CN101631898B - Manufacturing method of medical sterilized isotonic solution having low-concentratedly controlled free chlorine including hypochlorous acid therein - Google Patents

Manufacturing method of medical sterilized isotonic solution having low-concentratedly controlled free chlorine including hypochlorous acid therein Download PDF

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CN101631898B
CN101631898B CN2008800060325A CN200880006032A CN101631898B CN 101631898 B CN101631898 B CN 101631898B CN 2008800060325 A CN2008800060325 A CN 2008800060325A CN 200880006032 A CN200880006032 A CN 200880006032A CN 101631898 B CN101631898 B CN 101631898B
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electrode
salt solution
physiological salt
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anode
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CN101631898A (en
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金七泳
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DOLKI KOREA Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J3/00Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
    • A61J3/002Compounding apparatus specially for enteral or parenteral nutritive solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L12/00Methods or apparatus for disinfecting or sterilising contact lenses; Accessories therefor
    • A61L12/08Methods or apparatus for disinfecting or sterilising contact lenses; Accessories therefor using chemical substances
    • A61L12/12Non-macromolecular oxygen-containing compounds, e.g. hydrogen peroxide or ozone
    • A61L12/124Hydrogen peroxide; Peroxy compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/03Electric current
    • A61L2/035Electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction

Abstract

The present invention relates to a manufacturing method of medical sterilized normal saline, more specifically, to such a method for manufacturing sterilized normal saline for medical purpose with effective sterilizing efficacy comprising: a step of disposing at least one electrode set immersed in saline solution of pH 4.0 to pH 7.5 including a pair of electrodes with flat surface separated from each other by an interval between lmm and 3mm, the flat surfaces of the electrodes facing each other; and a step of supplying 30mA to 200mA direct current to the electrodes by applying 2.4V to 3.3V DC power to the electrodes; wherein free chlorine is reliably and stably generated as having concentration range between 0.17ppm and 6ppm from electrolysis between electrodes.

Description

Lower concentration with control contains the preparation method of the medical sterilization isotonic solution of hypochlorous acid free chlorine
Technical field
The present invention relates to a kind of preparation method, more specifically, relate to a kind of lower concentration for preparing control reliably by electrolysis and contain hypochlorous acid (HOCl) free chlorine so that to causing the various germ method of disinfecting of disease.
Background technology
As everyone knows, because air and soil are contaminated, environmental illness is in continuous increase, and happiness and healthy concern are also being increased.Therefore, the rhinitis patient who washes nose with commercially available physiological saline constantly increases.
Known hypochlorous acid (HOCl) not only can be killed multiple virus, and is the chemical effective and harmless to human body.But, Journal of Burns and Wounds, a medical journal of publishing on April 11st, 2007 shows in it is entitled as the article of " hypochlorous acid as aPotential Wound Care Agent ", and HOCl is never as the medical drug of treatment virus infection.
On the other hand, physiological saline can obtain by following four chemical formulas.
Chemical equation 1
Figure G2008800060325D00011
Chemical equation 2a
Figure G2008800060325D00012
Chemical equation 2b
Chemical equation 3
Figure G2008800060325D00014
That is, HOCl can produce by hydrolysis chlorine according to chemical equation 1, or produces by the electrolysis physiological salt solution according to chemical equation 2a and 2b, or produces by the oxidation hypochlorite according to chemical equation 3.But,, handle chlorine---it is the form of toxic gas sometimes---and comparatively bother also dangerous for chemical equation 1.In addition,, in above-mentioned article, write, be difficult to realize the index concentration of HOCl by electrolysis for chemical equation 2a and 2b.Therefore, above-mentioned magazine indicates, and wishes that very the hypochlorite that is purchased by use produces the HOCl that is used for medical usage according to chemical equation 3.
On the other hand, the 71st of above-mentioned magazine the page of minimum sterilization concentration of being write of HOCl (MBC) that is enough to kill virus is at normal temperatures showed as follows.
Table-1
Germ MBC(ppm)?
Intestinal bacteria (Escherichia coli) 0.7?
Pseudomonas aeruginosa (Pseudomonas aeruginosa) 0.35?
Streptococcus aureus (Staphylococcus aureus) 0.173?
Staphylococcus epidermidis (Staphylococcus epidermidis) 0.338?
Micrococcus luteus (Micrococcus luteus) 2.77?
No mycolic acids rod bacillus (Corynebacterium amycolatum) 0.169?
Hemophilus influenzae (Haemophilus influenzae) 0.338?
Proteus mirabilis (Proteus mirabilis) 0.340?
Staphylococcus hominis (Staphylococcus hominis) 1.4?
Staphylococcus haemolyticus (Staphylococcus haemolyticus) 0.338?
Staphylococcus saprophyticus (Staphylococcus saprophyticus) 0.35?
Candida albicans (Candida albicans) 2.7?
Pneumobacillus (Klebsiella pneumoniae) 1.7?
Clayey Serratia (Serratia marcescens) 0.169?
Streptococcus pyogenes (Sterptococcus pyogenes) 0.169?
Enteroaerogen (Enterobacter aerogenes) 0.676?
Candida albicans (Candida albicans) 0.17?
Methicillin resistant Staphylococcus aureus (Methicillin-resistent Staphylococcus aureus) 0.682?
Anti-vancocin faecium (Vancomycin-resistent Enterococcus faecium) 2.73?
From last table 1, even the HOCl of extremely low concentration also can effectively kill most of germs.But the solution with excessive concentrations HOCl can not be used for medical usage.Therefore, above-mentioned magazine is described, and the HOCl of electrolytic unreliable amount medically can't for example be used for the treatment of any infection by it directly being injected human body or being sprayed onto on the human body.Particularly, when the concentration of HOCl surpasses 6ppm, its to the sensitive part of human body for example nasal mucosa and eye mucosa have disadvantageous effect, it also causes the solution stench in addition, therefore, thinks that the solution of the HOCl concentration that surpasses 6ppm can not be used for therapeutic treatment.About this point; Environmental Protection Agency (U.SEnvironmental Protection Agency) was also once announced in the file of in January, 1994 distribution; advise that required free chlorine (in other words, it is called as ' the residual chlorine ') concentration of the adult of an individual weight 70Kgf is less than 6ppm.
Therefore, for HOCl is applied to therapeutic treatment, it is very important that preparation can keep the sterile saline of the free chlorine that contains HOCl of accurate lower concentration.In addition, need make the ratio maximization of HOCl in the free chlorine to obtain better sterilising effect.
On the other hand, HOCl has 44 hours relatively long transformation period in human body.But in water, as shown in figure 16, the transformation period of HOCl reduced to 3 minutes, thereby after the transformation period, the effective sterilizing effect of HOCl can't be expected.
In sum, because HOCl has sterilization functions to different germs, thereby the possible purposes of HOCl aspect therapeutic treatment extensively thought.But, because HOCl has the very short transformation period outside human body, and be controlled at the predetermined interior HOCl of low scope owing in fact still can't prepare concentration, therefore think that HOCl can not be applied to the patient reaches medical purpose, for example treats the disease by different courses of infection.
Therefore, be badly in need of the method that preparation has the HOCl that is scheduled to constant low concentration scope, described concentration range is enough to killing pathogenic bacteria and can cause that the patient detests sense, reaches medical purpose thereby the free chlorine that especially contains HOCl can be actually used in the patient.
Summary of the invention
Technical problem
These shortcomings of prior art can overcome by the present invention.One object of the present invention is for providing a kind of preparation method of medical sterilization physiological salt solution, this sterilization physiological salt solution has the lower concentration of the 0.17ppm to 6ppm of constant reliable control, thereby makes this sterilization physiological salt solution have the effective sterilizing effect but can not make the patient feel to detest.
Another object of the present invention is for providing a kind of preparation method with medical sterilization physiological salt solution of the regular free chloro concentration of controlling, can not cause trouble thereby this sterilization physiological salt solution is tasteless, therefore can cosily be used for responsive patient for example disease of lung mucous membrane, eye mucosa, nasal mucosa or mucocutaneous aspect.
A further object of the present invention is for providing a kind of mancarried device for preparing the medical sterilization physiological salt solution, thereby make the patient physiological salt solution of should sterilizing immediately be used for its treatment after preparation, this sterilization physiological salt solution contains have more short-decayed HOCl outside human body.
Therefore, the user can have the sterilization physiological salt solution of the lower concentration HOCl of control in the preparation Anywhere that they want, thereby the physiological salt solution of preparation can be used for different sites, for example inflamed sites, athletic pin, atopic dermatitis etc.
Another purpose of the present invention is the mancarried device of the physiological salt solution of the lower concentration HOCl that a kind of preparation is provided has control, and HOCl is by applying low current and low voltage is produced by electrolysis, thereby can extend the life of a cell.
A further object of the invention is for providing a kind of method by electrolytic preparation sterilization physiological salt solution, and electrolysis uses subacidity water or the neutral water of pH 4.0 to pH 7.5 to have the ratio of the HOCl of strong sterilization functions with raising.
Technical scheme
For realizing above-mentioned target, the invention provides the method that a kind of preparation has the medical sterilization physiological salt solution of effective sterilizing effect, this method comprises: the step that at least one electrode group is immersed the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises a pair of anode with flat surfaces and the negative electrode that is separated from each other out 1mm to 3mm spacing, and the flat surfaces of described electrode is faced mutually; Apply the step that 2.4V to 3.3V dc voltage is supplied with electrode 30mA to 200mA galvanic current by counter electrode; Wherein produce the free chlorine of concentration range between 0.17ppm and 6ppm by the electrolysis between the electrode.
For by the subacidity of using pH 4.0 to pH 7.5 or the medical physiological salt solution of the present invention that neutral physiological salt solution prepares, as shown in figure 13, ratio through HOCl in the electrolytic solution can increase at least 50% or maximum 100%, thereby even can reach high therapeutic efficiency, and can prevent that the acidity of solution from making patient's nasal mucosa or eye mucosa portion feel uncomfortable with a spot of free chlorine.In addition, medical physiological salt solution of the present invention can make by the tap water of salt and subacidity that is easy to obtain or neutral pH or underground water are mixed.
Herein, this solution can have maximum to 3% higher salt concentrations that is different from physiological salt solution, thereby the solution of this high density can be supplied with the non-sensitive organ of insensitive human body.
When the gap of described electrode pair during less than 1mm, the electric current between the electrode is too high, and can't overflow internal space between the electrode of the gas that produces in the electrolytic process, and therefore, free chlorine produces too much sometimes or produces very little sometimes.That is, when electrode gap during less than 1mm, the amount of the free chlorine of Chan Shenging is inconsistent therebetween.When the gap of electrode pair surpasses 3mm, need between electrode pair, flow through high electric current.But when when electrode pair is supplied with high electric current, electrorheological gets excessively to be increased, as shown in figure 14, thereby low current is flowed between electrode, so that can't produce the small-amount free chlorine of control, in addition, it is excessive that power consumption becomes, so that can't be applicable to mancarried device.That is, for produce the free chlorine of the lower concentration of control reliably by electrolysis, the electric current and the quantity of electric charge that need to keep consistently passing electrode are in extremely low.
Keep the interval between the electrode, when it was applied the dc voltage of 2.4V to 3.3V, the DC electric current of 30mA to 200mA flowed betwixt.When this DC electric current continues between electrode to flow, obtain having the solution of free chlorine of 0.17ppm to the 6.0ppm lower concentration of control.Herein, when counter electrode applied dc voltage less than 2.4V, because voltage difference can't overcome the resistance of physiological salt solution, so electric current can't flow between electrode.When the dc voltage that is applied to electrode during greater than 3.3V, because the electric current between the electrode sharply increases, keep the DC electric current in constant scope, to become very difficult, thereby the concentration of free chlorine is also sharply increased, thereby the free chlorine that produces the lower concentration of control becomes very difficult.
Thus, determine by the difference between oxidation current and the deoxidation electric current via an electrode stream to the net current of external circuit.Particularly, as shown in figure 14, according to Butler-Fu Ermo (Butler-Volmer) equation, when superpotential was less, net current increased pro rata, and when superpotential during greater than a preset value, net current exponentially ground increases.That is, the mobile electric current depends on its voltage that applies and the resistance between the electrode between the electrode in the physiological salt solution of immersion 0.3% to 3% concentration.Therefore, because the physiological salt solution that has respectively between the electrode of single flat surfaces plays the resistance effect, when counter electrode applies small voltage less than DC 2.4V, electric current can't flow.On the other hand, when the big voltage that it applied greater than DC 3.3V, excessive electric current will flow between electrode, and produces excessive free chlorine in the extremely short time, the concentration of therefore the controlling free chlorine very difficulty that becomes in lower scope.
Physiological salt solution with lower concentration residual chlorine of control can be by applying the DC low current and low dc voltage reliablely and stablely prepares.Do not have a pungency and do not have disgusting smell by the physiological salt solution of method for preparing, thereby can in the use range of broad, be used for medical purpose, for example be used for lung, eye, nose and skin and can not cause the patient to feel to detest.
Herein, because the physiological salt solution for preparing by the present invention is neutral or slightly acidic, so the most of free chlorine that produces in the electrolytic process becomes the HOCl with strong sterilization functions.Thereby hope is preset in the concentration of free chlorine and makes free chloro concentration surpass the minimizing possibility of 6ppm between 3ppm and the 4ppm.
Prepare for example ozone (O of oxygenant that contains of the present invention 3), hydrogen peroxide (H 2O 2), OH free radical, HOCl, OCl -The process of mechanism by following (1) to (5) of medical physiological salt solution realize.
(1) process of ozone generation is from H 2The electrolysis of O begins, and with O and O 2In conjunction with finishing.
[0040]? *H 2O-->H ++(OH) ads+e -
(OH) ads-->(O) ads+H ++e -
2(OH) ads-->O 2+2H ++2e -
2(O) ads-->O 2
(O) ads+O 2-->O 3
[0045](2) H 2O 2Pass through O 2Electrolytic straight-forward procedure and OH free radical---by O 3Produce intermediate---bonded roundabout process makes.That is,
Straight-forward procedure
[0047]?O 2+e --->O 2 -
O 2+2H ++2e --->H 2O 2
Roundabout process
OH·+OH·-->H 2O 2
(3) HOCl passes through H 2The Cl that exists in O and the water -The Cl that is combined into 2Chemical reaction and form.
2Cl --->Cl 2+2e -
2H 2O+2e --->H 2+2OH -
*Cl 2+H 2O-->HOCl+H ++Cl -
[0055](4) generation of OH free radical and disappear too fast so that can not be, but in water, exists under the situation of ozone to its direct measurement, by with HO 2 -(H 2O 2Conjugate base) or OH -Reaction forms the free radical chain circulation, finally forms the OH free radical,
O 3+ OH-->radical chain reaction-->OH
O 3+ HO 2 -(H 2O 2Conjugate base)-->radical chain reaction-->OH
(5) microorganism that exists in the water is removed or inactivation by oxygenant, and following microorganism is removed by electro-adsorption, below little organism (microorganics) by with e -Carry out direct electrolytic reaction and remove.
That is, for microorganism,
M (microorganism)-->electro-adsorption-->inactivation
[0061]And,
M (microorganism)+O 3-->inactivation
M+OH-->inactivation
M+HOCl-->inactivation.
[0065]With, for little organism,
M (little organism)+e --->M-
And,
M (little organism)+O 3-->product
M+OH-->product
M+HOCl-->product
That is, in the electrolytic process, oxidation or sterilization contain free chlorine for example HOCl, OCl by what form in (1) to (5) process -Carry out effectively at interior multiple oxygenant.In the electrolytic process and after the electrolysis,, thereby make germ be killed by the sterilization efficacy of contained HOCl in the medical physiological salt solution owing to most free chlorine produces in electrolytic process.
Herein, the H that produces in the electrolytic process 2O 2Can produce free radical, HO+O, and these free radicals resolve into low-molecular-weight peptide and amino acid with protein, thus protein transduction is changed into water-soluble substances and accumulate in two key ranges, form epoxide.(for example, C=C-R becomes C-C-R) more specifically, H 2O 2The middle free radical that forms has higher reactivity, and himself stablizes for example protein of other organic molecule of meeting attack for making, thereby, H 2O 2Oxygenizement can make protein resolve into water-soluble substances---amino acid, thus remove deproteinize, this is one of allergic reason.
Promptly, the oxygenant that comprises free chlorine that produces in the electrolytic process of the present invention has the effect of strong killing pathogenic bacteria, fungi, bacterium and virus, thereby and two key ranges of decomposing between carbon molecule and the nitrogen molecule remove the proteinic effect that causes allergy and atopic dermatitis.Therefore, medical physiological salt solution of the present invention can be used for treating allergy or atopic dermatitis.In addition, medical physiological salt solution of the present invention can cause that allergic protein treats rhinitis and allergy by conversion.In addition, free chlorine for example HOCl is effective to the uterus carcinoma that treatment HPV (human papillomavirus (human papillomavirus)) causes, therefore it can be conducted to the uterus.
On the other hand, inventor's new discovery of the present invention, the concentration of free chlorine can accurately be controlled by the sense of current between the transfer electron in electrolytic process.Particularly, compare, the current supply electrode is not being changed in electrolytic process under the situation of its direction with the situation of switching current direction, experiment shows, free chlorine is quicker and suddenly produce, and the concentration of the free chlorine of each test has bigger change, becomes different mutually.For increasing the effect of conversion DC electric current, wish that the cycle of conversion DC electric current was made as 1 second to 20 seconds.Under the situation that will be made as in the cycle more than 20 seconds, it is not remarkable that its effect becomes.In addition, consider by supply with the DC electric current to electrode to prepare less than the process of the medical physiological salt solution that contains free chlorine on a small quantity of 100ml and in 60 seconds, finished at 20 seconds, the described cycle be no more than 20 seconds comparatively effective.
The preparation method of the medical physiological salt solution of the present invention only can realize with the power supply of the container that holds physiological salt solution, the electrode in the container and supply electrode DC electric current.Thereby the inventive method can realize by the light-duty device that only has several required components.Therefore, the inventive method can realize a kind ofly not only being used by professional medical mechanism but also being the mancarried device that ordinary consumer is used by individual patient.
Especially, the HOCl that is produced in the medical sterilization physiological salt solution is extremely unstable in neutrality or subacidity scope, thereby is easy to only promptly be reduced to half in 3 minutes.Therefore, free chlorine should rise in 3 minutes at the medical physiological salt solution of preparation and supply with the patient.With regard to this viewpoint, by realizing the inventive method by a kind of mancarried device, many patients or human consumer can be used for zone to be treated with this medical physiological salt solution, for example in the nose, eye, allergic skin, tooth, gum, lung, throat, segmental bronchus, uterus etc., do not lose in its most of sterilization efficacy until free chlorine, that is, after they make medical physiological salt solution by oneself immediately.In case HOCl is conducted in the mammiferous body, the transformation period of HOCl promptly increases to 44 hours.Therefore, be conducted to rapidly behind the medical physiological salt solution in preparation and can obtain time enough in the body and kill or kill germ, fungi, the bacterium that causes disease.
On the other hand, the invention provides the method that a kind of preparation has the medical sterilization physiological salt solution of sterilization efficacy, this method comprises: the step that at least one electrode group is immersed the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises pair of electrodes, on the apparent surface of each electrode, have a plurality of territories that are separated from each other, a plurality of territories on the apparent surface of an electrode respectively with apparent surface at another electrode on a plurality of territories relative with the interval of 1mm to 3mm; Supply with the step of electrode 30mA to 180mA DC electric current by apply 2.2V to 3.2V dc voltage to electrode; The step of the DC sense of current between at least transfer electron, wherein the total area in a plurality of territories of each electrode account for each electrode the apparent surface the total area 4% to 25%, and produce the free chlorine of concentration range between 0.17ppm to 6ppm in the electrolytic process.
That is, form a plurality of territories on the surface of opposed facing electrode, and form a plurality of current channels between described a plurality of territories, therefore, the place produces constant and faint electrolysis in described a plurality of territory.Correspondingly, the place, a plurality of territories in more among a small circle takes place the constant chemical reaction that produces free chlorine on the whole surface of each electrode relatively, thereby is easier to the concentration of free chlorine accurately is controlled at accurate low level.
Promptly, compare in the situation that the electrode place that only has opposed facing single flat surfaces takes place with electrolysis, when electrolysis have a plurality of little multiple spots (being the territory) on the opposed facing surface thus when the electrode place that forms a plurality of current channels between described multiple spot takes place, find to produce in the electrolytic process equally distributed more more small bubbles.
Especially, for the situation that forms the multiple spot territory on the electrode, when charge concentration and the channel flow between the multiple spot territory, electric current can have 2.2V than service voltage or have between the electrode of reduced-current and flow, and can reduce the consumption of electric power, thereby and can extend the life of a cell reach the longer time.Especially, do not wish once to supply with the many electric charges in multiple spot territory, but wish electric charge is constant and supply with the multiple spot territory continuously inducing electrolysis, thereby owing to produce the reactant of HOCl and can have any obstruction ground and do not carry out, thereby can realize chemical reaction constant and equably.Therefore, when the electrode that has an opposed facing multiple spot territory of the same terms when use carries out electrolysis, free chlorine can more constantly produce more lentamente, thereby is easier to control the generation speed of free chlorine, thereby can control and be created in the free chlorine in the predetermined low concentration scope.
Similarly, supplying with in the process of dc voltage,, can control the concentration of free chlorine more accurately and reduce to less than 6ppm by comprising the step of the sense of current between the transfer electron to electrode.
Herein, described electrode group contains a kind of template anode, and this template anode has a plurality of anode posts of being separated by a plurality of anode slots that are parallel to each other that are in a direction; With a kind of template negative electrode, this template negative electrode has a plurality of cathode columns that separated by a plurality of cathode can that are parallel to each other that are in a direction, wherein in the parallel placement of anode with negative electrode, and anode posts not with the situation of the parallel placement of cathode column under, by with the vertical direction of electrode surface on the zone that overlaps form a plurality of territories.
Because this structure, make little electric current and the perpendicular direction of anode and cathode surface on flow between a plurality of territories of forming, the zone that overlaps, and electrolysis is taken place on equally distributed region constant ground, thereby can accurately control the concentration of free chlorine at lower level on the whole surface of electrode.
, wish that anode posts and cathode column are in right-angle array herein, thereby make the size in distance between the territory and territory can be constant.The width of anode posts is less than the width of anode slot, and the width of cathode column is less than the width of cathode can simultaneously.Therefore, the spread length between other territory of negative electrode territory and negative electrode is greater than the size in territory.In addition, produce the required reactant of free chlorine and disperseed better, thereby make reactant in the electrode surface homogeneous reaction.
On the other hand, described electrode comprises a plurality of anode salients that protrude from anode; Protrude and the negative electrode salient relative with each anode salient from negative electrode with a plurality of, wherein a plurality of territories form at the upper surface of opposed facing salient.Described salient can form conical or cylindrical or other shape.Situation for the territory is formed by salient can obtain same as described above or similar effects.
Herein, the conversion period that changes the sense of current between the electrode wishes to be located between 1 second and 20 seconds.In addition, when the amount of physiological salt solution was 10ml to 100ml, physiological salt solution can use the mancarried device preparation by ordinary consumer.In the case, the medical physiological salt solution of 0.17ppm to 6ppm free chloro concentration can obtain by supplying with 10 seconds to 60 seconds DC electric currents.
Beneficial effect
As mentioned above, the invention provides the method that a kind of preparation has the medical sterilization physiological salt solution of effective sterilizing effect, this method comprises: the step that at least one electrode group is immersed the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises a pair of anode with flat surfaces and the negative electrode that is separated from each other out 1mm to 3mm spacing, and the flat surfaces of described electrode is faced mutually; Supply with the galvanic step of electrode 30mA to 200mA by apply 2.4V to 3.3V dc voltage to electrode; Wherein produce the free chlorine of concentration range between 0.17ppm and 6ppm, can stablize and obtain reliably having the medical physiological salt solution of low free chloro concentration thus by the electrolysis between the electrode.
In addition, the invention enables and this medical physiological salt solution can be applied to responsive patient, because this medical physiological salt solution is by strictness and accurately controls free chloro concentration and make in low scope, thus to the sensitive part of body for example the mucous membrane of lung, eye, nose, skin do not have any stimulation and can not have undesirable smell owing to chlorine in a large number.
And, the invention enables patient or human consumer to make medical physiological salt solution with any place by oneself by electrolysis at any time, this physiological salt solution contains the free chloro concentration of accurate control, thereby the fresh medical physiological salt solution that can make patient or human consumer directly this be had bigger sterilization efficacy after preparation is used for himself purpose, thereby result of treatment is maximized.
And the present invention can make the battery of the mancarried device of the medical physiological salt solution of preparation use the longer time, because apply low voltage and low current can make electrolysis take place by counter electrode, thereby has reduced the consumption of electric power.
In addition, the present invention uses subacidity or the neutral water of pH 4.0 to pH 7.5 in electrolytic process, have the OCl of ratio thereby make -The content maximization of the big 80 times HOCl of sterilization efficacy, and provide medical physiological salt solution with high sterilization efficacy.
Description of drawings
Therefore, will take the detailed description of the preferred embodiments that relates to described accompanying drawing into consideration the present invention is understood best by consideration and with reference to the following drawings, wherein identical Reference numeral refers to identical structure among each figure, and in the accompanying drawings:
Fig. 1 is the skeleton view that obtains a device of medical sterilization physiological saline according to one embodiment of the invention.
Fig. 2 is the decomposition diagram of Fig. 1.
Fig. 3 is the part fragmentary, perspective view of Fig. 1.
Fig. 4 is the skeleton view of electrode among Fig. 1.
Fig. 5 is the dismounting skeleton view of Fig. 4.
Fig. 6 is the schematic circuit of the power supply of the electrode of displaying supply Fig. 4 device.
Fig. 7 is the schema of the principle of operation of exploded view 1 device.
Fig. 8 is the cross-sectional view along line of cut VI-VI.
Fig. 9 is the frontview of other structure that can be applicable to the electrode of Fig. 4 electrode.
Figure 10 is the partial enlarged drawing of second figure among Fig. 9.
Figure 11 is the perspective view when first graphics overlay is on second figure among Fig. 9.
Figure 12 is the view of another structure that can be applicable to the electrode of Fig. 4 electrode.
Figure 13 is the form of free chlorine when 20 ℃ and 100m/l and the graph of a relation between the pH.
Figure 14 is the superpotential of electrode and the Butler-Volmer equation graph of a relation between the electric current.
Figure 15 is for no matter the change of salt concn or the change that puts on the voltage of electrode still keep the schematic circuit of current constant between the electrode.
Figure 16 is the figure of amount of the free chlorine of 20 second operating time.
Figure 17 and Figure 18 are the skeleton view of the cleaning module of the contact lenses that combines with the import of Fig. 2 container.
Figure 19 is the synoptic diagram of inverted status of device that has the preparation medical saline of stopper.
Figure 20 is the details drawing of Figure 19.
Embodiment
When considered in conjunction with the accompanying drawings, aforementioned and other target, feature, aspect and advantage of the present invention will become more obvious from following detailed description of the present invention.
When present invention is described,, omitted detailed description to known function or structure for illustrating main points of the present invention.
Shown in Fig. 1-6, the device for preparing sterile saline according to one embodiment of the invention comprises: a container 110 is used to hold the used water of preparation sterile saline; A spray unit 120 is used for sterile saline is sprayed in wound area or the nose; A main body 130 is used for storage container 110 and pilot circuit; An electrode group 140, it is dipped under the physiological salt solution in the container 110, is used for producing the oxygenant that comprises HOCl by electrolysis; A lid 150 is used to hide the top of main body 130; With a supplying cell 160, be used for to electrode group 140 supply electric power.
Container 110 forms the physiological salt solution that is used to hold about 0.9% salt concn that forms by drinking mixed water and salt.For preparing the physiological salt solution of about 0.9% salt concn, indicate scale on the surface of container 110, be 4.0 to 7.5 water (for example 50ml or 100ml) so that hold the pH of exact amount.When holding solution pH 4.0 between 7.5 the time, wherein most of free chlorine of Chan Shenging can form the HOCl with strong sterilization efficacy.
In addition, for preparing the medical saline of 0.9% salt concn, physiological saline poured in the container 110 via inlet 110a into the amount of physiological saline reaches institute's indexing in container 110.Herein, not directly in container 110, to pour physiological saline into, but earlier pour neutral or slightly acidic tap water into to container 110, then can by with water with suitable the salt that disengages the salt packing bag of the amount that water becomes physiological saline is mixed prepare physiological saline from containing.
Spray unit 120 comprises a stopper 121 that combines with the inlet 110a of container 110, and the solution that is used for being held is hedged off from the outer world, and this stopper has a button that can move back and forth; A chamber 124, its have can with described button move back and forth and the volume that changes so that sterile solution is sucked from container 110; A spring 125, its surface is coated with platinum, and pushes and be installed in the chamber 124, so that make described button can return its home position; A spray line, it is the aqua sterilisa passage of a vertical direction, is used for sterile saline is sprayed to the outside from the inside of container 110; A sprinker 123, it is positioned on the outside surface of stopper 121, is used to spray formed sterile saline.
Herein, for sterile saline is sprayed to the outside by spray unit 120, the button of the downward press device of user, sterile saline is by the instantaneous volume change of vacuum chamber 124 then, be sucked in the spray unit 120 by spray line 122, and sterile saline can be sprayed with the form of small water droplet by spray unit 120.Physiological saline in the container 110 can otherwise be conducted to patient or human consumer's a certain position.
Main body 130 comprises a housing 131, thereby it forms the shell of device 100 around container 110; A battery cover 132 is used to open or close and is used for holding the battery accommodating part (not shown) that two of supply DC electric current saves the 1.5V batteries; A switch 133, being used to control to electrode group 140 supply DC electric currents is 0.17ppm to 6ppm until the concentration of the free chlorine that produces; First telltale 133a is used for for example red by color, yellow or green state of indicating operation; A circuit housing region 135 is used to install pilot circuit from the DC electric currents to electrode group 140 that for example supply; With a bottom section 139, form the lower surface of container 110.
When user's pressing operation switch 133, dc voltage feeds to electrode unit 140 and reaches one period scheduled time, thereby produces the free chlorine of predetermined amount.Particularly, in the time of 20 ℃, when pressing operation switch 133, the DC electric current feeds to the electrode group 140 about 20 seconds, is the physiological saline concentration of 3ppm to 4ppm thereby make the free chlorine of generation.With regard to this point with regard to, pushed continuously at operating switch 133 under twice the situation, can produce free chlorine more than desired amount, when importing any signal by pressing operation switch 133 in 2 minutes more than 2 times, relevant information is demonstrated by color signal or voice signal by telltale 134,134a.
Shown in Fig. 4 to 8, electrode group 140 comprises a negative plate 141, separate the positive plate 142 of 2mm with one with this negative plate, fixed electorde is to 141,142 supporting 143, leading electrode is to 141,142 and keep the side bearing 144 of spacing between the electrode 141,142 when electrode is fixed in the supporting 143, the base plate 145 of a fixed support 143,143 standing bolt and rubber bearings 147 that are used for preventing solution infiltration electronic package below base plate 145 that are fixed on the base plate 145 will be supported.
As shown in Figure 5, supporting 143 comprises recessed connective slot 1431 that is used for fixing negative plate 141 and the recessed connective slot 1432 that is used for fixing positive plate 142.As shown in Figure 5, cathode rays 161 is connected to the connective slot 1431 of negative plate 141, and anode line 162 is connected on the connective slot that supports the positive plate 142 in 143, thereby as long as can provide environment from electric power to battery lead plate 131,132 that supply in the groove 1431,1432 with battery lead plate 141,142 insertion supportings 143.Therefore, when the platinum of electrode 141,142 is used up, can be by from support the groove 1431,1432 of extracting old electrode 141,142 143 and new electrode 141,142 being inserted supporting 143 and more renew electrode.Therefore, but device 100 semipermanents ground use.
In addition, rubber bearing 147 be connected in the following of base plate 145 and be placed in base plate 149 and bottom section 139 between, thereby prevent that physiological saline from leaking out to the outside of container 110.Herein, rubber bearing 147 can form annular but not template, thereby and is connected in base plate 139 environment.Supply lead 161,162 as shown in Figure 6, is connected in the inside of housing 131 by base plate 145, thereby transmits the DC electric current from battery 160.
Simultaneously, shown in Figs. 9 to 11, the electrode group can be made of the anode 242 that a negative electrode 241 with a plurality of cathode column 241a that separated by vertical channel 241b and have a plurality of anode posts 242a that separated by level trough 242b.Herein, as shown in figure 11, cathode column 241a and the anode posts 242a arrangement that meets at right angles, and in the overlapping region 2412 of electrode 241,242, form a plurality of opposed facing territories, thus between the territory of the territory of negative electrode 241 and anode 242, form a plurality of current channels.Therefore, though a spot of voltage is conducted to a plurality of territories that are evenly distributed, there is electric current to flow betwixt, thereby prolonged the life-span of battery 160.In addition, by when electrolysis takes place the territory of electrode 241,242 supply small voltage, the chemical reaction that is produced HOCl by reactant takes place evenly distributedly.Therefore, compare,, therefore can accurately control the concentration of free chlorine owing to for example constant and generation evenly distributedly of amount of HOCl of free chlorine with the situation of using the flat pattern electrode.
, take place more tempestuously than at 2412 places, a plurality of territory at peripheral region 241c, 242c place along electrode 241,242 for preventing electrolysis herein, except that by the x among Fig. 9, the y institute region, regional around 241c, the last formation of 242c coating.In addition, the width of cathode column 241a and anode posts 242a is less than the width d2 of cathode can 241b and anode slot 242b.Therefore, the size in territory 2412 is less than the spacing between the territory 2412.Thereby the reactant that produces HOCl can be evenly and is distributed in effectively around the current channel between the territory 2412, thereby HOCl can and supply reactant continuously and produces consistently by abundance.Therefore, easier realization is to the accurate control of HOCl.
On the other hand, can form as shown in figure 12 electrode group with a plurality of opposed facing territories.Promptly, the electrode group of Figure 12 comprises a negative plate 341 with a plurality of negative electrode salient 341a that protrude from it, positive plate 342 with a plurality of anode salient 342a that protrude from it, each anode salient is relative with each negative electrode salient 341a, and the top area A of wherein said a plurality of negative electrode salient 341a and described a plurality of anode salient 342a forms a plurality of opposed facing territories.Similarly, negative plate 341 and positive plate 342 are fixed in the supporting 143 with constant interval d4, thereby negative electrode salient 341a and anode salient 342a on the apparent surface B are separated from each other by interval d3, make the top area A of charge concentration thus in salient 341a, 342a.Therefore, though supply with electrode 341,342 small voltages, still can there be electric current to flow between the opposed facing territory A of electrode 341,342.
Thereby violent electrolysis is induced on the surface that platinum is plated on electrode 141,142,241,242,341,342.
Be installed in pilot circuit in the circuit housing region 135 DC electric current that electrode 141,142,241,242,341,342 is supplied with in control according to the input condition of switch 133 and reach the scheduled time, indicate operational stage with control telltale 133a, 134,134a, and control per 3 seconds to the 7 seconds conversion directions of DC electric current that feed to electrode 141,142,241,242,341,342, thereby help the accurately concentration of control free chlorine.In addition, pilot circuit comprises a part of supplying with the DC electric current to electrode 141,142,241,242,341,342 consistently.Therefore, though the voltage of new battery 160 is 3.3V when beginning, but have only 2.2V to 2.5V to put on electrode 141,142,241,242,341,342, thereby make the DC electric current between the electrode 141,142,241,242,341,342 low as far as possible by pilot circuit.Because smooth electrode 141,142 needs higher voltage that the DC electric current is flowed betwixt, therefore supply with 2.4V herein, to electrode 141,142.On the other hand, because electrode 241,242,341,342 needs lower voltage that the DC electric current is flowed betwixt, therefore supply with 2.2V to electrode 241,242,341,342.
Particularly, circuit shown in Figure 15 can keep the DC electric current between the electrode 141,142,241,242,341,342 consistently, no matter and the consumption situation of battery 160 and salt concn different.In addition, pilot circuit is DC sense of current between the transfer electron 141,142,241,242,341,342 periodically, each initial negative electrode 141,241,341 can bring into play the anodic effect, and similarly, each initial anode 142,242,342 also can be brought into play the effect of negative electrode, thereby prevents that chemical reaction product from adhering on each electrode 141,142,241,242,341,342.For realizing this operation, will be connected in parallel as two couples of transistor T R1, TR2, TR3, TR4a of switching element, and electrode 141,142,241,242,341,342 is placed between each is to the node between the transistor 181,182.Therefore, as TR1 with TR4 is in out and TR2 and TR3 are in when closing, the DC electric current flows to second node 182 from first node 181, and when TR1 and TR4 were in pass and TR2 and TR3 and are in out, the DC electric current flowed to first node 181 from second node 182.
Herein, the physiological salt solution between the electrode 141,142,241,242,341,342 has played the effect of resistance 111a in circuit shown in Figure 15.Therefore, though indicated scale so that hold the physiological salt solution of constant basis on container 110, because user's carelessness, the salt concn of physiological salt solution may be different.Therefore, resistance 111a may be different, and the DC electric current also may be different from preset value.Be the difference of compensation DC electric current, actual DC electric current detects with battery 160 placed in-line resistance R 1 automatically by one.
For example, thus as TR1 with TR4 is in out and TR2 and TR3 are in to close and make the DC electric current when first node 181 flows to second node 182, the DC electric current on the resistance R 1 detects automatically and is impulse form 66.Herein, when the DC electric current is higher than preset value, if rheobasis I BIncrease slightly, because electric power consumes manyly at TR1 and TR4 place, the width of pulse 66 diminishes, thereby reduce the voltage that is applied to physiological salt solution, therefore, DC electric current between the electrode 141,142,241,242,341,342 diminishes, thereby but counter electrode 141,142,241,242,341,342 applies the goal-setting value of DC electric current.Similarly, when the DC electric current is lower than set(ting)value, if rheobasis I BReduce slightly, because electric power consumes less at TR1 and TR4 place, it is big that the width of pulse 66 becomes, thereby improved the voltage that is applied to physiological salt solution, and therefore, DC electrorheological between the electrode 141,142,241,242,341,342 is big, thereby but counter electrode 141,142,241,242,341,342 applies the goal-setting value of DC electric current.That is, because the difference of the DC electric current that difference caused of salt concn can be by the rheobasis I of IC 173 controlling flow to transistor T R1, TR2, TR3, TR4 BAnd and then be controlled at the pulse width of mobile DC electric current between the electrode and carry out constant compensation.
The similar operation principle also is applicable to the difference that compensates the DC electric current according to the pressure drop that use caused owing to battery 160.Though the initial voltage of battery 160 is 3.3V, because the use of battery 160, voltage is reduced to 2.3V.Therefore, when applying the DC electric current to electrode 141,142,241,242,341,342 and reach initial Preset Time, because loss of voltage, therefore when initially when it supplies with 3.3V, physiological saline may exceedingly be sterilized, and when afterwards when it supplies with 2.3V, physiological saline may sterilization functions a little less than.For addressing this problem, detect the DC electric current (, the DC electric current at R1 place is identical with electrode 141,142,241,242,341,342 places, because resistance R 1 is connected in series with electrode 141,142,241,242,341,342) at resistance R 1 place in real time herein.Thereafter, when the DC at R1 place electric current is higher than when waiting to be conducted to the preset value of electrode 141,142,241,242,341,342, with the rheobasis I that increases slightly BPressure drop takes place thereby induce at the transistor place in the transistor that the state of being applied to is out, and can make the DC electric current keep constant thus, no matter and the voltage of battery 160 changes.
By these structures, although salt concn and cell voltage potentially unstable, the DC electric current that is applied to electrode can keep constant, can reliablely and stablely obtain to have for example sterile saline of HOCl of constant lower concentration free chlorine thus.
Lid 150 is used for main body covered 130 top and is used to hold the salt packing bag, and the amount of described salt packing bag is weighed as and makes the salt concn about 0.9% of physiological saline in the container 110.Therefore, the user can carry the required salt that is arranged in holding portion 150a easily together with device 100.Lid 152 is by opening or closing holding portion 150a with bound fraction 151 associatings.
Constitute as the battery 160 of power supply battery by a pair of 1.5V voltage rating.Battery 160 is conducted to electrode 141,142,241,242,341,342 with 30mA to 200mA DC electric current via supply lead 161,162 by pilot circuit and reaches Preset Time.Need not the user intervene the periodically conversion in per 3 seconds to 7 seconds of the pilot circuit control DC sense of current.
In the time will putting on electrode from the dc voltage of battery 160, to (5), device 100 can prepare the sterile saline of the low residual concentration of 0.17ppm to 6ppm according to above process (1), and wherein most of free chlorine is made of HOCl.
Hereinafter, will the principle of the device of preparation sterile saline of the present invention be described.
When user's using appts 100 preparation sterile salines, this user puts into container 110 with the salt in subacidity or neutral tap water and the packing bag, and with its mixed must about 0.9% physiological salt solution.Afterwards, electric power is conducted to electrode 341,342 via groove 1431,1432., measure the electric current at resistance R 1 place that is connected in series with battery 160 herein, and after institute being surveyed electric current and predetermined current comparison, according to the difference between survey electric current and the predetermined current by controlling flow to transistorized rheobasis I BThe DC electric current that flows to electrode 341,342 is compensated.
Be conducted to the charge concentration of electrode 341,342 in opposed facing salient 341a, 342a herein.Therefore, electrolysis takes place in a plurality of current channels place between opposed facing salient 341a, 342a, and electrolytic reactant is reacted effectively.The for example electrolytic ozone of oxygenant in the physiological saline, H 2O 2, HOCl, OCl -, the OH free radical can be sterilized at short notice and kill pathogens, protein, fungi, bacterium etc.Especially, when physiological saline was neutrality or slightly acidic, most lower concentration free chlorine was made of the HOCl with strong sterilization efficacy, thereby can be applied to medical purpose and realize highly improved sterilising effect.
Device 100 must require only electrode group 241,242,341,342 to have a plurality of opposed facing territory A, and 2412, be enough to allow the user be convenient for carrying thereby can constitute a Miniature Portable Unit.
The embodiment of the sterile saline of first embodiment of the present invention hereinafter will be described.
The 1st embodiment
Electrode 141,142 is 1225mm by surface-area 2The template electrode constitute, described electrode is coated with platinum and arranges with the interval d that is separated from each other 2mm, and it is immersed in the 100ml physiological saline of pH6.45 ± 0.2.In addition, under per situation of periodically changing the DC sense of current in 5 seconds, supply with DC electric currents 20 seconds to electrode 141,142.At the change of voltage, to the measurement of concetration of free chlorine 5 times, as shown in following table 2.
Table 2
Sequence number Voltage is supplied with (VDC) DC electric current (mA) The mean concns of free chlorine The standard deviation of free chloro concentration
1-1? 2.2? Do not flow -? -?
1-2? 2.4? 80? 1.20? 0.45?
1-3? 2.7? 160? 2.10? 0.71?
1-4? 3.3? 200? 3.04? 0.81?
1-5? 3.5? 350? 5.81? 1.24?
1-6? 4.5? 520? 7.14? 1.72?
[0147]Shown in the experimental result in the table 2, when DC 2.2V being conducted to electrode 141,142, the DC electric current does not flow between electrode 141,142, and when DC 2.4V is conducted to electrode, the average DC electric current of 80mA flows between electrode 141,142, thereby produce the free chlorine of extremely low concentration (that is average 1.2ppm).When supplying with DC 3.3V, average DC 200mA flows between electrode 141,142, thereby generation still is the free chlorine of lower concentration (that is average 3.04ppm).But when when electrode 141,142 is supplied with DC 3.5V, the DC electric current of the average 350mA that raises flows between electrode 141,142 suddenly, thereby produces the free chlorine of 5.81ppm concentration.That is to say that be conducted at the DC 3.5V with a little higher than DC 3.3V under the situation of electrode 141,142, the DC electric current between the electrode 141,142 is more violent.Though the concentration of 5.81ppm is slightly smaller than 6ppm, in view of standard deviation is 1.24 higher relatively value, so deducibility, supply with DC 3.5V and can not guarantee that free chlorine is less than 6ppm.
The 2nd embodiment
The width d1 of post 241a, the 242a of electrode 241,242 forms 0.7mm, and the width d2 of groove 241b, the 242b of electrode 241,242 forms 1.3mm.Electrode 241,242 is arranged as makes cathode column 241a and the anode posts 242a placement that meets at right angles.Each central zone (being the whole surf zone of described post and groove) by the IncFlds that the x among Fig. 9, y surround is respectively 841mm 2And be coated with platinum, and other surf zone of electrode 241,242 (that is, peripheral region 241b, 242b except that the central zone) scribbles insulation layer, takes place to prevent the regional around 241b of electrolysis, 242b place.Electrode 241,242 is separated from each other 2mm and arranges and immerse in the 50ml physiological saline of pH 6.37 ± 0.2.In addition, under per situation of periodically changing the DC sense of current in 5 seconds, supply with DC electric currents 20 seconds to electrode 241,242.At the change of voltage, to the measurement of concetration of free chlorine 5 times, as shown in following table 3.
Table 3
Sequence number Voltage is supplied with (VDC) DC electric current (mA) The mean concns of free chlorine (ppm) The standard deviation of free chloro concentration
2-1? 2.1? Do not flow -? -?
2-2? 2.2? 40? 1.01? 0.21?
2-3? 2.4? 50? 1.62? 0.31?
2-4? 2.6? 65? 2.83? 0.25?
2-5? 2.7? 75? 3.04? 0.33?
[0152]?
2-6? 2.9? 85? 3.20? 0.30?
2-7? 3.0? 100? 3.57? 0.66?
2-8? 3.2? 120? 4.30? 0.78?
2-9? 3.4? 160? 5.57? 1.51?
Shown in the experimental result in the table 3, when DC 2.1V being conducted to electrode 241,242, the DC electric current does not flow between electrode 241,242, and when DC 2.3V is conducted to electrode, the average DC electric current of 40mA flows between electrode 241,242, thereby produce the free chlorine of extremely low concentration (that is average 1.01ppm).When supplying with DC 3.2V, average DC 120mA flows between electrode 241,242, thereby generation still is the free chlorine of lower concentration (that is average 4.3ppm).But when DC 3.3V was conducted to electrode 241,242, the average DC electric current of the 160mA that raises flowed between electrode 241,242 suddenly, thereby produced the free chlorine of 5.57ppm concentration.That is to say that be conducted at the DC 3.4V with a little higher than DC 3.2V under the situation of electrode 241,242, the DC electric current between the electrode 241,242 sharply increases according to Butler-Volmer equation.Though the concentration of 5.57ppm is slightly smaller than 6ppm, because standard deviation is 1.51 higher relatively value, so deducibility, supply with DC 3.5V and can not guarantee that free chlorine is less than 6ppm.
Though last table 3 is not shown, the in a small amount physiological saline for less than 150ml confirms that by experiment the amount of electrolytic free chlorine increases to The above results in the same manner, difference be need be longer operating time.
The 3rd embodiment
The width d1 of post 241a, the 242a of electrode 241,242 forms 0.3mm, and the width d2 of groove 241b, the 242b of electrode 241,242 forms 0.8mm.Electrode 241,242 is arranged as and makes cathode column 241a and the anode posts 242a placement that meets at right angles.Each central zone (being the whole surf zone of described post and groove) by the IncFlds that the x among Fig. 9, y surround is respectively 841mm 2And be coated with platinum, and other surf zone of electrode 241,242 (that is, peripheral region 241b, 242b except that the central zone) scribbles insulation layer, takes place to prevent the regional around 241b of electrolysis, 242b place.Electrode 241,242 is separated from each other 2mm and arranges and immerse in the 50ml physiological saline of pH 6.45 ± 0.2.In addition, under the situation of the change-over period that changes the DC sense of current, supply with DC2.7V to electrode 241,242 and reach 20 seconds.At the change of change-over period, to the measurement of concetration of free chlorine 5 times, as shown in following table 4.
Table 4
Sequence number The sense of current change-over period (second) DC electric current (mA) The mean concns of free chlorine The standard deviation of free chloro concentration
3-1? 1? Can't measure 1.61? 0.47?
3-2? 2? Can't measure 2.16? 0.51?
3-3? 5? 70? 2.97? 0.40?
3-4? 7? 70? 3.40? 0.89?
3-5? 12? 70? 3.73? 0.51?
3-6? 15? 70? 4.11? 0.61?
3-7? 18? 70? 4.63? 0.66?
3-8? 19? 70? 4.80? 0.78?
3-9? Do not change 70? 5.53? 0.95?
The experimental result of table 4 shows that along with the change-over period shortens, the mean concns of free chlorine diminishes.On the other hand, under 20 seconds immovable situations of the DC sense of current, experimental result shows that the possibility that free chloro concentration surpasses 6ppm increases.But if the change-over period becomes too short, the DC electric current can't be measured, and will be slightly high but its concentration deviation shows.Therefore, can conclude that cycle of 5 seconds is only for concentration that keeps below 6ppm and the deviation that reduces concentration.That is, the situation of 5 seconds situation of compare cycle and no change-over period, free cl concn and deviation thereof become half of dissociate in a kind of situation of not having a change-over period in back cl concn and deviation thereof in preceding a kind of situation with change-over period.
Simultaneously, though go up the data that do not show single smooth electrode 141,142 in the table 4, confirm that the trend and the said circumstances of smooth electrode 141,142 are similar.That is, compare, use 5 second cycle and change the free chlorine of about half concentration amounts of situation generation of the DC sense of current, and show the concentration distribution deviation of half with the situation of not using the change-over period.
The 4th embodiment
Experimentize to determine what influence the width of change post 241a, 242a and the width of groove 241b, 242b have to free chloro concentration.Similar with the 2nd embodiment, electrode 241,242 is arranged as makes cathode column 241a and the anode posts 242a placement that meets at right angles.Each central zone (being the whole surf zone of described post and groove) by the IncFlds that the x among Fig. 9, y surround is respectively 841mm 2And be coated with platinum, and other surf zone of electrode 241,242 (that is, peripheral region 241b, 242b except that the central zone) scribbles insulation layer, takes place to prevent the regional around 241b of electrolysis, 242b place.Electrode 241,242 is separated from each other 2mm and arranges and immerse in the 50ml physiological saline of pH 6.45 ± 0.2.In addition, under the situation of the change-over period that changes the DC sense of current, supply with DC 3.0V to electrode 241,242 and reach 20 seconds.At the change of change-over period, to the measurement of concetration of free chlorine 5 times, as shown in following table 5.
Table 5
Sequence number Post width (mm) Well width (mm) DC electric current (mA) The mean concns of free chlorine The standard deviation of free chloro concentration
4-1? 0.7? 1.3? 100? 3.57? 0.66?
4-2? 0.3? 0.8? 80? 3.01? 0.49?
4-3? 0.5? 1.0? 85? 3.24? 0.61?
4-4? 1.0? 1.0? 110? 4.07? 1.11?
The experimental result of table 5 shows, along with the area in opposed facing territory 2412 diminishes, diminishes with respect to the DC electric current of unit surface, and wider with respect to the distribution of unit surface.Therefore, can infer that a plurality of as far as possible little territories 2412 that form that distribute equably are more effective for the concentration of accurate control free chlorine.
The sterilising effect of physiological saline of the present invention
Prepared the sterile saline that 35ml has 0.85% salt concn in 20 seconds by electrolysis, apply it to streptococcus aureus MRSA (Staphylococcus aureusMRSA) germ then and only carried out timeliness sterile test (Time Kill Test) in 30 seconds, test is undertaken by U.S. Polymer Solution Incorporated.Test-results is as follows.
Table 6
Initial CFU/ml Content The 1st experiment The 2nd experiment
2.8x10 6 The CFL of survival Less than 5 Less than 5
2.8x10 6 Kill percentage 99.9998%? 99.9998%?
2.8x10 6 Log10 (speed of minimizing) 5.75? 5.75?
[0170]Herein, CFL means the number of survival germ, and CFU/mL means the number of survival germ population.Above-mentioned test-results shows, only contacts with sterile saline the germ of 99.9998% streptococcus aureus MRSA by name is killed.
In addition, 50ml has the sterile saline of 0.80% salt concn by electrolysis preparation in 20 seconds, thereby the free chlorine with 3ppm to 4ppm concentration, it is applied to following germ carries out the timeliness sterile test.Test-results is as follows.
Figure G2008800060325D00231
Listed germ A, B, C item are represented the Mycophyta germ, and its C, D, E, F, H item are represented bacterium class germ.Above-mentioned experimental result shows that germ contacts 30 seconds with sterile saline of the present invention can realize 95.5% to 99.9% the effect of killing.
Industrial applicibility
Medical sterilization physiological saline of the present invention can be used for causing that by conversion allergic albumen treats rhinallergosis, and can directly be sprayed onto throat after preparation and come to be sterilized in oral cavity and throat inside.In addition, sterile saline can be treated athletic sufficient, inflammation and injured area by sprinkling immediately after preparation.In addition, this sterilization physiological solution can be used for killing the scurf germ of head, and can be used for killing germ or microorganism in the footwear.And this sterile saline can be used for uterus or vagina treats HPV (human papillomavirus) and infects, is used for tooth and germ, and is used for the oral cavity and gargles.
More specifically, the inlet 110a that can be used to be fixed in container 110 of the contact lenses cleaning module 420 shown in Figure 17 and 18 comes the cleaning contact lenses sheet.Promptly, contact lenses module 420 comprises a stopper 421 that is used for being fixed in inlet 110a, an extended extending element 422 from stopper 421, thus an eyeglass accommodating chamber 423 that is arranged in extending element 422 places makes the eyeglass that is contained in chamber 423 can be placed in sterile saline.Herein, the wall of eyeglass accommodating chamber 423 is made of silk screen, so that sterile saline can enter chamber 423 and each eyeglass in the chamber 423 is sterilized.Therefore, germ, the bacterium on the contact lenses can be killed or kill to the electrolytic oxygenant that comprises free chlorine, and the peroxidation Hydrogen Energy is removed the contact lenses proteins on surfaces.
On the other hand, the supplying module shown in Figure 19 and 20 500 can be used for by the inlet 110a that is fixed in container 110 sterile saline being conducted to dark position.Herein, supplying module 500 contains a stopper that can be fixed in inlet 110a with the blocking-up airflow; The blast main 510 that when container 110 is inverted, can extend on the physiological saline surface from stopper; One extends to the external world so that the effusive fluid hose 520 of sterile saline from lid.When this supplying module being fixed in inlet 110a and will install 110 inversions, though do not comprise the drive unit of any discharge or sprinkling physiological saline, but when user's head is positioned at the bottom when following, air is introduced in the container 110 by blast main 510, thus, sterile saline can be entered the inside of nose or lung by container by fluid hose 520.For preventing fluid hose 520 infringement person's windpipes, the protection bearing (protect socket) 521 that will have rounded form is connected in the end of fluid hose 520.In addition, discharge rapidly from container, air balls is connected in the end of blast main 510 for making sterile saline.
Have the structure of long tube 520 by this, can be with medical sterilization physiological saline from easily being conducted to depths, uterus, throat depths or lung depths.In addition, can connect mirror or eyeglass, make the operator be easy to check whether the supply of physiological saline is suitable at the end of managing 520.
In addition, a reservoir of being inverted cup-shaped can be connected in the end of the fluid hose 520 of supplying module 500, thus the oxygenant in the sterilization physiological solution can be conducted to continuously for example reach on the skin 30 seconds in addition time of 2 minutes.Herein, be the oxygenant that makes new generation and user's skin contact, can be by supplying with low currents continuously and cause electrolysis consistently to electrode group 140, also can be by sterile saline being oozed out via an aperture and fresh oxygenant being conducted to the reservoir from container 110 continuously.In addition, can fill with rubber to prevent sterile saline seepage between user's skin and reservoir inside forming sealing around the reservoir.
On the other hand, when the user wishes that this sterile saline is conducted to uterus or vagina, need use the uterus supplying module to comprise the supply bearing at the end of supply-pipe, wherein said supply bearing has the hole of radial direction, and this hole can make sterile saline be conducted in the uterus equably.Though do not illustrate in the drawings, the place can connect at least one spherical mirror in the supply bearing, makes the user can insert supplying module voluntarily, and is similar to the splanchnoscopy principle.
Because the present invention can implement under the situation that does not depart from its purport or essential characteristic in a variety of forms, what therefore will also be understood that is, unless otherwise, otherwise above-mentioned embodiment is not subject to any aforementioned details, and in the purport and scope that should broadly be interpreted as limiting at appended claims, therefore fall into all changes and improvements in claims boundary, the equivalent way in the perhaps described boundary all should be included in the appended claims.

Claims (18)

1. method for preparing medical sterilization physiological salt solution with sterilization efficacy, this method comprises:
With the step that at least one electrode group immerses the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises a pair of electrode with flat surfaces that is separated from each other out 1mm to 3mm spacing, and the flat surfaces of described electrode is faced mutually;
By applying the step that 2.4V to 3.3V volts DS is supplied with electrode 30mA to 200mA galvanic current to described electrode;
Wherein the free chloro concentration scope that is produced by the electrolysis between the electrode is between 0.17ppm and 6ppm.
2. the method that is used to prepare the medical sterilization physiological salt solution that claim 1 is claimed, wherein said physiological salt solution are physiological saline.
3. the method that is used to prepare the medical sterilization physiological salt solution that claim 2 is claimed, the direction of wherein said galvanic current are changed in electrolytic process at least one time.
4. the method that is used to prepare the medical sterilization physiological salt solution that claim 3 is claimed, the direction of wherein said galvanic current was changed in per 1 second to per 20 seconds.
5. the method that is used to prepare the medical sterilization physiological salt solution that claim 1 is claimed, the amount of wherein said physiological salt solution are that 10ml to 100ml and described physiological salt solution directly prepare by a kind of mancarried device.
6. be used to prepare the method for the medical sterilization physiological salt solution with sterilization efficacy, this method comprises:
At least one electrode group is immersed the step of the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises pair of electrodes, on the apparent surface of each electrode, have a plurality of territories that are separated from each other, relative with the interval of 1mm to 3mm in a plurality of territories on the apparent surface of an electrode with a plurality of territories on the apparent surface at another electrode; With
By applying the step that 2.2V to 3.2V direct current is supplied with electrode 30mA to 180mA galvanic current to described electrode,
Wherein the area in a plurality of territories of each electrode account for each electrode the apparent surface the total area 4% to 25%, and produce the free chlorine of concentration range between 0.17ppm to 6ppm in the electrolytic process.
7. the method that is used to prepare the medical sterilization physiological salt solution that claim 6 is claimed, wherein said physiological salt solution are physiological saline.
8. the method that is used to prepare the medical sterilization physiological salt solution that claim 7 is claimed, this method also comprises:
At least once change the step of the direction of the galvanic current that flows through described electrode in the electrolytic process.
9. the claimed method of claim 6, wherein said electrode group comprises:
A template anode, it has a plurality of anode posts of being separated by a plurality of anode slots that are in a direction and are parallel to each other; With
A template negative electrode, it has a plurality of cathode columns that separated by a plurality of cathode can that are in a direction and are parallel to each other,
Wherein when the parallel placement of anode and when making anode posts and the not parallel placement of cathode column with negative electrode, with the perpendicular direction of electrode surface on the zone that overlaps form a plurality of territories.
10. the method that is used to prepare the medical sterilization physiological salt solution that claim 9 is claimed, wherein said anode posts and described cathode column are in right-angle array.
Be used to prepare the method for physiological salt solution of sterilizing 11. claim 9 is claimed, wherein the width of anode posts is narrower than the width of anode slot, and the width of cathode column is narrower than the width of cathode can.
12. the method that is used to prepare the medical sterilization physiological salt solution that claim 6 is claimed, wherein said electrode comprises:
Protrude a plurality of anode salients that form at anode; With
Protrude a plurality of negative electrode salients of formation the apparent surface of negative electrode;
Wherein the end surface areas by opposed facing anode salient and negative electrode salient forms a plurality of territories.
13. the method that is used to prepare the medical sterilization physiological salt solution that claim 6 is claimed, the direction that wherein flows through the galvanic current of described electrode was changed in per 1 second to per 20 seconds.
14. being 10ml to 100ml and described physiological salt solution, the method that is used to prepare the medical sterilization physiological salt solution that claim 6 is claimed, the amount of wherein said physiological salt solution directly prepare by a kind of mancarried device.
15. the method that is used to prepare the medical sterilization physiological salt solution that claim 6 is claimed, the amount of wherein said physiological salt solution are 10ml to 100ml and supplied with galvanic current 10 to 60 seconds to electrode.
16. be used to prepare the method for the medical sterilization physiological salt solution with sterilization efficacy, this method comprises:
At least one electrode group is immersed the step of the physiological salt solution of pH 4.0 to pH 7.5, this electrode group comprises pair of electrodes, on the apparent surface of each electrode, have a plurality of territories that are separated from each other, relative with the interval of 1mm to 3mm in a plurality of territories on the apparent surface of an electrode with a plurality of territories on the apparent surface at another electrode, wherein the area in a plurality of territories of each electrode account for each electrode the apparent surface the total area 4% to 25%; With
By supplying with DC and electrolytic step to electrode.
17. the method that claim 16 is claimed also comprises:
At least once change the step of the direction of the galvanic current that flows through described electrode in the electrolytic process.
18. by the medical sterilization physiological salt solution of the method for one of claim 1 to 17 preparation, wherein prepared physiological salt solution is used for one of following purposes: spray nose inside, spray throat, the inside, oral cavity of washing one's face and rinsing one's mouth, spray tooth or gum, sterilization postoperative body part, spray skin, spray hair, spray segmental bronchus or lung, inside, sprinkling uterus carries out disinfection and spray athletic foot.
CN2008800060325A 2007-02-26 2008-02-26 Manufacturing method of medical sterilized isotonic solution having low-concentratedly controlled free chlorine including hypochlorous acid therein Expired - Fee Related CN101631898B (en)

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KR1020070018791 2007-02-26
KR1020070018791A KR100849618B1 (en) 2007-02-26 2007-02-26 Mobile apparatus for manufacturing sterilized odorless isotonic solution having lowly controlled residual chlorine content therein
KR10-2007-0018791 2007-02-26
KR1020070084223A KR100945188B1 (en) 2007-08-21 2007-08-21 Manufacturing method of medical sterilized isotonic solution having low-concentratedly controlled free chlorine including hypochlorous acid therein
KR10-2007-0084223 2007-08-21
KR1020070084223 2007-08-21
PCT/KR2008/001096 WO2008105613A1 (en) 2007-02-26 2008-02-26 Manufacturing method of medical sterilized isotonic solution having low-concentratedly controlled free chlorine including hypochlorous acid therein

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ITMI20101098A1 (en) * 2010-06-17 2011-12-18 Industrie De Nora Spa ELECTRODE FOR ELECTROCLORATION
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JP6487217B2 (en) * 2014-02-06 2019-03-20 有限会社ターナープロセス Method and apparatus for controlling free chlorine concentration, and sterilization method and sterilization apparatus using them
CN105386079B (en) * 2015-12-14 2017-11-17 泉州师范学院 Miniature sterilization liquid generator
CN107291018A (en) * 2017-08-04 2017-10-24 张永超 A kind of drive control circuit for disinfecting device

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