CN100451175C - Preparation of hypochlorous and disinfectant liquid - Google Patents
Preparation of hypochlorous and disinfectant liquid Download PDFInfo
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- CN100451175C CN100451175C CNB2005100237658A CN200510023765A CN100451175C CN 100451175 C CN100451175 C CN 100451175C CN B2005100237658 A CNB2005100237658 A CN B2005100237658A CN 200510023765 A CN200510023765 A CN 200510023765A CN 100451175 C CN100451175 C CN 100451175C
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Abstract
The present invention discloses two preparation methods of hypochlorous disinfectant liquid. The steps of the first technical scheme comprise: a, an NaCl solution is electrolyzed in a mode of no diaphragm, and the molar ratio of NaCl and NaClO in the generated solution after electrolysis is more than 1 to 1; b, the electrolytically generated solution prepared in step a continues to be electrolyzed at the anode side of an ion diaphragm electrolytic tank, and the generated HCl after the electrolysis is used for neutralizing NaClO generated in step a to form HClO. The steps of the second technical scheme comprise: a, the NaCl solution is electrolyzed in the mode of no diaphragm, and NaCl is maximally converted to NaClO; b, the NaCl solution is electrolyzed in a mode of ion diaphragms, and HClO and HCl are generated at the anode side; c, the electrolytically generated solutions at the anode side in step a and step b are proportionally mixed, and HCl generated in step b neutralizes NaClO generated in step a to form HClO. The disinfectant liquid with high hypochlorous content, proper acidity and low salt residual quantity can be prepared by the two methods.
Description
Technical field
The present invention relates to the method for electrolysis production chlorine-containing disinfectant, relate to the method for electrolysis production hypochlorous acid thimerosal in particular.
Background technology
Chlorine-containing disinfectant is one of effective sterilised products the most frequently used in agricultural, foodstuffs industry and the environment protection, and its effective constituent is hypochlorous acid or hypochlorous acid salt.According to U.S. environment protection mechanism (EPA) research, hypochlorous acid sterilizing ability under the same conditions is the tens of to hundreds of times of hypochlorous acid salt.In order to bring into play the maximum germ-killing efficiency of hypochlorite, people use this series products as much as possible in sour environment, even with acids products such as hydrochloric acid hypochlorite transferring to acidity earlier before use, operation has not only increased cost like this, and very inconvenient in actual use.
Utilize common salt, generating the hypochlorous acid thimerosal by electrolytic method is one of focus of international community's research in recent years.At present, electrolytic process is produced the hypochlorous acid thimerosal and is adopted the diaphragm type electrolyzer more, forms hypochlorous acid and hydrochloric acid in anode side, forms sodium hydroxide solution at cathode side.Equimolar hydrochloric acid of the water-soluble generation of chlorine and hypochlorous acid in theory, chlorion only have 50% to generate the hypochlorous acid that needs.It is worthy of note the chlorine that generates in anode side under different acidity can with chlorine, hypochlorous acid molecule or hypochlorite totally three kinds of forms exist in solution, in the pH value is mainly to exist with hypoclorous acid form in the solution in 4～6 o'clock, in the pH value is that the chlorine of hypochlorous acid form in 2 o'clock solution drops to below 80%, in the pH value is only to have 30% at 1 o'clock, the chlorine major part that generate this moment exists with gaseous form, just can separate out in a large number from solution when the concentration of gaseous chlorine in water surpasses its saturation concentration.Produce thimerosal with common diaphragm type electrolysis process, when generating high concentration cl concentration, also can generate the hydrochloric acid of high density, thereby have the phenomenon that chlorine escapes usually, and escape phenomenon with acidity raising and aggravation rapidly.In addition, the high acidity of hypochlorous acid thimerosal also makes its application in many occasions be restricted, and production unit also is subject to acid corrosion.
When thimerosal used in reality, effective chlorine density was generally at 10～100ppm.In order to reach effective disinfection concentration, prevent from simultaneously to separate out because of too high acidity causes chlorine, generally be that thimerosal electrolysis terminal point is controlled to pH value 2～2.7.When reaching this electrolysis degree, the available chlorine content of generation is generally about 60ppm, and this moment, existing chlorine was separated out, and presents obvious chlorine flavor.Make available chlorine keep the hypochlorous acid form in advance, then require electrolytic sterilizing liquid pH value to reach 4～6.If only use common diaphragm formula electrolyzer, when electrolysis during to pH4～6, the effective chlorine density in the thimerosal is very low, and far not reaching actual sterilization needs concentration; Making available chlorine reach sterilization needs concentration, and then the pH value of electrolytic sterilizing liquid is far below pH4～6.In a word, only with the direct electrolysis production thimerosal of existing common diaphragm mode, be difficult to reach simultaneously the effect of available chlorine 10～100ppm and pH4～6.
Consider electrolytic efficiency and reduce problems such as chlorine is excessive as far as possible, the concentration of salt solution that at present general electrolysis process adopts is generally 0.1%～0.2%, and the salt residue amount is too high.
Summary of the invention
Technical problem to be solved by this invention is to overcome existing electrolytic process to produce that the hypochlorous acid content that the hypochlorous acid thimerosal exists is low, thimerosal is acid strong, the shortcoming that the salt residue amount is too high, the method of two kinds of electrolysis production hypochlorous acid thimerosals is provided, and these two kinds of methods have strengthened the practicality that electrolytic process is produced the hypochlorous acid thimerosal.
Technical scheme of the present invention: a kind of preparation method of hypochlorous acid disinfecting liquid, comprise the following steps: a. electrolysis NaCl solution under no barrier film mode, make after the electrolysis mol ratio of NaCl and NaClO in the Generation Liquid＞1: 1; B. the electroanalysis produced fluid that step a is made continues electrolysis in the anode side of ion diaphragm electrolyzer, and the HCl that generates when the anode side electrolysis is used for the NaClO formation HClO that neutralization procedure a generates.
Another kind of technical scheme of the present invention is: a kind of preparation method of hypochlorous acid disinfecting liquid, comprise the following steps: a. electrolysis NaCl solution under no barrier film mode, and make NaCl farthest be converted into NaClO; B. electrolysis NaCl solution under the barrier film mode generates HClO and HCl in anode side; C. the electrolysis Generation Liquid of step a and the anode side electrolysis Generation Liquid of step b are mixed in proportion, the NaClO that the HCl neutralization procedure a that step b is generated generates forms HClO.
Above-mentioned two kinds of schemes all are based on HCl that step b generates and are used for NaClO that neutralization procedure a generates and form HClO and finish.
The invention has the beneficial effects as follows: the electrolytic reaction of sodium chloride aqueous solution is as follows usually:
NaCl＝Na
++Cl
-
H
2O＝H
++OH
-
Electrode reaction in DC electric field is:
Anode: 2Cl
--2e=Cl
2
Negative electrode: 2H
++ 2e=H
2↑
Exist between two electrodes under the situation of ion exchange membrane, following reaction: Cl takes place in the chlorine that anode side generates
2+ H
2O=HCl+HClO
Cathode side is owing to hydrionic consumption, and hydroxide radical is enrichment gradually, forms NaOH solution.
Between two electrodes during no ion exchange membrane, resultant generation secondary reaction:
HCl+HClO+2NaOH＝NaCl+NaClO+2H
2O
Technical scheme one: step a adopts diaphragm-free electrolysis: 2NaCl+H
2O=NaClO+NaCl+H
2The desirable electrolysis degree of ↑ this step is that the mol ratio of NaCl and NaClO was slightly larger than 1: 1 in the Generation Liquid, enters step b then.Step b continues electrolysis with above-mentioned electrolytic solution in ion diaphragm anode electrolytic cell side, reaches 4～6 up to the pH value of solution value, and the electrolytic reaction of anode side is: (1) 2Cl
--2e=Cl
2, (2) Cl
2+ H
2O=HCl+HClO, (3) HCl+NaClO=HClO+NaCl.
Electrolytic reaction formula according to anode side among the step b, in and 1 mole of NaClO need 1 mole of HCl, generating 1 mole of HCl needs 2 moles of NaCl of electrolysis, so the NaClO among the fully middle step b, and making the electrolysis Generation Liquid be acid, then electrolytic NaCl mole number need reach more than 2 times of NaClO.Because among the HCl and NaClO can generate equimolar NaCl, so the mole number of NaCl needs mole number greater than NaClO or NaCl mole number in the electrolysis Generation Liquid of step a: NaClO mole number＞1: 1.Consider that NaCl too much can increase the residual quantity of salt in the final electrolytic sterilizing liquid, in the electrolysis Generation Liquid of step a NaCl and NaClO comparatively the ideal molar ratio be to be slightly larger than 1: 1.In order to improve the electrolytic efficiency of step a, need suitably to improve the mol ratio of NaCl and NaClO in this Generation Liquid in the practical application, but salt residual quantity can increase accordingly also, therefore, finally mol ratio should be taken into account current efficiency and salt is residual and definite.The net reaction of technical scheme one is: NaCl+2H
2O=HClO+NaOH+H
2↑.
Because step a can adopt the salts solution of high density, generate NaCl with high concentration O, step b is in generating HCl and in the NaClO, generate HClO again, therefore, the HClO in the electrolytic sterilizing liquid is dense, and residual salt amount greatly reduces with respect to usual way in every mole of available chlorine.Because the present invention's preparation is the high density sterilized water, needs Macrodilution when practical application, the residual quantity of salt is very low in the final sterilized water that uses, and almost can ignore.In addition, because this programme can use the salt solution of higher concentration to carry out electrolysis, the ionic strength of electrolytic solution is held higher, only needs to adopt low voltage just can realize efficient electrolysis, reaches energy-saving effect.
Technical scheme two: step a adopts no barrier film mode electrolysis NaCl solution, and this step should make NaCl farthest convert NaClO to.Step b adopts the electrolysis of barrier film mode to the NaCl dilute solution, generates HClO and HCl in anode side.Step c is mixed in proportion step a, step b anode side Generation Liquid, and the NaClO in the step a Generation Liquid is neutralized by the HCl in the step b Generation Liquid, forms HClO and NaCl.Technical scheme two is by dividing one-step electrolysis and mixing, and electrolytic sterilizing liquid can reach controlling acidity, the energy-conservation and residual effect of minimizing salt equally, and makes available chlorine mainly remain the HClO form.In sum, the hypochlorous acid content that the present invention has effectively overcome the existence of existing electrolytic process production hypochlorous acid thimerosal is low, thimerosal is acid strong, and the shortcoming that the salt residue amount is too high is having remarkable advantages aspect safety in utilization and the saving cost.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail: technical scheme one, a kind of preparation method of hypochlorous acid disinfecting liquid, comprise the following steps: a. electrolysis NaCl solution under no barrier film mode, make after the electrolysis mol ratio of NaCl and NaClO in the Generation Liquid＞1: 1; B. the electroanalysis produced fluid that step a is made continues electrolysis in ion diaphragm anode electrolytic cell side, and the HCl of generation is used for the NaClO formation HClO that neutralization procedure a generates.
Embodiment 1
The first step, the NaCl to 0.5% carries out diaphragm-free electrolysis, and the available chlorine of Generation Liquid is 1210ppm, and acidity is pH8.6.
Second step, above electrolysis Generation Liquid is carried out the ion diaphragm electrolysis, its acidity constantly descends with electrolysis, and when pH reached 4.64, available chlorine was 1702ppm in the electrolysis Generation Liquid.
Embodiment 2
The first step, the NaCl to 1.0% carries out diaphragm-free electrolysis, and the available chlorine of Generation Liquid is 2162ppm, and acidity is pH8.9.
Second step, above electrolysis Generation Liquid is carried out the ion diaphragm electrolysis, its acidity constantly descends with electrolysis, and when pH reached 4.82, available chlorine was 3193ppm in the electrolysis Generation Liquid.
Technical scheme two, a kind of preparation method of hypochlorous acid disinfecting liquid comprises the following steps: a. electrolysis NaCl solution under no barrier film mode, makes NaCl farthest be converted into NaClO; B. electrolysis NaCl solution under the ion diaphragm mode generates HClO and HCl in anode side; C. step a, step b anode side electrolysis Generation Liquid are mixed in proportion, the NaClO that the HCl neutralization procedure a that step b is generated generates forms HClO.
Embodiment 3
The first step, the NaCl to 0.5% carries out diaphragm-free electrolysis, and the available chlorine of Generation Liquid is 1205ppm, and acidity is pH8.6.
Second step, 0.1%NaCl is carried out the ion diaphragm electrolysis, when pH reached 2.24, available chlorine was 62ppm in the electrolysis Generation Liquid.
The 3rd step, by the first step electrolysis Generation Liquid: the mixed of the second step Generation Liquid=1: 9.2, obtaining acidity is pH5.01, available chlorine is the thimerosal of 167ppm.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. the preparation method of a hypochlorous acid disinfecting liquid is characterized in that, the step of method is:
A. electrolysis NaCl solution under no barrier film mode makes the mol ratio of NaCl and NaClO in the electrolysis Generation Liquid＞1: 1;
B. the electrolysis Generation Liquid that step a is made continues electrolysis in the anode side of ion diaphragm electrolyzer, forms HClO with the rapid NaClO that generates of previous step among the HCl that generates after the electrolysis.
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| CN100451175C true CN100451175C (en) | 2009-01-14 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI427189B (en) * | 2009-07-14 | 2014-02-21 | Wei Fang | Method and apparatus for producing high concentration hypochlorochloride sterilized water |
| EP4261262A4 (en) * | 2020-12-08 | 2024-05-22 | Bridgestone Corp | Vulcanized rubber surface processing agent, adhesion structure manufacturing method, adhesion structure, and tire |
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| CN101367570B (en) * | 2007-08-17 | 2013-11-20 | 株式会社北越 | Subacid electrolysis water generating method and apparatus |
| CN100586841C (en) * | 2008-06-26 | 2010-02-03 | 同济大学 | Method for preparing composite chlorine dioxide |
| CN106943429A (en) * | 2016-06-28 | 2017-07-14 | 黄坚文 | The preparation method of hypochlorite solution a kind of and its clinical medicine application |
| CN110697949B (en) * | 2019-09-24 | 2021-12-17 | 无锡迅朗联大机能水技术研究院有限公司 | Method for reducing residual quantity of chloride ions in diaphragm-free electrolyzed water |
| CN111188052B (en) * | 2020-02-27 | 2021-01-12 | 上海广锋生物科技有限公司 | Preparation method of high-performance hypochlorous acid |
| CN113652702B (en) * | 2020-05-12 | 2022-12-06 | 广州久道家用电器有限公司 | Subacid electrolyzed water disinfectant and preparation method thereof |
| CN111560623B (en) * | 2020-05-27 | 2021-08-10 | 李晓奉 | Method for continuously and stably preparing hypochlorous acid |
| CN112167264B (en) * | 2020-10-28 | 2021-10-26 | 广州吾同生态科技有限公司 | Hypochlorous acid electrolyte, hypochlorous acid disinfectant and preparation method thereof |
| CN112868664A (en) * | 2021-02-01 | 2021-06-01 | 哈尔滨瑞康源生物科技有限公司 | Low-freezing-point hypochlorous acid disinfectant and preparation method thereof |
| CN113215596B (en) * | 2021-05-08 | 2023-05-16 | 广西康巴科技有限公司 | System suitable for hypochlorous acid sterilizing water in industrial production |
| CN113322482A (en) * | 2021-06-29 | 2021-08-31 | 南京橙子电子科技有限公司 | Micro-acid and hypochlorous acid generator capable of continuously generating and generating method |
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Patent Citations (5)
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| JPH10140384A (en) * | 1996-09-15 | 1998-05-26 | Yoshiya Okazaki | Device for simultaneously generating strongly alkaline water and hypochlorous acid sterilizing water by electrolysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI427189B (en) * | 2009-07-14 | 2014-02-21 | Wei Fang | Method and apparatus for producing high concentration hypochlorochloride sterilized water |
| EP4261262A4 (en) * | 2020-12-08 | 2024-05-22 | Bridgestone Corp | Vulcanized rubber surface processing agent, adhesion structure manufacturing method, adhesion structure, and tire |
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|---|---|
| CN1680627A (en) | 2005-10-12 |
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