CN114108007A - Composition for preparing hypochlorous acid water and application thereof - Google Patents
Composition for preparing hypochlorous acid water and application thereof Download PDFInfo
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- CN114108007A CN114108007A CN202010893838.3A CN202010893838A CN114108007A CN 114108007 A CN114108007 A CN 114108007A CN 202010893838 A CN202010893838 A CN 202010893838A CN 114108007 A CN114108007 A CN 114108007A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
- C25B1/265—Chlorates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
- C02F2001/46185—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water only anodic or acidic water, e.g. for oxidizing or sterilizing
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- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a composition for preparing hypochlorous acid water and application thereof. The composition for preparing hypochlorous acid water comprises chloride salt and inorganic flocculant, wherein the chloride salt comprises NaCl, KCl and CaCl2And the inorganic flocculant includes polyaluminum chloride and/or polyferric chloride. The composition prepared by the invention has simple formula, is solid at room temperature, is convenient to store and transport, and is matched with water asThe solvent is used for preparing the electrolyte, and can use various water sources, such as pure water, deionized water, tap water, and even water containing suspended solids, organic matters, colloidal particles, microorganisms or heavy metal ions such as arsenic, mercury and the like, so that the requirement on water quality is reduced; meanwhile, when the composition prepared by the invention is used for preparing hypochlorous acid water without a diaphragm, the effect of a pH regulator is provided, and chloride ions are provided, so that the yield of hypochlorous acid is obviously improved.
Description
Technical Field
The invention belongs to the technical field of disinfectant fluid, and particularly relates to a composition for preparing hypochlorous acid water and application thereof, in particular to a composition for preparing hypochlorous acid water, electrolyte and application thereof.
Background
According to the prior studies, chlorine gas (Cl) exists in the electrolyte generated by electrolyzing the saline solution2) Hypochlorous acid (HClO), hypochlorite (ClO)-) The dynamic balance of (2) is that in the existing scheme for producing the disinfectant by electrolyzing the saline solution without the diaphragm, the pH value of the solution is gradually increased, and when the pH value is more than 8, hypochlorite in the solution is dominant. The final product is mainly sodium hypochlorite solution, although hypochlorite has a certain sterilization effect, the surface of the bacteria has negative charges, so the hypochlorite ions (ClO) with negative charges-) Will repel the bacteria surface and the ability of hypochlorite ions to kill the bacteria is not strong enough. Hypochlorous acid (HClO) exists in the form of molecules without electric charges, and thus easily penetrates the cell wall of bacteria, and has the bactericidal activity of hypochlorite (HClO) of hypochlorite (ClO) at the same Cl-containing concentration-) More than 60 times of the total weight of the composition.
At present, the method for preparing disinfectant fluid by electrolyzing saline solution mainly comprises the following two methods:
1. there is a separating film to electrolyze the salt solution. In patent CN210458375U, an ion exchange membrane or other means for regulating the passage of ions is added between the electrolysis electrodes (positive and negative electrodes), however, due to the addition of the membrane material, periodic maintenance is required, and the membrane material has a certain service life, which undoubtedly increases the complexity and cost in use; the electrolysis principle is shown as the following formula:
[ Anode)]H2O→1/202+2H++2e-
2Cl→Cl2+2e-
Cl2-+H2O→HCl+HClO
[ cathode ]]2H2O+2e-→H2+2OH-
2. Non-diaphragm electrolysis of saline solution, one way is to mix hydrochloric acid solution and saline solution in advance, in patent CN1557993A, acidic hypochlorous acid disinfectant is prepared by controlling the pH value of the aqueous solution below 2.7; the electrolysis principle is shown as the following formula:
[ Anode)]H2O→1/2O2+2H++2e-
2Cl→Cl2+2e-
Cl2-+H2O→HCl+HClO
[ cathode ]]2H2O+2e-→H2+2OH-
2H++2e-→H2
Another diaphragm-free electrolysis solution of salt in water is disclosed in patent CN 111218694A, in which after electrolysis, the pH value of the solution is adjusted by adding dilute hydrochloric acid solution, and finally the solution is mixed with neutralizer prepared from anhydrous disodium hydrogen phosphate and potassium dihydrogen phosphate to prepare slightly acidic hypochlorous acid disinfectant with pH value between 6 and 6.5. The two electrolytic salt solutions for preparing the disinfectant fluid need hydrochloric acid, which is not beneficial to safe storage and transportation. Therefore, it is an urgent problem to develop a composition for preparing hypochlorous acid water which is safe, fast, and convenient to store and transport.
Disclosure of Invention
The invention mainly aims to provide a composition for preparing hypochlorous acid water and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a composition for preparing hypochlorous acid water generated by diaphragm-free electrolysis, which comprises the following components: chloride salt and inorganic flocculant, wherein the chloride salt comprises NaCl, KCl and CaCl2And the inorganic flocculant includes polyaluminum chloride and/or polyferric chloride.
The embodiment of the invention also provides an electrolyte for preparing hypochlorous acid water, which comprises the composition and water.
The embodiment of the invention also provides a preparation method of hypochlorous acid water, which comprises the following steps:
providing the electrolyte;
and carrying out electrolytic treatment on the electrolyte to obtain hypochlorous acid water.
Compared with the prior art, the invention has the beneficial effects that:
the composition for preparing hypochlorous acid water is simple in formula, is solid at room temperature and is convenient to store and transport, the electrolyte is prepared by matching water as a solvent, and the solvent can use various water sources, such as pure water, deionized water, tap water, and even water containing solid suspended matters, organic matters, colloidal particles, microorganisms or heavy metal ions such as arsenic, mercury and the like, so that the requirement on water quality is reduced; when the composition for preparing hypochlorous acid water prepared by the invention is used for preparing hypochlorous acid water without a diaphragm, not only the function of a pH regulator is provided, but also chloride ions are provided, and finally, the yield and the efficiency of hypochlorous acid are obviously improved.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a composition for preparing hypochlorous acid water, including: chloride salt and inorganic flocculant, wherein the chloride salt comprises NaCl, KCl and CaCl2And the inorganic flocculant includes polyaluminum chloride and/or polyferric chloride.
In some specific embodiments, the mass ratio of the chloride salt to the inorganic flocculant is 10:1 to 1: 10.
In some more specific embodiments, the composition further comprises a surfactant.
Further, the surfactant includes any one of a cationic surfactant, an anionic surfactant, or a zwitterionic surfactant, and is not limited thereto.
Further, the surfactant includes any one of a quaternary ammonium surfactant, a stearic acid surfactant, and a lecithin surfactant, and is not limited thereto.
In some more specific embodiments, the composition further comprises a buffering agent.
Further, the buffer includes any one or a combination of two or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium hydroxide, and sodium hydroxide, and is not limited thereto.
In some more specific embodiments, the composition further comprises a carbonic acid foaming agent.
Further, the composition also comprises a perfume and/or a coloring agent.
Further, the composition is a bar and/or powder composition.
Further, the surface of the block composition is coated with a water-soluble coating.
Further, the water-soluble coating includes gelatin, and is not limited thereto.
Further, the powdery composition is packaged in a container such as a pill.
The invention relates to a composition for generating hypochlorous acid water by diaphragm-free electrolysis, wherein the main medicament of the formula of the composition is chloride salt (NaCl, CaCl)2One or more of salts such as KCl) and an inorganic polymer flocculant (one or a combination of two of polyaluminium chloride and polyferric chloride). The composition mainly comprises chloride salt and an inorganic flocculant (10/1-1/10) in a certain mass ratio.
The composition of the present invention is solid at room temperature, and water is used as a solvent to prepare an electrolyte. The solvent may be any of various water sources such as pure water, deionized water, tap water, and even water containing suspended solids, organics, colloidal particles, microorganisms, or heavy metal ions such as arsenic, mercury, and the like.
The inorganic polymeric flocculant such as polyaluminum chloride PAC (polyaluminum chloride) used as the main ingredient in the present invention is between AlCl3And Al (OH)3A water-soluble inorganic high molecular polymer of the general chemical formulaIs [ Al ]2(OH)nCl6-n]mN is 1-5, and m is less than 10. The important technical index basicity (or basification) is defined as the equivalent percentage of OH and Al in the PAC molecule, B ═ OH]/3[Al]X 100%. During the hydrolysis of PAC, Al is present3+、Al(OH)2+、Al(OH)2 +、Al(OH)3(aq) and Al (OH)4 -Five monomer ions; al (Al)2(OH)2 4+、Al3(OH)4 5+And Al13(OH)3 27+And the like, a plurality of multimeric polymeric ions; and Al (OH)3(s) a solid. PAC is acidic after hydrolysis of aqueous solutions, and its pH is related to the basicity, increasing with increasing basicity. When the concentration of PAC with the same basicity is different, the pH value is different, and the pH value is reduced along with the increase of the concentration of the solution. Therefore, for PAC with the same basicity, the pH value of the solution can be regulated to be between 3.5 and 6.5 by regulating the concentration.
In the composition, PAC and NaCl salt are uniformly dissolved in electrolyte formed after water, and Cl is-The PAC and NaCl hydrolysis product is provided together, the mass ratio of the added composition to the solvent water is 1/10000-1/33, and the pH value of the dissolved solution is 3.5-6.5. In the electrolytic cell, the electrolysis reaction at the cathode and anode occurs as follows:
if another inorganic polymeric flocculant is used, the hydrolysis mechanism is similar to PAC.
In addition, if water containing suspended solids, organic substances, colloidal particles, microorganisms or heavy metal ions such as arsenic and mercury is used as a solvent, the hydrolysis of the inorganic polymer flocculant in the agent is accompanied by physicochemical processes such as coagulation, adsorption and precipitation. The agent can also partially or completely remove suspended solid, organic matters, colloidal particles, microorganisms, heavy metal ions such as arsenic, mercury and the like in water, and finally produce hypochlorous acid water with the pH value of 3.5-6.5.
The agents used in the electrolytic formulation may contain surfactants, such as for washing, according to the application requirements of the slightly acidic hypochlorous acid water to be produced. And a buffering agent (one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium hydroxide, sodium hydroxide and the like) can be further contained, so that the PAC can prevent the generation of chlorine gas and reduce the concentration of available chlorine during the process of adjusting the pH value. A carbonic acid foaming agent can also be included, as can the pH. Some perfume or colorant and the like can also be included.
The preparation can be made into various block solid forms (such as medicine or pill), powder form or combination of two forms, and the block preparation can be coated with water soluble coating such as gelatin. Powdered medicaments may be enclosed by various types of containers.
When the inorganic flocculant of the composition for preparing hypochlorous acid water in the invention is polyaluminium chloride:
in water, at various pH values, aluminum ions are generally present in aqueous solution in the form of hydrated ions, and in acidic (pH < 3) aqueous solutions, aluminum coordinates with six water molecules to form Al (H)2O)6 3+When the pH value is more than 4, the hydrated aluminum ions generate a series of stepwise hydrolysis reactions,
the first order hydrolysis equation is:
Al(H2O)6 3++H2O＝Al(OH)(H2O)5 2++H3O+
at pH below 6.5, Al is mainly used3+、Al(OH)2+Is present in the form of an ion of (a),
two unique effects of pH adjustment of the electrolyte by PAC:
1. the same PH value is adjusted, the concentration of Cl cannot be increased by adding organic acid such as citric acid or inorganic acid salt, the addition of hydrochloric acid can provide extra Cl for generating HClO by electrolysis, but the addition of PAC is several times more than the addition of Cl by adding hydrochloric acid, the conductivity of the electrolyte is increased, and the electrolysis reaction is accelerated under the same electrolysis potential condition;
2. aluminum chloride belongs to Lewis acid, and has a pH below 6.5 and hydrolyzed ion of Al (H)2O)6 3+，Al(OH)(H2O)5 2+More positive than hydrated Na ionsCharged, the cathode is more attractive to it. When H is produced by cathode electrolysis, the PAC hydrolysis balance is destroyed, and H can be rapidly generated at the cathode3O+Therefore, the electrolysis rate is higher under the same electrolysis point position condition. In contrast, HCl and citric acid or H were added2PO4 -Neither has the above-mentioned effect.
Another aspect of the embodiments of the present invention also provides a method for preparing a composition for preparing hypochlorous acid water, which includes: mixing the above materials, and making into block and/or powder.
Further, the preparation method further comprises the following steps: coating a water-soluble coating on the surface of the block composition; preferably, the water-soluble coating comprises gelatin;
further, the preparation method further comprises the following steps: and (3) packaging the powdery composition.
In another aspect of the embodiment of the present invention, an electrolyte for preparing hypochlorous acid water is further provided, which includes the composition described above and water.
Further, the mass ratio of the composition to water is 1: 10000-1: 33.
Further, the water includes any one or a combination of two or more of pure water, deionized water, tap water, or a source water containing impurities, and is not limited thereto.
Further, the impurities in the water source containing impurities include any one or a combination of two or more of solid suspended matter, organic matter, colloidal particles, microorganisms, and heavy metal ions, but are not limited thereto.
Another aspect of the embodiments of the present invention also provides a method for preparing hypochlorous acid water, which includes:
providing the electrolyte;
and carrying out electrolytic treatment on the electrolyte to obtain hypochlorous acid water.
Further, the pH value of the hypochlorous acid water is 3.5-6.5.
Further, the concentration of the hypochlorous acid water is 1-400 ppm.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
Mixing NaCl and polyaluminium chloride according to the mass ratio of 1:1 to form a block, and coating the block with gelatin to prepare a composition for preparing hypochlorous acid water;
mixing the composition with water according to a mass ratio of 1: 600 to form an electrolyte, and electrolyzing for 5 minutes under the conditions that an electrolytic voltage is 6V and the distance between Ti mesh electrodes is 8cm to obtain hypochlorous acid water, wherein the pH value of the hypochlorous acid water is 4.4, and the concentration of the hypochlorous acid water is 50 ppm.
Example 2
Adding CaCl2Mixing with polyaluminium chloride at a mass ratio of 10:1 to form a block, and coating with gelatin to obtain a composition for preparing hypochlorous acid water;
mixing the composition with water according to the mass ratio of 1:10000 to form electrolyte, and electrolyzing for 5 minutes under the conditions that the electrolytic voltage is 6V and the distance between Ti mesh electrodes is 8cm to prepare hypochlorous acid water, wherein the pH value of the hypochlorous acid water is 6.5, and the concentration of the hypochlorous acid water is 5 ppm.
Example 3
Mixing NaCl and polyferric chloride according to the mass ratio of 1:10 to form a powder mixture, and packaging by using a container to prepare the composition for preparing hypochlorous acid water;
mixing the composition with water according to a mass ratio of 1:33 to form an electrolyte, and electrolyzing for 5 minutes under the conditions that an electrolytic voltage is 6V and the distance between Ti mesh electrodes is 8cm to obtain hypochlorous acid water, wherein the pH value of the hypochlorous acid water is 3.5, and the concentration of the hypochlorous acid water is 400 ppm.
Example 4
Adding CaCl2With poly (ferric chloride)Mixing at a mass ratio of 1: 2 to form a powder mixture, and packaging with a container to obtain a composition for preparing hypochlorous acid water;
mixing the composition with water according to the mass ratio of 1:1000 to form an electrolyte, and electrolyzing for 5 minutes under the conditions that the electrolytic voltage is 6V and the distance between Ti mesh electrodes is 8cm to obtain hypochlorous acid water, wherein the pH value of the hypochlorous acid water is 4.5, and the concentration of the hypochlorous acid water is 50 ppm.
Comparative example 1
Mixing NaCl and sodium dihydrogen phosphate according to the mass ratio of 1:1 to form a block, and coating with gelatin to obtain a composition for preparing hypochlorous acid water;
mixing the composition with water according to a mass ratio of 1: 600 to form an electrolyte, and then electrolyzing for 5 minutes under the conditions that an electrolytic voltage is 6V and the distance between Ti mesh electrodes is 8cm to obtain hypochlorous acid water, wherein the pH value of the hypochlorous acid water is 5.6, and the concentration of the hypochlorous acid water is 10 ppm.
Example 1 the concentration of the finally obtained hypochlorous acid water was greatly increased as compared with comparative example 1, which shows that the electrolysis efficiency was greatly improved using the composition for preparing hypochlorous acid water of the present invention.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A composition for the preparation of hypochlorous acid water, characterized in that it comprises: chloride salt and inorganic flocculant, wherein the chloride salt comprises NaCl, KCl and CaCl2And the inorganic flocculant includes polyaluminum chloride and/or polyferric chloride.
2. The composition of claim 1, wherein: the mass ratio of the chloride salt to the inorganic flocculant is 10: 1-1: 10.
3. The composition of claim 1, wherein: the composition further comprises a surfactant; preferably, the surfactant comprises any one of a cationic surfactant, an anionic surfactant or a zwitterionic surfactant; preferably, the surfactant includes any one of a quaternary ammonium surfactant, a stearic acid surfactant, and a lecithin surfactant.
4. The composition of claim 1, wherein: the composition further comprises a perfume and/or a colorant.
5. The composition of claim 1, wherein: the composition is a bar and/or powder composition.
6. The composition of claim 5, wherein: the surface of the block composition is coated with a water-soluble coating; preferably, the water-soluble coating comprises gelatin.
7. An electrolyte for producing hypochlorous acid water, comprising: the composition of any one of claims 1-6 and water.
8. The electrolyte of claim 7, wherein: the mass ratio of the composition to water is 1: 10000-1: 33.
9. The electrolyte of claim 7, wherein: the water comprises any one or the combination of more than two of pure water, deionized water, tap water or a water source containing impurities;
preferably, the impurities in the water source containing impurities comprise any one or a combination of more than two of solid suspended matters, organic matters, colloidal particles, microorganisms and heavy metal ions.
10. A method for preparing hypochlorous acid water is characterized by comprising the following steps:
providing the electrolyte of any one of claims 7-9;
carrying out electrolytic treatment on the electrolyte to prepare hypochlorous acid water;
preferably, the pH value of the hypochlorous acid water is 3.5-6.5;
preferably, the concentration of the hypochlorous acid water is 1-400 ppm.
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