CN1259252C - Anolyte and its making method - Google Patents
Anolyte and its making method Download PDFInfo
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- CN1259252C CN1259252C CN 02128244 CN02128244A CN1259252C CN 1259252 C CN1259252 C CN 1259252C CN 02128244 CN02128244 CN 02128244 CN 02128244 A CN02128244 A CN 02128244A CN 1259252 C CN1259252 C CN 1259252C
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- anolyte
- electrolysis
- disproportionation
- peroxide radical
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Abstract
The present invention discloses anolyte with the free radical dismutation of peroxides, and a manufacture method thereof. In the anolyte, the content of water-solubility inorganic salts is below 0.1mM, the ascorbic acid content is from 1 to 50mM, the oxidation reduction potential is from 85 to 50mV, the dissolved oxygen is from 8 to 15 mg/l and the pH is from 3.70 to 2.80. The anolyte has the wide application in the fields of sterilization and disinfection, health care, beauty treatment, etc.
Description
Technical field
The present invention relates to have the anolyte and the manufacture method thereof of the effect of disproportionation peroxide radical.In more detail, relate to electrolysis and only contain the aqueous electrolyte liquid of xitix, take out the manufacture method of the anolyte of the anolyte that is created on anode side as the electrolysis auxiliary agent, and the anolyte with described disproportionation.
Background technology
Utilization across barrier film at the electrolyzer of internal configuration by the noble electrode of forming by platinum, platinum alloy etc., the electrolytical thin aqueous solution such as the alkali-metal muriate of electrolysis, taking-up is at the low anolyte (sour water) of pH that anode side generates, and this anolyte is used for sterilization or the disinfectant technology is known.Also have, the barrier film use is made membranaceous charged membrane to ion exchange resin or is had the non-charged membrane of microporous structure.
Contain hypochlorous acid in the described anolyte.Being used for described sterilization or sterilization is exactly to have utilized hypochlorous strong oxidation and chlorization.This method of utilizing is popularized in medical office etc.And the ozone that contains of trace or dissolved oxygen are because of having granulation generation promoter action, so also carrying out the research that utilizes as the surgical intervention supplementary means in the anolyte.
On the other hand, be created on the catholyte (alkaline water) of cathode side, can replace above-mentioned ionogen dilute solution with tap water, this obtains by electrolysis.It was used for tap water etc. in the past.In above-mentioned aqueous electrolyte liquid or tap water, it also is known adding as additive and not making method of electrolyte (USP5,736,027) as organic acids such as the xitix of electrolysis auxiliary agent or gallic acids.
In these methods, xitix uses in the presence of the electrolysis auxiliary agent.The adding purpose of xitix is, suppresses the pH of catholyte, and the free chlorine in the division anolyte.
Though do not have direct relation with aforesaid method, the Cole that people know is that organic acids such as electrolysis such as carboxylic acid when anode side is emitted carbonic acid gas, generate the reaction in conjunction with the compound of two organic acid residues than reaction.For example, utilize Cole than reaction from acetic acid generate methods of citric acid etc. also be before just by known to the people.
Xitix has the OH base at intramolecular 2 and 3 bit positions.Xitix is at acidic region.3-OH dissociates into-O
-And H
+, show acid.In the alkalescence zone.2-OH dissociates into-O
-And H
+But, because of this dissociation degree is low, so fail as the electrolysis auxiliary agent.And the electrolytic process complexity during the electrolysis aqueous ascorbic acid though intermediate product is not specific, is thought redox reaction basically.
Xitix itself is a strong reductant.Automatic autoxidation takes place in the aqueous solution, thereby reducing power descends, this also is known.In general, xitix is according to following process autoxidation.
Here, AsA, MDA, DHA and DKG represent xitix, single L-dehydroascorbic acid, L-dehydroascorbic acid and 2 separately, 3-dioxo gulonic acid.
In recent years, the clear and definite peroxide radical that is widely known by the people as active oxygen is by xitix disproportionation and situation about eliminating.Xitix is attracted attention by the people as oxidation inhibitor for this reason.
Here, the disproportionation reaction of peroxide radical is as shown in the formula shown in (2).Be that peroxide radical disappears, generate hydrogen peroxide.
Xitix is the useful material that can eliminate peroxide radical as mentioned above, but the anolyte that increases the disproportionation of peroxide radical by the electrolysis aqueous ascorbic acid does not still have report.
Summary of the invention
The inventor is conceived to the ability of the disproportionation peroxide radical that above-mentioned xitix has, and has inquired into the anolyte that how to obtain to have this ability.It found that, be not inorganic electrolytes such as water-soluble metal salts as the electrolysis auxiliary agent, but the aqueous solution of the simple xitix of electrolysis low concentration, the anolyte of the disproportionation peroxide radical ability that just can be improved.
The present invention just is based on that above-mentioned discovery is accomplished, and to its objective is provide the anolyte that improves disproportionation peroxide radical ability.
The present invention who achieves the above object is described below.
[1] a kind of anolyte wherein, contains water-soluble inorganic salt＜0.1mM, xitix 1～50mM, redox potential and is 85～50mV, dissolved oxygen and be 8～15mg/l, pH and be 3.70～2.80 and have a disproportionation of peroxide radical.
[2] a kind of manufacture method of anolyte of the disproportionation with peroxide radical, it is characterized in that: brine electrolysis dissolubility inorganic salt content is lower than the aqueous electrolyte liquid of 0.1mM, ascorbic acid content 1～50mM, takes out the anolyte as [1] record.
[3], use to have membranous electrolyzer and carry out electrolysis as the manufacture method of anolyte of the disproportionation with peroxide radical of above-mentioned [2] record.
[4] as the manufacture method of anolyte of the disproportionation with peroxide radical of above-mentioned [2] record, wherein, the current density during electrolysis is 0.003～0.03A/cm
2
[5] as the manufacture method of anolyte of the disproportionation with peroxide radical of [2] record, it is characterized in that: the aqueous electrolyte liquid that the water-soluble inorganic salts contg is lower than 0.1mM, ascorbic acid content 1～50mM supplies to the flow of 500～3000ml/min has membranous continuous flow electrolyzer, with 0.003～0.03A/cm
2Electrolytic current density carry out continuous electrolysis.
[6] as the manufacture method of anolyte of the disproportionation with peroxide radical of [2] record, it is characterized in that: the aqueous electrolyte liquid that the water-soluble inorganic salts contg is lower than 0.1mM, ascorbic acid content 1～50mM supplies to the flow of 4～50ml/min does not have membranous continuous flow electrolyzer, with 0.003～0.03A/cm
2Electrolytic current density carry out continuous electrolysis.
The used for electrolyte that the electrolyte aqueous solution is obtained uses tap water as aqueous electrolyte liquid when tap water or sterilization, sterilization are used etc., perhaps added the tap water of water-soluble inorganic salts such as sodium-chlor or Repone K.Tap water is because of itself containing a certain amount of inorganic salt, so can play electrolytical effect.
On the other hand, the report aqueous electrolyte liquid that has electrolysis to add ionogen and xitix is made the technology of electrolytic solution.This moment, xitix was to use (for example the spy opens flat 11-33552 number) as removing basicity with additive.Also have, electrolysis contains the aqueous electrolyte liquid as the xitix of additive, is created on the hypochlorous acid in the electrolytic solution of anode side with the xitix reduction, thereby suppresses the method also known (spy opens flat 8-229563 number) of the generation of free chlorine in the electrolytic solution.
At this moment, the ionogen of being made up of water-soluble inorganic salt in whole aqueous electrolyte liquid contains as the electrolysis auxiliary agent, and the xitix that coexisting.Xitix is all the time as not having the additive of direct relation to use with electrolysis.
In general, following reaction takes place during just like the aqueous electrolyte liquid of the ionogen (electrolysis auxiliary agent) of sodium-chlor and xitix (additive) in electrolytic dissolution.
1. cathode side
Here, AsANa represents sodium ascorbate.Xitix in the catholyte passes through 3 H
+Replaced by sodium ion, become sodium salt.Its result has only 2 H
+Be used for the disproportionation superoxide.So the disproportionation ability reduces by half.
2. anode side
In anode side shown in (9) formula because hypochlorous chlorization and oxygenizement, 2 and 3 H of xitix
+Disappear, so the change of superoxide does not take place fully.
Below just be to use an ionogen to use, dipolar electrolytic reaction during aqueous electrolyte liquid that xitix is added as additive as the electrolysis auxiliary agent.At this moment, though only in the disproportionation of cathode side generation superoxide, this disproportionation reaction amount has only reduced the amount that generates sodium ascorbate.
Also have, in anode side as previously mentioned, the chlorization and the oxygenizement of the xitix that causes by hypochlorous acid, 2 and 3 H of xitix
+Disappear, so the disproportionation reaction of superoxide does not take place fully.
Dipolar electrolytic reaction when on the other hand, electrolysis is only dissolved the aqueous electrolyte liquid of xitix as ionogen is as follows.
1. cathode side
Shown in (11) formula, by electrolysis, in the xitix 2 and 3 s' hydrogen cathode surface cause electron reaction, produce hydrogen at cathode side.The DHA that generates by electrolysis can not emit H
+, so the disproportionation of peroxide radical does not take place.And xitix negatively charged ion anode side is carried, so the disproportionation of the peroxide radical that the xitix negatively charged ion causes does not take place yet.
2. anode side
Shown in (13) formula, the xitix negatively charged ion is at anode and the H that the water oxidation is generated
+Reaction becomes xitix.On the other hand, shown in (14) formula, the oxygen that generates at anode is by becoming 2 to Ascorbic Acid Oxidation, 3-dioxo gulonic acid and being consumed, and the direction of dissolved oxygen content plays a role in reducing anolyte.But this ratio is little.
And, except the reaction of representing with (13) formula, also have micro-excess hydrogen ion because of the xitix negatively charged ion is different with hydrionic velocity of diffusion at anode.So, to compare with the situation that only has xitix, proton has increased.Its result, the disproportionation amount of peroxide radical increases in anode side.
Sum up the above:
1) electrolysis is used water-soluble ionogen such as sodium-chlor or chlorine potassium as the electrolysis auxiliary agent, and xitix during as the aqueous electrolyte liquid of additive and usefulness, though catholyte shows disproportionation, just become the amount that sodium ascorbate or potassium ascorbate consume, a little less than the disproportionation.Anolyte contains hypochlorous acid, and most of xitix is consumed by this hypochlorous acid.So anolyte does not show disproportionation.
When 2) xitix is only used in electrolysis as the aqueous electrolyte liquid of electrolysis auxiliary agent, 2,3 hydrogen of negative electrode xitix by electron reaction is initiated and becomes L-dehydroascorbic acid.So, think hardly that at cathode side disproportionation reaction is arranged.
Also have, in anode side, the hydrogen ion reaction that the xitix negatively charged ion of carrying from negative electrode and the electrode reaction of water produce and get back to xitix shows disproportionation.And because the superfluous hydrogen ion of trace that generates, the disproportionation of anolyte increases.The amount of the xitix of dissolved oxygen consumption is extremely few.
In the present invention, the aqueous electrolyte liquid of xitix as the electrolysis auxiliary agent only used in electrolysis, and making redox potential (ORP) is that 85～50mV, pH are 3.70～2.80.The anolyte that obtains is like this compared with the anolyte beyond described redox potential and the pH scope, and the disproportionation ability of peroxide radical is especially high.So obtain utilizing in the various uses such as this anolyte generates at sterilization and disinfection, granulation, keeps fit, beauty treatment.And xitix is that human safety has been obtained the VITAMIN confirmed, so use it the anolyte security of making very high as the electrolysis auxiliary agent.
Description of drawings
One example of Fig. 1 anolyte manufacturing installation of the present invention constitutes synoptic diagram.
Fig. 2 represents the example that the ESR of the disproportionation ability of the peroxide radical that example 1 anolyte has composes.
One example of the ESR spectrum of the peroxide radical of Fig. 3 embodiment 1 catholyte.
Fig. 4 represents another example of ESR spectrum of disproportionation ability of peroxide radical of the anolyte of embodiment 2.
Another example of the ESR spectrum of the peroxide radical of Fig. 5 embodiment 2 catholytes.
Fig. 6 represents another example of ESR spectrum of disproportionation ability of the peroxide radical of embodiment 3 anolytes.
Another example of the ESR spectrum of the peroxide radical of Fig. 7 embodiment 3 catholytes.
One example of the ESR spectrum of the peroxide radical of Fig. 8 comparative example 1 anolyte.
One example of the ESR spectrum of the peroxide radical of Fig. 9 comparative example 1 catholyte.
Figure 10 represents the example that the ESR of the peroxide radical of comparative example 2 distilled water composes.
When Figure 11 carries out the electrolysis of the aqueous electrolyte liquid shown in the embodiment 1, the curve of expression electrolytic current density and dissolved oxygen content relation.
2 aqueous electrolyte liquid grooves; 4 aqueous electrolyte liquids; 6 pumps; 8 aqueous electrolyte liquid supply-pipes; 10 electrolyzers; 12 anodes; 14 negative electrodes; 16 barrier films; 18 anolyte compartments; 20 cathode compartments; 22 electrolysis powers; 24 anolyte take-off pipes; 26 catholyte take-off pipes
Embodiment
Below, present invention will be described in detail with reference to the accompanying.
The electrolyzer that uses during anolyte of the present invention that manufacturing has the peroxide radical disproportionation is not particularly limited, and can use any existing electrolytic solution manufacturing installation.Promptly can use any and electrolyzer size, electrolyzer septation irrelevant electrolyzer such as have or not.
Fig. 1 is the synoptic diagram that expression is used to have electrolyzer one example that the anolyte of the present invention of peroxide radical disproportionation makes.
Among Fig. 1,2 is the aqueous electrolyte liquid groove, and portion contains aqueous electrolyte liquid 4 within it.
Described aqueous electrolyte liquid 4 contains the xitix of 1～50mM, preferred 2～20mM.The pH of this aqueous electrolyte liquid is about 3.70～2.80.If the concentration of xitix is less than 1mM, electric conductivity is low and be difficult to electrolysis.Also have,, when the gained anolyte is used for skin etc., have the sense of being clamminess, according to utilizing method to have inappropriate situation if surpass 50mM.
Preferably be substantially devoid of xitix ionogen such as water-soluble inorganic salt in addition in the above-mentioned aqueous electrolyte liquid 4.Preferred each the water-soluble inorganic ionogen of the electrolytical content of water-soluble inorganic amounts to below the 0.1mM, below the preferred especially 0.02mM.
The preparation method of this aqueous electrolyte liquid 4 has for example, in Purified Waters such as distilled water or deionized water (pure water), dissolution of ascorbic acid is become the method for above-mentioned concentration range.
The 6th, be contained in the pump on the aqueous electrolyte liquid supply-pipe 8, by making this pump 6 work, aqueous electrolyte liquid 4 is delivered to electrolyzer 10 by supply-pipe 8.
Described electrolyzer 10 has with given interval opposite one another anode 12 and negative electrode 14 and at the barrier film 16 of described two interpolars and the two poles of the earth separate configuration separately.In the described electrolyzer 10, between described anode 12 and barrier film 16, be formed with anolyte compartment 18, and between described negative electrode 14 and barrier film 16, be formed with cathode compartment 20.Described anode 12, negative electrode 14 are formed by electrochemistry inert metallic substance.The preferred platinum of electrode materials, platinum alloy etc.Barrier film 16 is to play the anolyte that prevents in the anolyte compartment 18 and the catholyte blended effect in the cathode compartment 14, and is made of the material of conduction Faradaic current.The suitable use of barrier film is existing to be used for electrolytic ion-exchange membrane, non-charged membrane etc. as electrolytic film.
Described supply-pipe 8 is divided into manifold 8a, 8b at the upstream side of electrolyzer 10, and manifold 8a, 8b are connected in described anolyte compartment 18, cathode compartment 20 separately.
22 is electrolysis power, and its plus end is connected anode 12, and negative terminal is connected negative electrode 14.
Be sent to the aqueous electrolyte liquid electrolysis here of anolyte compartment 18, cathode compartment 20 by described manifold 8a, 8b.Preferred 0.003～the 0.03A/cm of electrolytic current density
2, more preferably 0.01～0.02A/cm
2If electrolytic current density is less than 0.003A/cm
2, can't make the dissolved oxygen content from the effusive anolyte in anolyte compartment be higher than aqueous electrolyte liquid.Also have, if electrolytic current density surpasses 0.03A/cm
2, the growing amount of anolyte does not increase with current value, and is uneconomical.
So,, can make dissolved oxygen content from the effusive anolyte in anolyte compartment more than aqueous electrolyte liquid, preferably at 8～15mg/l, more preferably at 9～14mg/l by electrolytic current density being controlled in the above-mentioned scope.
Among the present invention, by being adjusted in the above-mentioned scope electrolytic current density is suitable, the pH that makes the gained anolyte is 3.70～2.80, and to make its redox potential (ORP) be 85～50mV.
The anolyte that generates by the aforesaid method electrolysis is discharged to the outside by anolyte take-off pipe 24.Also have, similarly catholyte is discharged to the outside by catholyte take-off pipe 26.
Above-mentioned electrolyzer 10 is provided with membranous structure for portion within it, but is not limited thereto, and the electrolyzer that is not provided with membranous no barrier film structure also can use well.
Electrolyzer as this no barrier film structure can have for example, between positive plate and negative plate, do not place barrier film, but two-plate near configuration, between described yin, yang two-plate, supply with aqueous electrolyte liquid and electrolysis simultaneously, near this structure of the anolyte anodic downstream side takes out anode surface continuously continuously.Specifically there is the spy to open disclosed electrolyzer etc. in the flat 6-246272 communique.
Also have, having or not of the peroxide radical disproportionation of electrolytic solution is to judge having or not of signal by according to the peroxide radical of spectrum device described later (ESR).
Embodiment
Further specify the present invention below by embodiment.
Use electrolyzer electrolysis shown in Figure 1 to contain the aqueous electrolyte liquid of xitix.(7.5cm * 11.5cm) arrange with mutual 2.5mm spaced and parallel has adorned non-charged membrane betwixt with 5 platinum plates in the electrolyzer.Then, by described platinum plate is replaced as anode, negative electrode, make amounting to 4 structures that electrolyzer is arranged side by side together.The electrolyzer internal volume is 86.4ml, and aqueous electrolyte liquid is supplied with this electrolyzer with the flow of 2000ml/min, obtains anolyte and catholyte.Electrolytic current density is adjusted to 0.02A/cm
2
The pH of gained anolyte is 3.68, and ORP is 82mV.
Aqueous electrolyte liquid prepares by add xitix to 2mM concentration in deionized water.Also have, because of having used deionized water, the content of the water-soluble inorganic salt in the aqueous electrolyte liquid is trace (less than 0.01mM) extremely.
The electrolytic solution of making as sample, is used ESR, and having or not of the disappearance that caused by the peroxide radical disproportionation reaction investigated in following record.
1) generation of peroxide radical
Peroxide radical uses the xanthoglobulin of 2mM and the XOD of 0.4mM unit/ml to generate.
2) utilize the spin trapping of DMPO
2mM xanthoglobulin-phosphate buffered saline buffer 50 μ l
5.5mM DETAPAC (diethylene triaminepentaacetic acid(DTPA))-phosphate buffered saline buffer 35 μ l
DMPO (5-oxynitride) 16 μ l
0.4unit/ml XOD-phosphate buffered saline buffer 50 μ l
Above-mentioned substance is put into flat partially electrolyzer, be installed on the ESR device, begin scanning after 1 minute, confirm having or not based on the signal of peroxide radical.
3) ESR condition determination
Measure temperature: room temperature
Microwave output: 3.7mW
Scanning magnetic field: 339.1mT ± 5.5mT
Magnetic field modulation: 100kHz (external modulation mode)
Modulated amplitude: 0.1mT
Time constant: 0.12sec
Sweep time: 1min
4) measurement result
With gained ESR spectral representation at Fig. 2 and Fig. 3.Fig. 2 represents the situation that anolyte uses as sample.Peroxide radical can be described by disproportionation from signal that can't see peroxide radical, and peroxide radical disappears almost.
Also have, dissolved oxygen content is 14.99mg/l.
Fig. 3 is the collection of illustrative plates of catholyte when using as sample.Can see the signal (signal of representing with arrow a among the figure) of peroxide radical, illustrate that peroxide radical does not disappear, also not by disproportionation.
Embodiment 2
Except the ascorbic acid concentrations in the aqueous electrolyte liquid is that 50mM, current density are 0.01A/cm
2In addition, all the other are identical with embodiment 1, make electrolytic solution.
Gained anode and catholyte are used ESR and the example 1 same signal of observing peroxide radical respectively.
With gained ESR spectral representation at Fig. 4 and Fig. 5.Fig. 4 is the collection of illustrative plates of anolyte.Can illustrate that from signal that can't see peroxide radical peroxide radical is almost disappeared by disproportionation and peroxide radical.
Also have, dissolved oxygen content is 12.3mg/l.And pH is 2.87, and ORP is 55mV.
Fig. 5 is the collection of illustrative plates when using catholyte.Can see the signal (signal of representing with arrow a among the figure) of peroxide radical.Illustrate that promptly peroxide radical does not disappear, also not by disproportionation.
(benchmark test of anolyte)
The anolyte that use is made according to the foregoing description 2 carries out the sense test of nursing skin.For relatively, using under similarity condition with same device electrolysis concentration is that anolyte (strong oxidized water) that the NaCl aqueous solution of 0.25 weight % obtains carries out sense and tests.
The following record of test method.
1) measured: people 14 people of the easy roughen of skin among the healthy people (healthy woman).
2) testing method: the 7 human electrolysis of 14 philtrums contain the anolyte (the present invention's product) that the aqueous electrolyte liquid of xitix obtains, the anolyte (relatively product) that the aqueous electrolyte liquid that other 7 human electrolysis contain NaCl obtains, twice on the one ground were coated in hand and on the face in continuous 21 days.The test result that obtains is shown in table l.
The sense test result of the relevant pachylosis of table 1
| Xitix anolyte group % | NaCl anolyte group % | |
| There is pungency to have moisture retention to have refrigerant sense frowziness to have whitening effect to improve | 0 86 100 0 43 86 | 43 29 86 86 29 57 |
It is that the general so-called electrolysis of using generates water, its pH=2.5, redox potential (ORP)=1250mV that electrolysis contains the anolyte that the aqueous electrolyte liquid of NaCl obtains.The anolyte of the embodiment of the invention 2 does not have pungency and stink fully, and it is good also to contain the anolyte that the aqueous electrolyte liquid of NaCl obtains than electrolysis for moisture retention.Anolyte of the present invention shows the reason of so good character, has improved the antioxygenation of anolyte just by electrolysis.The pH of gained anolyte is 2.85, ORP is 52mV.
Embodiment 3
Except the ascorbic acid concentrations in the aqueous electrolyte liquid is that 20mM, current density are 0.02A/cm
2In addition, all the other are identical with embodiment 1, make anolyte.
Gained anode and catholyte are observed similarly to Example 1 the signal of peroxide radical respectively with ESR.
With gained ESR spectral representation at Fig. 6 and Fig. 7.Fig. 6 is for using the situation of anolyte.Peroxide radical can be described by disproportionation from signal that can't see peroxide radical, and peroxide radical disappears almost.
Fig. 7 is for using the situation of catholyte.Can see the signal (signal of representing with arrow a among the figure) of peroxide radical.Illustrate that peroxide radical does not disappear, also not by disproportionation.
Comparative example 1
Use 2mM NaCl as aqueous electrolyte liquid, carry out electrolysis similarly to Example 1.Anolyte, catholyte and the embodiment 1 identical ESR spectrum that obtains with gained.
Represent that at Fig. 8 and Fig. 9 the ESR of anolyte, catholyte composes.Use NaCl to be, all confirm to have the signal of peroxide radical, illustrate that these electrolytic solution do not eliminate the ability of peroxide radical for any one electrolytic solution as the situation of the comparative example 1 of electrolysis auxiliary agent.
Comparative example 2
Use and not carry out electrolytic distilled water, use the disproportionation ability of the study on determination method peroxide radical identical with embodiment 1.Represent that at Figure 10 the ESR that is measured composes.During pure water, can't see the elimination of peroxide radical fully, therefore explanation does not have the disproportionation ability.
Also have, dissolved oxygen content is 9.65mg/l.
Reference example 1
Usually, if dissolution of ascorbic acid in Purified Water, then consume the dissolved oxygen in the Purified Water, dissolved oxygen content shows the value that 8mg/l is following.To this, if the electrolysis aqueous ascorbic acid then generates oxygen by the electrolysis at anodic water.So, if the electrolysis aqueous ascorbic acid, except before electrolysis, being dissolved in the dissolved oxygen in the aqueous ascorbic acid, the oxygen that in electrolysis, generates in addition, thus increase than dissolved oxygen concentration with former water before the electrolysis.
Therefore, aqueous ascorbic acid before the electrolysis and the electrolytic solution after the electrolysis were not passing through after the electrolysis under the long situation, can easily discern by comparing dissolved oxygen content.
When Figure 11 is to use the electrolyzer identical with embodiment 1 to carry out the electrolysis of the aqueous ascorbic acid shown in the embodiment 1, the curve of expression electrolytic current density and dissolved oxygen content relation.Carry out electrolysis and must increase the dissolved oxygen content of anolyte.
Also have, the dissolved oxygen that dissolved oxygen generates during as the electrolysis auxiliary agent with use NaCl is the same, has skin regeneration and skin repair effect.
Claims (6)
1. anolyte, water-soluble inorganic salts contg wherein is lower than 0.1mM, and ascorbic acid content is 1～50mM, redox potential is 85～50mV, dissolved oxygen is 8～15mg/l, and pH is 3.70～2.80, and has the disproportionation of peroxide radical.
2. as the manufacture method of the anolyte of the disproportionation with peroxide radical of claim 1 record, it is characterized in that: brine electrolysis dissolubility inorganic salt content is lower than the aqueous electrolyte liquid of 0.1mM, ascorbic acid content 1～50mM, takes out anolyte.
3. as the manufacture method of the anolyte of the disproportionation with peroxide radical of claim 2 record, wherein use to have membranous electrolyzer and carry out electrolysis.
4. as the manufacture method of the anolyte of the disproportionation with peroxide radical of claim 2 record, wherein, the current density during electrolysis is 0.003～0.03A/cm
2
5. as the manufacture method of the anolyte of the disproportionation with peroxide radical of claim 2 record, wherein, the aqueous electrolyte liquid that the water-soluble inorganic salts contg is lower than 0.1mM, ascorbic acid content 1～50mM is supplied with the flow of 500～3000ml/min has membranous continuous flow electrolyzer, with 0.003～0.03A/cm
2Electrolytic current density carry out continuous electrolysis.
6. as the manufacture method of the anolyte of the disproportionation with peroxide radical of claim 2 record, wherein, the aqueous electrolyte liquid that the water-soluble inorganic salts contg is lower than 0.1mM, ascorbic acid content 1～50mM is supplied with the flow of 4～50ml/min does not have membranous continuous flow electrolyzer, with 0.003～0.03A/cm
2Electrolytic current density carry out continuous electrolysis.
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