CN108975277B - Preparation method of high-purity chlorine dioxide - Google Patents
Preparation method of high-purity chlorine dioxide Download PDFInfo
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- CN108975277B CN108975277B CN201810966932.XA CN201810966932A CN108975277B CN 108975277 B CN108975277 B CN 108975277B CN 201810966932 A CN201810966932 A CN 201810966932A CN 108975277 B CN108975277 B CN 108975277B
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- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
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Abstract
The invention discloses a preparation method of high-purity chlorine dioxide, which comprises the following steps of 1) adding sulfuric acid, sodium chlorate and a reducing agent into a reactor; 2) introducing the mixed solution in the step 1) into an aerator, and blowing out gaseous chlorine dioxide in the mixed solution from the bottom of the aerator and then into a water injector from the top of the aerator; 3) and (3) enabling the mixed solution in the step (2) to flow out from the bottom of the aerator and enter a residual liquid separator through a communicating pipe, enabling residual chlorine dioxide to flow in the communicating pipe and continuously overflow, enabling gaseous chlorine dioxide to enter a water ejector from the top of the residual liquid separator, enabling the residual mixed solution to flow into the residual liquid separator and be discharged from the lower part of the residual liquid separator. The method for preparing the chlorine dioxide has the advantages of high efficiency, simple production process, low consumption of power water, and basically no excessive acid and salt byproducts in the generated chlorine dioxide disinfectant, so that the yield and the purity of the chlorine dioxide product are greatly improved, and the purity of the chlorine dioxide disinfectant can be up to 99 percent.
Description
Technical Field
The invention relates to chlorine dioxide production equipment, in particular to a preparation method of high-purity chlorine dioxide.
Background
Chlorine dioxide is a high-efficiency, broad-spectrum and safe disinfectant and high-efficiency oxidant, and is widely applied to the fields of water treatment, purification and disinfection, sterilization and bath, paper pulp bleaching, food preservation, deodorization and deodorization, aquaculture and the like. At present, the prior production process of chlorine dioxide mainly prepares chlorate under the conditions of strong acid environment and reducing agent, but has the technical problems of low production yield, low purity of chlorine dioxide products and high production cost of chlorine dioxide.
Disclosure of Invention
The invention aims to solve the technical problems that the prior production process of chlorine dioxide mainly prepares chlorate in a strong acid environment in the presence of a reducing agent, but has the technical problems of complex production equipment, high consumption of power water, low yield of chlorine dioxide, low purity of a chlorine dioxide product and high production cost of chlorine dioxide, and aims to provide a preparation method of high-purity chlorine dioxide, the method has simple process, high efficiency and low consumption of power water, and the generated chlorine dioxide disinfectant basically does not contain excessive acid and salt byproducts, so that the yield and the purity of the chlorine dioxide product are greatly improved, the purity of the chlorine dioxide disinfectant can reach 99 percent, and the production cost is reduced.
The invention is realized by the following technical scheme:
a preparation method of high-purity chlorine dioxide comprises the following steps of 1) adding a sulfuric acid solution, a sodium chlorate solution and a reducing agent into a reactor to generate a mixed solution of chlorine dioxide, acid and sodium chlorate; 2) introducing the mixed solution obtained in the step 1) into an aerator for keeping for 5-15min, and blowing out gaseous chlorine dioxide in the mixed solution from air entering from the bottom of the aerator and then entering a water ejector from the top of the aerator to form chlorine dioxide disinfectant with water; 3) enabling the mixed solution in the step 2) to flow out from the bottom of the aerator and enter a residual liquid separator through a communicating pipe, enabling residual chlorine dioxide in the mixed solution to continuously overflow in the flowing process of the communicating pipe, enabling gaseous chlorine dioxide to enter a water injector from the top of the residual liquid separator and form chlorine dioxide disinfectant with water, enabling the residual mixed solution to flow into the residual liquid separator due to the action of gravity, and discharging the residual mixed solution from the lower part of the residual liquid separator.
According to the preparation method of the chlorine dioxide, the chlorine dioxide disinfectant generated by the method does not contain excessive acid and salt byproducts basically, so that the yield and the purity of the chlorine dioxide product are greatly improved, the purity of the chlorine dioxide disinfectant can reach 99%, and the production cost is reduced. The preparation method comprises the steps of firstly putting raw materials into a reactor for reaction, introducing a reaction mixed solution into an aerator after the reaction is finished, wherein the aerator is of a columnar structure, and preferably has the length of 400-800 mm, and most preferably 500-800 mm; continuously introducing air from the bottom of the aerator by using the internal diameter of 100-200mm, preferably 150-180mm, and blowing the gaseous chlorine dioxide in the reaction mixed solution from the top of the aerator into the water injector; in the aerator, unreacted raw materials still exist in the reaction mixed solution, so in the aeration process, the raw materials can continuously react, in the process, 85% -90% of chlorine dioxide is generated in the reactor by the chlorine dioxide, 5% -15% of chlorine dioxide is generated in the aerator, the yield of the chlorine dioxide is greatly improved, the reaction mixed solution coming out from the bottom of the aerator enters the residual liquid separator through the communicating pipe, the chlorine dioxide in the reaction mixed solution flows in the communicating pipe and continuously overflows, gaseous chlorine dioxide enters the water ejector from the top of the residual liquid separator, the residual reaction mixed solution flows into the residual liquid separator under the action of gravity, in the process, 90% -95% of the chlorine dioxide generated in the aerator is blown out by air, and 5% -9% of the chlorine dioxide is separated in the residual liquid separator, so that the finally formed disinfectant has high purity and high yield of chlorine dioxide.
The reactor includes tubular reactor, it has first inlet pipe and the second inlet pipe that the level set up respectively to link along the diameter direction both ends on tubular reactor's the bottom outer wall, form contained angle A between the tangent plane of first inlet pipe and tubular reactor outer wall junction, form contained angle B between the tangent plane of second inlet pipe and tubular reactor outer wall junction, contained angle A and contained angle B are 45-60, first inlet pipe and second inlet pipe parallel arrangement, be equipped with first feed nozzle on the first inlet pipe, be equipped with second feed nozzle on the second inlet pipe, there is the drain pipe at tubular reactor's top, the drain pipe links to each other with the aerator.
The equipment for preparing chlorine dioxide can ensure that the reaction raw materials are sprayed into the reactor along the direction with a certain inclination of the inner wall of the reactor through the special arrangement structure of the reactor, the reaction raw materials can be fully mixed and rapidly dispersed into the reactor, and the decomposition of chlorine dioxide caused by overhigh local concentration is prevented, thereby improving the yield and the production efficiency. Sodium chlorate and a reducing agent are led into a tubular reactor through a first feeding pipe, sulfuric acid is led into the tubular reactor through a second feeding pipe, wherein two feeding nozzles are provided with jet holes, so that the raw materials can form a jet flow state when entering the reactor, the two raw materials can be fully and uniformly mixed, meanwhile, the two feeding nozzles are directly opposite to the inner wall of the tubular reactor through a special connection mode between the first feeding pipe, the second feeding pipe and the outer wall of the tubular reactor, when the materials pass through the feeding nozzles, the materials can be directly jetted on the inner wall of the tubular reactor, so that the raw materials can be fully mixed and rapidly dispersed into the reactor, compared with the condition that the materials directly fall to the bottom of a container when passing through, the special structures of the first feeding pipe and the second feeding pipe ensure that the materials are jetted on the inner wall of the reactor in the jet flow state, and the generation of the chlorine dioxide is uniform, the situation that chlorine dioxide is decomposed due to overhigh local concentration is avoided; the first feeding pipe and the second feeding pipe are connected to the outer wall of the bottom of the tubular reactor, namely reaction mixing among raw materials always occurs at the bottom of the tubular reactor, then reaction liquid flows from the lower end of the tubular reactor to the upper end of the tubular reactor, and flows out of the top of the tubular reactor and enters the aerator; the materials of the invention react at the bottom of the reaction liquid all the time and then the reaction liquid is gradually pushed upwards, so the concentration in the reaction liquid is more uniform and the condition of overhigh local concentration is avoided.
The inner diameter of the tubular reactor is 25-200mm, the aperture of the first feeding nozzle and the aperture of the second feeding nozzle are 0.5-6mm, wherein the aperture of the two feeding nozzles is matched with the size of the reactor in a direct proportion relation, namely if the inner diameter of the tubular reactor is increased, the aperture of the first feeding nozzle and the aperture of the second feeding nozzle are increased by certain size.
The tubular reactor adopts one of a PVC pipe, a CPVC pipe, a tetrafluoride pipe, a steel lining rubber pipe and an enamel pipe.
The inner wall of the tubular reactor is connected with two dispersing screen plates which are respectively opposite to the first feeding nozzle and the second feeding nozzle, when materials are fed in from the feeding nozzles, the materials are firstly sprayed on the dispersing screen plates to enable liquid flow to be divided and then sprayed on the inner wall, and the materials are further fully mixed and rapidly dispersed; the dispersing screen plate is obliquely arranged in the vertical direction and is arc-shaped, the included angle between the axis of the dispersing screen plate and a vertical straight line is 30-45 degrees, namely, the material is sprayed on the dispersing screen plate and then passes through the dispersing screen plate in a fan shape, and the material can be dispersed in all fan-shaped directions after being shunted by the dispersing screen plate; the lower half part of the dispersing screen is of a net structure, the upper half part of the dispersing screen is of a solid structure, the material is sprayed to the dispersing screen, one part of the material can penetrate through the net structure to be sprayed on the inner wall of the tubular reactor, the other part of the material is sprayed on the solid structure, and the material is sprayed on the solid structure and then reflected upwards due to the inclined arrangement of the dispersing screen, so that the material can be sprayed in a three-dimensional space instead of being only dispersed on a plane on which the material is sprayed.
The ratio of the inner diameter of the tubular reactor to the length of the tubular reactor is 1: 6-10.
The reaction conditions in the reactor in the step 1) are that the temperature is 50-65 ℃, and the pressure is-0.08 to-0.85 MPa.
The sulfuric acid solution contains sulfuric acid and oxalic acid, the mass percentage concentration of the sulfuric acid in the sulfuric acid solution is 65-85%, and the mass percentage concentration of the oxalic acid in the sulfuric acid solution is 0.3-3%.
The sodium chlorate solution contains 20-45% of sodium chlorate, 4.0-10.0% of hydrogen peroxide and 0.3-2.0% of urea by mass.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the preparation method of the high-purity chlorine dioxide, the chlorine dioxide disinfectant generated by the method basically does not contain excessive acid and salt byproducts, so that the yield and the purity of a chlorine dioxide product are greatly improved, the purity of the chlorine dioxide disinfectant can reach 99%, and the production cost is reduced;
2. the invention relates to a preparation method of high-purity chlorine dioxide, which is suitable for producing chlorine dioxide with small-scale yield, such as the production speed of 0.2-50Kg ClO2Per hour, particularly suitable for producing 5-30Kg ClO2Production of chlorine dioxide.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a flow diagram of the chlorine dioxide production process of the present invention;
FIG. 2 is a schematic view of the structure of the reactor of the present invention;
FIG. 3 is a schematic cross-sectional view of a tubular reactor according to the present invention;
FIG. 4 is a schematic view of the structure of a dispersing screen and the inner wall of a tubular reactor.
Reference numbers and corresponding part names in the drawings:
1-tubular reactor, 2-water ejector, 3-first feeding pipe, 4-second feeding pipe, 5-first feeding nozzle, 6-second feeding nozzle, 7-liquid outlet pipe, 8-dispersing screen plate, 9-reactor, 10-aerator, 11-communicating pipe and 12-residue separator.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
As shown in fig. 1, the method for preparing high-purity chlorine dioxide according to the present invention comprises the steps of 1) adding a sulfuric acid solution and a sodium chlorate solution and a reducing agent into a reactor 9 to generate a mixed solution of chlorine dioxide and acid and sodium chlorate; 2) introducing the mixed solution obtained in the step 1) into an aerator 10 for keeping for 5-15min, and blowing out gaseous chlorine dioxide in the mixed solution from air entering from the bottom of the aerator and then entering a water ejector 2 from the top of the aerator to form chlorine dioxide disinfectant with water; 3) the mixed solution in the step 2) flows out from the bottom of the aerator and enters a residual liquid separator 12 through a communicating pipe 11, residual chlorine dioxide in the mixed solution continuously overflows in the flowing process of the communicating pipe 11, gaseous chlorine dioxide enters a water injector 2 from the top of the residual liquid separator 12 to form chlorine dioxide disinfectant with water, and the residual mixed solution flows into the residual liquid separator due to the action of gravity and is discharged from the lower part of the residual liquid separator 12.
According to the preparation method of the chlorine dioxide, the chlorine dioxide disinfectant generated by the method does not contain excessive acid and salt byproducts basically, so that the yield and the purity of the chlorine dioxide product are greatly improved, the purity of the chlorine dioxide disinfectant can reach 99%, and the production cost is reduced. The preparation method comprises the steps of firstly putting raw materials into a reactor for reaction, introducing a reaction mixed solution into an aerator after the reaction is finished, wherein the aerator is of a columnar structure, and preferably has the length of 400-800 mm, and most preferably 500-800 mm; continuously introducing air from the bottom of the aerator by using the internal diameter of 100-200mm, preferably 150-180mm, and blowing the gaseous chlorine dioxide in the reaction mixed solution from the top of the aerator into the water injector; in the aerator, unreacted raw materials still exist in the reaction mixed solution, so in the aeration process, the raw materials can continuously react, in the process, 85% -90% of chlorine dioxide is generated in the reactor by the chlorine dioxide, 5% -15% of chlorine dioxide is generated in the aerator, the yield of the chlorine dioxide is greatly improved, the reaction mixed solution coming out from the bottom of the aerator enters the residual liquid separator through the communicating pipe, the chlorine dioxide in the reaction mixed solution flows in the communicating pipe and continuously overflows, gaseous chlorine dioxide enters the water ejector from the top of the residual liquid separator, the residual reaction mixed solution flows into the residual liquid separator under the action of gravity, in the process, 90% -95% of the chlorine dioxide generated in the aerator is blown out by air, and 5% -9% of the chlorine dioxide is separated in the residual liquid separator, so that the finally formed disinfectant has high purity and high yield of chlorine dioxide.
Example 2
As shown in fig. 2 and fig. 3, the method for preparing high-purity chlorine dioxide of the present invention comprises a tubular reactor 1 and a water injector 2, wherein a first feeding pipe 3 and a second feeding pipe 4 horizontally arranged are respectively connected to two ends of the outer wall of the bottom of the tubular reactor 1 along the diameter direction, an included angle a is formed between the tangent planes of the joint of the first feeding pipe 3 and the outer wall of the tubular reactor 1, an included angle B is formed between the tangent planes of the joint of the second feeding pipe 4 and the outer wall of the tubular reactor 1, both the included angle a and the included angle B are 45 °, the first feeding pipe 3 and the second feeding pipe 4 are arranged in parallel, a first feeding nozzle 5 is arranged on the first feeding pipe 3, a second feeding nozzle 6 is arranged on the second feeding pipe 4, a liquid outlet pipe 7 is connected to the top of the tubular reactor 1, and the liquid outlet pipe.
The equipment for preparing chlorine dioxide can ensure that the reaction raw materials are sprayed into the reactor along the direction with a certain inclination of the inner wall of the reactor through the special arrangement structure of the feeding pipe, the reaction raw materials can be fully mixed and rapidly dispersed into the reactor, and the decomposition of chlorine dioxide caused by overhigh local concentration is prevented, thereby improving the yield and the production efficiency. Sodium chlorate and a reducing agent are led into a tubular reactor through a first feeding pipe, sulfuric acid is led into the tubular reactor through a second feeding pipe, wherein two feeding nozzles are provided with jet holes, so that the raw materials can form a jet flow state when entering the reactor, the two raw materials can be fully and uniformly mixed, meanwhile, the two feeding nozzles are directly opposite to the inner wall of the tubular reactor through a special connection mode between the first feeding pipe, the second feeding pipe and the outer wall of the tubular reactor, when the materials pass through the feeding nozzles, the materials can be directly jetted on the inner wall of the tubular reactor, so that the raw materials can be fully mixed and rapidly dispersed into the reactor, compared with the condition that the materials directly fall to the bottom of a container when passing through, the special structures of the first feeding pipe and the second feeding pipe ensure that the materials are jetted on the inner wall of the reactor in the jet flow state, and the generation of the chlorine dioxide is uniform, the situation that chlorine dioxide is decomposed due to overhigh local concentration is avoided; the first feeding pipe and the second feeding pipe are connected to the outer wall of the bottom of the tubular reactor, namely reaction mixing among raw materials always occurs at the bottom of the tubular reactor, then reaction liquid flows from the lower end of the tubular reactor to the upper end of the tubular reactor, and the reaction liquid flows out of the top of the tubular reactor and is mixed with water in a water injector to form disinfectant; the materials of the invention react at the bottom of the reaction liquid all the time and then the reaction liquid is gradually pushed upwards, so the concentration in the reaction liquid is more uniform and the condition of overhigh local concentration is avoided.
Example 3
As shown in fig. 2 and 3, based on the embodiment 2, the invention provides a method for preparing high-purity chlorine dioxide, the reactor comprises a tubular reactor 1, the outer wall of the bottom of the tubular reactor 1 is connected with a first feeding pipe 3 and a second feeding pipe 4 which are horizontally arranged along the diameter direction, an included angle a is formed between the tangent planes of the connection part of the first feeding pipe 3 and the outer wall of the tubular reactor 1, an included angle B is formed between the tangent plane of the connection part of the second feeding pipe 4 and the outer wall of the tubular reactor 1, both the included angle a and the included angle B are 45-60 degrees, the first feeding pipe 3 and the second feeding pipe 4 are arranged in parallel, the first feeding pipe 3 is provided with a first feeding nozzle 5, the second feeding pipe 4 is provided with a second feeding nozzle 6, the top of the tubular reactor 1 is connected with a liquid outlet pipe 7, the liquid outlet pipe 7 is connected with an aerator 10, preferably, the inner diameter of the tubular reactor is 25-200mm, the aperture of the first feeding nozzle and the aperture of the second feeding nozzle are 0.5-6mm, the ratio of the inner diameter of the tubular reactor to the length of the tubular reactor is 1:6-10, and the tubular reactor adopts a CPVC (chlorinated polyvinyl chloride) pipe or a tetrafluoro pipe.
Preferably, as shown in fig. 4, the inner wall of the tubular reactor is connected with two dispersing screen plates respectively facing the first feeding nozzle and the second feeding nozzle, when the material is introduced from the feeding nozzle, the material is firstly sprayed on the dispersing screen plates to divide the liquid flow, and then is sprayed on the inner wall to further fully mix and rapidly disperse the material; the dispersing screen plate is obliquely arranged in the vertical direction and is arc-shaped, the included angle between the axis of the dispersing screen plate and a vertical straight line is 30-45 degrees, namely, the material is sprayed on the dispersing screen plate and then passes through the dispersing screen plate in a fan shape, and the material can be dispersed in all fan-shaped directions after being shunted by the dispersing screen plate; the lower half part of the dispersing screen is of a net structure, the upper half part of the dispersing screen is of a solid structure, the material is sprayed to the dispersing screen, one part of the material can penetrate through the net structure to be sprayed on the inner wall of the tubular reactor, the other part of the material is sprayed on the solid structure, and the material is sprayed on the solid structure and then reflected upwards due to the inclined arrangement of the dispersing screen, so that the material can be sprayed in a three-dimensional space instead of being only dispersed on a plane on which the material is sprayed.
Preferably, the ratio of the internal diameter of the tubular reactor to the length of the tubular reactor is from 1:6 to 10.
Preferably, the reaction conditions in the reactor in the step 1) are that the temperature is 50-65 ℃, and the pressure is-0.08 to-0.85 MPa.
Preferably, the sulfuric acid solution contains sulfuric acid and oxalic acid, the mass percentage concentration of the sulfuric acid in the sulfuric acid solution is 65-85%, and the mass percentage concentration of the oxalic acid in the sulfuric acid solution is 0.3-3%.
Preferably, the sodium chlorate solution contains 20-45% of sodium chlorate, 4.0-10.0% of hydrogen peroxide and 0.3-2.0% of urea by mass.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of high-purity chlorine dioxide is characterized by comprising the following steps of 1) adding a sulfuric acid solution, a sodium chlorate solution and a reducing agent into a reactor (9) to generate a mixed solution of chlorine dioxide, acid and sodium chlorate; 2) introducing the mixed solution obtained in the step 1) into an aerator (10) for keeping for 5-15min, and blowing out gaseous chlorine dioxide in the mixed solution through air entering from the bottom of the aerator and then entering a water injector (2) from the top of the aerator to form chlorine dioxide disinfectant with water; 3) enabling the mixed solution in the step 2) to flow out from the bottom of the aerator and enter a residual liquid separator (12) through a communicating pipe (11), enabling residual chlorine dioxide in the mixed solution to continuously overflow in the flowing process of the communicating pipe (11), enabling gaseous chlorine dioxide to enter a water ejector (2) from the top of the residual liquid separator (12) and form chlorine dioxide disinfectant with water, enabling the residual mixed solution to flow into the residual liquid separator under the action of gravity, and discharging the residual mixed solution from the lower part of the residual liquid separator (12); the reactor includes tubular reactor (1), it has first inlet pipe (3) and second inlet pipe (4) that the level set up to link respectively along the diameter direction both ends on the bottom outer wall of tubular reactor (1), form contained angle A between the tangent plane of first inlet pipe (3) and tubular reactor (1) outer wall junction, form contained angle B between the tangent plane of second inlet pipe (4) and tubular reactor (1) outer wall junction, contained angle A and contained angle B are 45-60, first inlet pipe (3) and second inlet pipe (4) parallel arrangement, be equipped with first feed nozzle (5) on first inlet pipe (3), be equipped with second feed nozzle (6) on second inlet pipe (4), the top of tubular reactor (1) even has drain pipe (7), drain pipe (7) link to each other with aerator (10), it has two on the inner wall of tubular reactor (1) to link to have respectively with first feed nozzle (5), A dispersion screen (8) opposite to the second feeding nozzle (6).
2. A process for preparing high purity chlorine dioxide as claimed in claim 1, wherein the inner diameter of the tubular reactor (1) is 25 to 200mm, and the diameters of the first feed nozzle (5) and the second feed nozzle (6) are 0.5 to 6 mm.
3. The method for preparing high-purity chlorine dioxide according to claim 1, wherein the tubular reactor (1) is one of a PVC pipe, a CPVC pipe, a tetrafluoride pipe, a steel-lined rubber pipe and an enamel pipe.
4. A process for preparing high purity chlorine dioxide as claimed in claim 1, wherein the ratio of the inner diameter of the tubular reactor (1) to the length of the tubular reactor (1) is 1: 6-10.
5. A method for preparing high purity chlorine dioxide as claimed in claim 1, wherein the reaction conditions in the reactor (9) in step 1) are a temperature of 50-65 ℃ and a pressure of-0.08 to-0.85 MPa.
6. The method according to claim 1, wherein the sulfuric acid solution contains sulfuric acid and oxalic acid, the mass percentage concentration of sulfuric acid in the sulfuric acid solution is 65-85%, and the mass percentage concentration of oxalic acid in the sulfuric acid solution is 0.3-3%.
7. The method for preparing high-purity chlorine dioxide according to claim 1, wherein the sodium chlorate solution comprises 20-45% by mass of sodium chlorate, 4.0-10.0% by mass of hydrogen peroxide and 0.3-2.0% by mass of urea.
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| US20040175322A1 (en) * | 2003-03-03 | 2004-09-09 | Woodruff Thomas E. | Process for producing chlorine dioxide |
| JP3949088B2 (en) * | 2003-08-04 | 2007-07-25 | 大幸薬品株式会社 | Chlorine dioxide production equipment |
| CN201437505U (en) * | 2009-07-03 | 2010-04-14 | 中国石油天然气股份有限公司 | Inclined plate type chlorine dioxide reactor |
| CN202823368U (en) * | 2012-09-13 | 2013-03-27 | 成都益友科技发展有限公司 | Multi-loop mixed reaction equipment |
| CN205527737U (en) * | 2016-03-16 | 2016-08-31 | 四川齐力绿源水处理科技有限公司 | Chlorine dioxide's apparatus for producing |
| CN106082131A (en) * | 2016-06-02 | 2016-11-09 | 四川齐力绿源水处理科技有限公司 | Liquid chlorine dioxide releasing agent and preparation method |
| CN106115624B (en) * | 2016-08-12 | 2018-11-09 | 深圳中科欧泰华环保科技有限公司 | Low acid amount prepares the method and device of chlorine dioxide |
| CN205917021U (en) * | 2016-08-26 | 2017-02-01 | 天津鑫洁源科技有限公司 | Disk mixing chlorine dioxide generator |
| CN106348249A (en) * | 2016-10-26 | 2017-01-25 | 吴予奇 | Manufacturing method for chlorine dioxide gas synthesis device |
| CN106698353A (en) * | 2016-12-26 | 2017-05-24 | 四川齐力绿源水处理科技有限公司 | Method for preparing chlorine dioxide from composite chlorate |
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