earlier, generate dioxide peroxide by chlorine and Textone reaction again, operate comparatively loaded down with trivial details, the apparatus structure more 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 gas generating unit 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 generating unit completely.
Chlorine dioxide gas generating apparatus of the present invention includes:
A reactor, sodium chlorate solution and hydrochloric acid produce the mixed gas of chlorine and dioxide peroxide in this reaction;
An air aeration head is placed on the bottom of reactor, is used for to reactor internal reaction system bubbling air;
One first pneumatic pump is connected with air aeration head in the reactor by aeration tube, is used for providing air to the air aeration head;
A heating unit is connected on the aeration tube, is used for the air heating in the aeration tube;
The a plurality of air-washers that are cascaded, be installed in the top of reactor, inside is filled with the bulk thread chlorinated polyvinyl chloride material of load Textone solid, and the chlorine that is used in the mixed gas of chlorine that reactor is produced and dioxide peroxide further is converted into chlorine dioxide; And
A waste liquid tank is connected reactor bottom by valve, is used for discharging, reclaims reacted waste liquid.
Chlorine dioxide gas generating apparatus of the present invention also includes:
Sodium chlorate solution's storage tank is connected with reactor with valve by pipeline, is used for feeding the sodium chlorate solution to reactor;
A hydrochloric acid storage tank is connected with reactor with valve by pipeline, is used for feeding hydrochloric acid soln to reactor.
Further, chlorine dioxide gas generating apparatus of the present invention can also comprise:
An airstream device is installed in the exit of air-washer, and the chlorine dioxide that is used for producing is derived.
Wherein, the present invention puts out quick-fried dividing plate all being equipped with between a plurality of air-washers 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.
Hydrochloric acid soln of the present invention is pressed in the reactor with air, specifically is with a pipeline hydrochloric acid storage tank to be communicated with first pneumatic pump, and the portion of air that first pneumatic pump produces feeds in the hydrochloric acid storage tank, and hydrochloric acid soln is pressed in the reactor.
The present invention be to use another one independently second pneumatic pump be provided for deriving the air of dioxide peroxide to the airstream device.
The present invention is equipped with the air cushioning jar between first pneumatic pump, second pneumatic pump and gas pipeline, the air that pneumatic pump produces all earlier through after the air cushioning jar buffering, enters gas pipeline separately again.
The heating unit that is connected on the aeration tube can be interchanger, electric heater, heating tube etc., the preferred heating unit of the present invention is a stainless heat exchanger, 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 chlorinated polyvinyl chloride material of air aeration, transmitters such as temperature, pressure are corrosion-resistant.
Chlorine dioxide gas generating apparatus of the present invention utilizes following reaction formula to produce chlorine dioxide:
2NaClO 3+4HCl→2ClO 2+Cl 2+2NaCl+2H 2O
2NaClO 2+Cl 2→2ClO 2+2NaCl
Particularly, chlorine dioxide with high purity gas generating unit of the present invention is that raw material sodium chlorate solution and hydrochloric acid are fed in the reactor, feeding warm air by the air aeration head to reaction system reacts, 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.
Chlorine dioxide gas generating apparatus of the present invention has carried out organic combination with original sodium chlorate method producer gas generator and Textone method producer gas generator, adopt generating unit of the present invention, reaction is carried out thoroughly, the transformation efficiency height of sodium chlorate, can reach more than 95%, the chlorine dioxide purity that obtains reaches more than 98%, and yield is more than 95%.
The present invention has increased hot aeration performance in the reactor of gas generating unit, provide required heat for reaction system on the one hand, make reaction can be fast, steadily carry out, again the reaction liquid phase has been played the effect of stirring on the other hand, guarantee that reaction 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 air-washer of gas generating unit of the present invention is made up of multilevel hierarchy, add the puffy filler of forming by thread chlorinated polyvinyl chloride and solid Textone in every level structure, this filling method of Textone, can guarantee that the chlorine that produces all is converted into chlorine dioxide, can guarantee again simultaneously that the resistance when gas passes through air-washer is less, be beneficial to gas and pass through smoothly.What be provided with between reactor top and air-washer and multi-stage scrubbing device puts out quick-fried dividing plate, has guaranteed the security of reactor system again.
Chlorine dioxide gas generating apparatus of the present invention can directly produce highly purified chlorine dioxide, is used for 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 uses.
Description of drawings
Fig. 1 is the structural representation of chlorine dioxide gas generating apparatus of the present invention.
Embodiment
The structure of chlorine dioxide gas generating apparatus of the present invention comprises reactor 7 as shown in Figure 1, air-washer 5, sodium chlorate solution's storage tank 4, hydrochloric acid storage tank 11, air aeration head 8, aeration tube 10, heating unit 12, first pneumatic pump, 13, the second pneumatic pumps 2, assemblies such as airstream device 3 and waste liquid tank 9.
Sodium chlorate solution's storage tank 4 is connected with reactor 7 by pipeline, valve and under meter with hydrochloric acid storage tank 11, and the control of sodium chlorate solution and hydrochloric acid is entered in the reactor 7.Bottom in reactor 7 is placed with an air aeration head 8, and is connected with first pneumatic pump 13 with air cushioning jar 14 by aeration tube 10, is used for to reactor 7 internal reaction system bubbling airs.Heating unit 12 is installed on aeration tube 10, is used for the air heating in the aeration tube 10.Portion of air in the air cushioning jar 14 enters in the hydrochloric acid storage tank 11, is used for hydrochloric acid is pressed into reactor 7.Be provided with the pressure and temperature display unit on the top of reactor 7, with reaction pressure and the temperature in the Indicator Reaction device 7, the bottom of reactor 7 is used for discharging, reclaims reacted waste liquid by valve and waste liquid tank 9 of pipe connection.
Three groups of air-washers 5 are cascaded, be connected the top of reactor 7, and being filled with the bulk thread chlorinated polyvinyl chloride material of load Textone solid in the inside of air-washer 5, the chlorine that is used in the mixed gas of chlorine that reactor 7 is produced and dioxide peroxide further is converted into chlorine dioxide.Be equipped with between the air-washer 5 and between air-washer 5 and the reactor 7 and put out quick-fried dividing plate 6.An airstream device 3 is installed in the exit of air-washer 5, and airstream device 3 is connected with second pneumatic pump 2 with air cushioning jar 1 by pipeline, and the chlorine dioxide that is used for producing is derived.
All materials such as reactor, air-washer, air aeration head, aeration tube, solution storage tank, airstream device and gas piping all adopt impregnating material CORZAN CPVC to make.

Claims (11)

1, a kind of chlorine dioxide gas generating apparatus, described device includes:
A reactor (7), sodium chlorate solution and hydrochloric acid produce the mixed gas of chlorine and dioxide peroxide in this reaction;
An air aeration head (8) is placed on the bottom of reactor (7), is used for to reactor (7) internal reaction system bubbling air;
One first pneumatic pump (13), the air aeration head (8) interior by aeration tube (10) and reactor (7) is connected, and is used for providing air to air aeration head (8);
A heating unit (12) is connected on the aeration tube (10), is used for the air heating in the aeration tube (10);
The a plurality of air-washers (5) that are cascaded, be installed in the top of reactor (7), inside is filled with the bulk thread chlorinated polyvinyl chloride material of load Textone solid, and the chlorine that is used in the mixed gas of chlorine that reactor (7) is produced and dioxide peroxide further is converted into chlorine dioxide; And
A waste liquid tank (9) is connected reactor (7) bottom by valve, is used for discharging, reclaims reacted waste liquid.
2, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that described device also includes:
Sodium chlorate solution's storage tank (4) is connected with reactor (7) with valve by pipeline, is used for feeding the sodium chlorate solution to reactor (7);
A hydrochloric acid storage tank (11) is connected with reactor (7) with valve by pipeline, is used for feeding hydrochloric acid soln to reactor (7).
3, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that described device also includes:
An airstream device (3) is installed in the exit of air-washer (5), and the chlorine dioxide that is used for producing is derived.
4, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that putting out quick-fried dividing plate (6) being equipped with between a plurality of air-washers (5) and between air-washer (5) and the reactor (7).
5, chlorine dioxide gas generating apparatus according to claim 3 is characterized in that described airstream device (3) is by one second pneumatic pump of pipe connection (2).
6, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that between first pneumatic pump (13) and aeration tube (10) an air cushioning jar (14) being installed.
7, chlorine dioxide gas generating apparatus according to claim 2, it is characterized in that hydrochloric acid storage tank (11) is connected with first pneumatic pump (13) by pipeline, the portion of air that first pneumatic pump (13) produces feeds in the hydrochloric acid storage tank (11), and hydrochloric acid soln is pressed in the reactor (7).
8, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that described heating unit (12) is an interchanger.
9, chlorine dioxide gas generating apparatus according to claim 1 is characterized in that described reactor (7), air-washer (5), air aeration head (8), aeration tube (10) all adopt the manufacturing of chlorinated polyvinyl chloride material.
10, chlorine dioxide gas generating apparatus according to claim 2 is characterized in that described sodium chlorate solution's storage tank (4) and hydrochloric acid storage tank (11) adopt the manufacturing of chlorinated polyvinyl chloride material.
11, chlorine dioxide gas generating apparatus according to claim 3 is characterized in that described airstream device (3) adopts the manufacturing of chlorinated polyvinyl chloride material.
CNB2007100615148A 2007-02-09 2007-02-09 A chlorine dioxide gas generating device Expired - Fee Related CN100491237C (en)

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CN100491237C true CN100491237C (en) 2009-05-27

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CN101537203A (en) * 2008-03-18 2009-09-23 陈红锋 Machine for sterilizing and purifying molecular air
CN101913566B (en) * 2010-07-26 2011-11-09 中北大学 Generator capable of releasing chlorine dioxide gas for a long time
CN102297489A (en) * 2011-06-08 2011-12-28 中北大学 Air disinfection and humidification integrating device
CN102218152A (en) * 2011-06-08 2011-10-19 中北大学 Gasifying device for air disinfection
CN102976272B (en) * 2012-09-24 2014-10-22 潍坊海洁环保设备有限公司 Chlorine dioxide generator
CN105417499B (en) * 2015-12-15 2017-11-17 重庆市帝丰环保科技有限公司 Chlorine dioxide generator
CN105417498B (en) * 2015-12-15 2017-10-10 重庆市帝丰环保科技有限公司 Chlorine dioxide generator
CN106219491B (en) * 2016-07-27 2018-02-27 广西博世科环保科技股份有限公司 The synthesis chlorine dioxide preparing process recycled based on heat energy and byproduct
CN109205563A (en) * 2017-07-05 2019-01-15 冠亚腾达(北京)科技有限公司 A kind of chlorine dioxide generator with reaction of high order and raffinate separator
CN112357886A (en) * 2020-11-10 2021-02-12 深圳市加德圣环保科技有限公司 Preparation device of high-purity chlorine dioxide
CN115385304A (en) * 2022-04-12 2022-11-25 四川齐力绿源水处理科技有限公司 A kind of preparation method and preservation method of high-purity chlorine dioxide solution

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