CN107973273A - Chlorine dioxide purification process and application - Google Patents
Chlorine dioxide purification process and application Download PDFInfo
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- CN107973273A CN107973273A CN201610925850.1A CN201610925850A CN107973273A CN 107973273 A CN107973273 A CN 107973273A CN 201610925850 A CN201610925850 A CN 201610925850A CN 107973273 A CN107973273 A CN 107973273A
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- Prior art keywords
- chlorine
- chlorine dioxide
- purification process
- water
- gas component
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/028—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A kind of chlorine dioxide purification process, comprises the steps of：The gas component comprising chlorine dioxide and chlorine is provided, which is formed using generating mode, and the generating mode is selected from chlorite method, chlorate process or electrolysis；Purification process is carried out to the gas component, which includes being used for the condensing process for making the chlorine dioxide be transformed into liquid by gaseous state.
Description
Technical field
The present invention relates to a kind of purification process, more particularly to a kind of chlorine dioxide purification process.
Background technology
Chlorine dioxide is widely used in the fields such as drinking water, cleaning supplies or food, as disinfectant or to kill
Microbial inoculum.The generating mode of the chlorine dioxide is such as chlorite method, chlorate process or electrolysis.Utilizing the generation side
During formula generation chlorine dioxide, it can all be accompanied by chlorine and produce so that the purity of chlorine dioxide is not high, so that
In applying in above-mentioned field, because of the presence of chlorine, cause have poisoning, carcinogenic, allergy or corrosion equivalent risk, and using above depositing
There is the problem of security.
China's Mainland discloses No. 1405082 Patent Case and discloses a kind of preparation method of chlorine dioxide with high purity, comprising with
Lower step：It is that purification process is carried out to the mixed gas of traditional chlorate process production, wherein, which includes chlorine dioxide
And chlorine, and the purification process is to handle the mixed gas by chlorite solution, makes the chlorine and the chlorite anti-
Should, and promote the chlorine to decompose and be transformed into chlorine dioxide, then obtain the chlorine dioxide of high-purity.
The content of the invention
The first object of the present invention is to provide a kind of chlorine dioxide purification process.
Chlorine dioxide purification process of the present invention, comprises the steps of：Gas component comprising chlorine dioxide and chlorine is provided,
The gas component is formed using generating mode, and the generating mode is selected from chlorite method, chlorate process or electrolysis；It is right
The gas component carries out purification process, which includes being used for the condensation journey for making the chlorine dioxide be transformed into liquid by gaseous state
Sequence.
The chlorine dioxide purification process of the present invention, the temperature range of the condensing process is -33 DEG C to 10 DEG C.
The chlorine dioxide purification process of the present invention, which, which also includes, is used for making the chlorine be transformed into chlorine dioxide
Response procedures.
The chlorine dioxide purification process of the present invention, the response procedures are utilized containing chloritic reactive component and the chlorine
Contact, so that the chlorine is transformed into chlorine dioxide.
The chlorine dioxide purification process of the present invention, the reactive component is also comprising the dissolving chloritic solvent.
The chlorine dioxide purification process of the present invention, the purification process also include and utilize the reaction containing thiosulfate and water
Component is contacted with the chlorine, so that the decomposing program that the chlorine resolves into chlorion and is dissolved in the water.
The chlorine dioxide and water obtained another object of the present invention is to provide a kind of above-mentioned chlorine dioxide purification process
It is mixed for farming animals aquatic products, food fresh keeping, people's livelihood articles for use, environmental sanitation, medical supplies, drinking water and industrial water handle, is clear
The application of clean articles for use or cosmetology articles for use.
The beneficial effects of the present invention are：By the condensing process, which is transformed into liquid by gaseous state, and with
The chlorine separates, to lift the purity of chlorine dioxide.
It will be described in detail below with regard to present invention.
The chlorite method is not particularly limited, and can be used and is generally used to prepare chlorine dioxide and can produce the Asia of chlorine
Chlorate process, for example, reacted using chlorite and acid, the chlorite such as sodium chlorite (NaClO2), the acid example
Such as but it is not limited to hydrochloric acid or citric acid.The chlorate process is not particularly limited, and can be used and is generally used to prepare chlorine dioxide
And the chlorate process of chlorine can be produced, for example, reacted using chlorate and hydrochloric acid, the chlorate such as sodium chlorate
(NaClO3) or potassium chlorate etc..The electrolysis is not particularly limited, and can be used and is generally used to prepare chlorine dioxide and can produce
The electrolysis of chlorine, for example, electrolytic sodium chloride aqueous solution.
The temperature range of the condensing process is -33 DEG C to 10 DEG C.The condensing process is to utilize a cooling constant temperature circulating sink
Or freezing thermostat circulating water chennel carries out.
The purification process, which also includes, to be used for making at least a portion of the chlorine be transformed into the response procedures of chlorine dioxide.This is anti-
Program is answered to be carried out before the condensing process or after the condensing process.When the response procedures are carried out before the condensing process, this is anti-
Program is answered to be used for making the chlorine be transformed into chlorine dioxide, and the condensing process is used in the gas component by the response procedures
Chlorine dioxide and the chlorine dioxide formed in the response procedures process liquid is transformed into by gaseous state.When the response procedures exist
Carried out after the condensing process, which is used for making the chlorine in the gas component by the condensing process be transformed into titanium dioxide
Chlorine.The response procedures containing chloritic reactive component with the chlorine using contacting, so that the chlorine is transformed into chlorine dioxide.
The chlorite is such as, but not limited to sodium chlorite, lithium chlorite, potassium chlorite, magnesium chlorite, calcium chlorite or barium chlorite
Deng.The reactive component is also comprising the dissolving chloritic solvent.The solvent is such as, but not limited to water.For more effectively by the chlorine
Gas is transformed into chlorine dioxide to lift purifying benefit, it is preferred that the gas component is with 0.5 liter/min to 10 liters/min of flow
Contacted with the reactive component.More preferably, which is connect with 1 liter/min to 10 liters/min of flow and the reactive component
Touch.
The purification process is also included and contacted using the reactive component containing thiosulfate and water with the chlorine so that the chlorine
The decomposing program that gas resolves into chlorion and is dissolved in the water.The decomposing program can be before the condensing process, the condensing process
Afterwards, carried out before the response procedures or after the response procedures.When the decomposing program is carried out before the response procedures, the decomposing program
It is and the response procedures at least one of of the chlorine to be transformed into chlorion and make the chlorion be dissolved in the water
For the chlorine for being not converted into chlorion is transformed into chlorine dioxide., should when the decomposing program carries out after the response procedures
Decomposing program is for the chlorine for being not converted into chlorine dioxide is decomposed.The thiosulfate is such as, but not limited to thio sulphur
Sour sodium, potassium thiosulfate, ATS (Ammonium thiosulphate), barium hyposulfite, calcium thiosulfate or Sanocrysin etc..More effectively will
The chlorine resolves into chlorion to lift purifying benefit, it is preferred that the gas component is with 0.5 liter/min to 10 liters/min of stream
Amount is contacted with the reactive component.More preferably, which is connect with 1 liter/min to 10 liters/min of flow and the reactive component
Touch.
The chlorine dioxide with high purity that chlorine dioxide purification process of the present invention is obtained can be mixed to form chlorine dioxide water with water
Solution, and be used in medical supplies, cleaning supplies or cosmetology articles for use.The medical supplies are such as, but not limited to disinfectant or disappear
Malicious gauze etc..The cleaning supplies be such as, but not limited to mouthwash, toothpaste, denture cleanser, mouth sprays, hand cleanser, bath oil,
Wash hair care breast, wash face liquid, disinfecting liquid, floor cleaner, wash the dishes essence, laundry paks, Closestool cleanser or kitchen cleaning agent etc..
The cosmetology articles for use are such as, but not limited to gel, facial mask, sun-proof articles, toner, Essence, exfoliating articles for use or make up remover
Deng.
Embodiment
The present invention will be described further with regard to following embodiments, however, it should be noted that the embodiment is only to illustrate
With, and it is not necessarily to be construed as the limitation that the present invention is implemented.
Embodiment 1
25wt% sodium-chloride water solutions after electrolysis unit electrolysis, are extracted and generated by step (a) with venturi principle
Gas component, it is and soluble in water, form mixed solution, wherein, counted using the total amount of the gas component as 100wt%, the dioxy
The content for changing chlorine is 75wt%, and the content of the chlorine is 25wt%.Step (b) is by cleaned air with 0.5 liter/min of flow
Import in the mixed solution, departed from forcing the most gas component to be replaced from the mixed solution, then make this
Chlorine dioxide and chlorine are by the condenser pipe of freezing thermostat circulating water chennel, and by temperature control in -10 DEG C, the chlorine dioxide at this time
Liquid is gradually condensed into condenser pipe, and is collected in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is
90wt%, and the content of the chlorine is 10wt%.
Embodiment 2
Step (a) by after the combined of the sodium chlorite aqueous solution of 1 liter of 7.5wt% and 1 liter of 9wt%,
That is gas component of the generation comprising chlorine dioxide and chlorine, and it is soluble in water, mixed solution is formed, wherein, with the gas component
Total amount be 100wt% meter, the content of the chlorine dioxide is 32wt%, and the content of the chlorine is 68wt%.Step (b) will be dry
Net air is imported in the mixed solution with 1 liter/min of flow, mixed from this to force the most gas component to be replaced
Close and depart from solution, the gas component is contacted with 1 liter/min of flow with reactive component, wherein, the reactive component bag
Water containing 390 grams of sodium chlorites and 1000 grams.Step (c) will be circulated by the gas component of step (b) by freezing thermostat
The condenser pipe of sink, and by temperature control in -20 DEG C, the chlorine dioxide is gradually condensed into liquid in the condenser pipe at this time, and
It is collected in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is 92wt%, and the content of the chlorine is 8wt%.
Embodiment 3
Step (a) is by 1 (label of titanium dioxide chlorine tablets：General power；Model：Pu Li -600) be dissolved in 1 liter of water, i.e. generation includes
The gas component of chlorine dioxide and chlorine, and soluble in water, forms mixed solution, wherein, using the total amount of the gas component as
100wt% is counted, and the content of the chlorine dioxide is 5wt%, and the content of the chlorine is 95wt%.Step (b) by cleaned air with
10 liters/min of flow is imported in the mixed solution, to force the most gas component to be replaced from the mixed solution
Middle disengaging, then makes the gas component be contacted with 10 liters/min of flow with reactive component, wherein, which includes 730
Gram sodium thiosulfate and 1000 grams of water.Step (c) by by the gas component of step (b) by cooling down constant temperature circulating sink
Condenser pipe, and by temperature control in 4 DEG C, the chlorine dioxide is gradually condensed into liquid in the condenser pipe at this time, and is collected in 4
DEG C reverse osmosis (RO) water in, the content of the chlorine dioxide is 98wt%, and the content of the chlorine is 2wt%.
Embodiment 4
Step (a) is given birth to after the combined of the sodium chlorate aqueous solution of 1 liter of 7wt% and 1 liter of 9wt%
Into the gas component for including chlorine dioxide and chlorine, and it is soluble in water, a mixed solution is formed, wherein, with the gas component
Total amount is counted for 100wt%, and the content of the chlorine dioxide is 54wt%, and the content of the chlorine is 46wt%.Step (b) will be clean
Air is imported in the mixed solution with 5 liters/min of flow, to force the most gas component to be replaced from the mixing
Depart from solution, the gas component is contacted with 5 liters/min of flow with reactive component, wherein, which includes
390 grams of sodium chlorite and 1000 grams of water.Step (c) will by the gas component of step (b) with 5 liters/min of flow with
Another reactive component contact, wherein, which includes 730 grams of sodium thiosulfate and 1000 grams of water.Step (d) will be logical
The gas component of step (c) is crossed by cooling down the condenser pipe of constant temperature circulating sink, and by temperature control in 0 DEG C, at this time the dioxy
Change chlorine and liquid is gradually condensed into the condenser pipe, and be collected in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is
99.9wt%, and the content of the chlorine is 0.1wt%.
Embodiment 5
Step (a) by after the combined of the sodium chlorite aqueous solution of 1 liter of 7.5wt% and 1 liter of 9wt%,
That is gas component of the generation comprising chlorine dioxide and chlorine, and it is soluble in water, mixed solution is formed, wherein, with the gas component
Total amount be 100wt% meter, the content of the chlorine dioxide is 32wt%, and the content of the chlorine is 68wt%.Step (b) will be dry
Net air is imported in the mixed solution with 0.5 liter/min of flow, certainly should with forcing the most gas component to be replaced
Depart from mixed solution, the gas component is contacted with 0.5 liter/min of flow with reactive component, wherein, the reaction group
Subpackage contains 390 grams of sodium chlorite and 1000 grams of water.Step (c) will pass through freezing thermostat by the gas component of step (b)
The condenser pipe of circulating water chennel, and by temperature control in -20 DEG C, the chlorine dioxide is gradually condensed into liquid in the condenser pipe at this time
State, and be collected in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is 91wt%, and the content of the chlorine is
9wt%.
Embodiment 6
Step (a) by after the combined of the sodium chlorite aqueous solution of 1 liter of 7.5wt% and 1 liter of 9wt%,
That is gas component of the generation comprising chlorine dioxide and chlorine, and it is soluble in water, mixed solution is formed, wherein, with the gas component
Total amount be 100wt% meter, the content of the chlorine dioxide is 32wt%, and the content of the chlorine is 68wt%.Step (b) will be dry
Net air is imported in the mixed solution with 15 liters/min of flow, certainly should with forcing the most gas component to be replaced
Depart from mixed solution, the gas component is contacted with 15 liters/min of flow with reactive component, wherein, the reaction group
Subpackage contains 390 grams of sodium chlorite and 1000 grams of water.Step (c) will pass through freezing thermostat by the gas component of step (b)
The condenser pipe of circulating water chennel, and by temperature control in -20 DEG C, the chlorine dioxide is gradually condensed into liquid in the condenser pipe at this time
State, and be collected in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is 87wt%, and the content of the chlorine is
13wt%.
Comparative example 1
25wt% sodium-chloride water solutions after electrolysis unit electrolysis, are extracted and generated by step (a) with venturi principle
Gas component, it is and soluble in water, form mixed solution, wherein, counted using the total amount of the gas component as 100wt%, the dioxy
The content for changing chlorine is 75wt%, and the content of the chlorine is 25wt%.Step (b) leads cleaned air with 3 liters/min of flow
Enter in the mixed solution, departed from forcing the most gas component to be replaced from the mixed solution, then make the gas
Body component is contacted with 3 liters/min of flow with reactive component, wherein, which includes 500 grams of sodium chlorite.Step
(c) being collected in by the gas component of step (b) in 4 DEG C reverse osmosis (RO) water, the content of the chlorine dioxide is 80wt%,
And the content of the chlorine is 20wt%.
Comparative example 2
Step (a) is by after the combined of 1 liter of 7.5wt% sodium chlorite aqueous solutions and 1 liter of 9wt%, i.e.,
Gas component of the generation comprising chlorine dioxide and chlorine, and it is soluble in water, mixed solution is formed, wherein, with the gas component
Total amount is counted for 100wt%, and the content of the chlorine dioxide is 32wt%, and the content of the chlorine is 68wt%.Step (b) will be clean
Air is imported in the mixed solution with 5 liters/min of flow, to force the most gas component to be replaced from the mixing
Depart from solution, the gas component is contacted with 5 liters/min of flow with reactive component, wherein, which includes
730 grams of sodium thiosulfate and 1000 grams of water.Step (c) will be collected in 4 DEG C of reverse osmosis by the gas component of step (b)
(RO) in water, the content of the chlorine dioxide is 88wt%, and the content of the chlorine is 12wt%.
Assessment item
Chlorine dioxide content is analyzed：According to the Hydraulic Projects association of the U.S. of American Public Health Association and water pollution control joint
The water that club publishes and 4500-ClO in waste water standard test method the 22nd edition2C and 4500-ClO2E is analyzed
(American Public Health Association, American Water Works Association＆Water
Pollution Control Federation, Standard method for the examination of water and
Wastewater, 22nd Ed.).
Chlorine content is analyzed：Hydraulic Projects association of the U.S. and institute of Water Pollution Control Federation according to American Public Health Association
The water of publication is analyzed (Standard with 4500-Cl D and 4500-Cl E in waste water standard test method the 22nd edition
Methods for the Examination of Water and Wastewater, 22nd Edition).
Security test：Embodiment 1 to 5 is subjected to subchronic toxicity test.Subchronic toxicity test is according to ISO10093-
10 specifications are tested.○：No subchronic toxicity reaction；X：There is subchronic toxicity reaction；--：Do not tested.
Security test：Embodiment 1 to 5 is subjected to hypersensitive test.The hypersensitive test be according to IS010093-10 specifications into
Row test.○：Without allergic reaction；X：There is allergic reaction；--：Do not tested.
Table 1
In conclusion the purification process, is transformed into liquid by the chlorine dioxide by gaseous state, and separated with the chlorine, and will
The chlorine is transformed into chlorine dioxide and chlorion, to lift the purity of chlorine dioxide, so can reach the purpose of the present invention really.
The chlorine dioxide with high purity that chlorine dioxide purification process of the present invention is obtained can be mixed to form chlorine dioxide water with water
Solution, and be used in medical supplies, cleaning supplies or cosmetology articles for use.The medical supplies are such as, but not limited to disinfectant or disappear
Malicious gauze etc..The cleaning supplies be such as, but not limited to mouthwash, toothpaste, denture cleanser, mouth sprays, hand cleanser, bath oil,
Wash hair care breast, wash face liquid, disinfecting liquid, floor cleaner, wash the dishes essence, laundry paks, Closestool cleanser or kitchen cleaning agent etc..
The cosmetology articles for use are such as, but not limited to gel, facial mask, sun-proof articles, toner, Essence, exfoliating articles for use or make up remover
Deng.
Claims (8)
1. a kind of chlorine dioxide purification process, it is characterised in that comprise the steps of：
The gas component comprising chlorine dioxide and chlorine is provided, which is formed using generating mode, and the generation side
Formula is selected from chlorite method, chlorate process or electrolysis；
Purification process is carried out to the gas component, which includes being used for making the chlorine dioxide be transformed into liquid by gaseous state
Condensing process.
2. chlorine dioxide purification process according to claim 1, it is characterised in that：The temperature range of the condensing process for-
33 DEG C to 10 DEG C.
3. chlorine dioxide purification process according to claim 1, it is characterised in that：The purification process, which also includes, to be used for making this
Chlorine is transformed into the response procedures of chlorine dioxide.
4. chlorine dioxide purification process according to claim 3, it is characterised in that：The response procedures, which utilize, contains chlorous acid
The reactive component of salt is contacted with the chlorine, so that the chlorine is transformed into chlorine dioxide.
5. chlorine dioxide purification process according to claim 4, it is characterised in that：The reactive component is also comprising the dissolving Asia
The solvent of chlorate.
6. the chlorine dioxide purification process according to any claim in claim 3 to 5, it is characterised in that：The purifying
Processing is also included and contacted using the reactive component containing thiosulfate and water with the chlorine, so that the chlorine resolves into chlorion
And it is dissolved in the decomposing program in the water.
7. chlorine dioxide purification process according to claim 1, it is characterised in that：The purification process, which also includes to utilize, to be contained
The reactive component of thiosulfate and water is contacted with the chlorine, so that the chlorine resolves into chlorion and is dissolved in point in the water
Solve program.
A kind of 8. chlorine dioxide that chlorine dioxide purification process as described in any claim in claim 1 to 7 is obtained
It is mixed for water at farming animals aquatic products, food fresh keeping, people's livelihood articles for use, environmental sanitation, medical supplies, drinking water and industrial water
The application of reason, cleaning supplies or cosmetology articles for use.
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| CN201610925850.1A CN107973273A (en) | 2016-10-24 | 2016-10-24 | Chlorine dioxide purification process and application |
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Family
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Application publication date: 20180501 |