CN1762840A

CN1762840A - Reduced water generation device

Info

Publication number: CN1762840A
Application number: CNA2005100935147A
Authority: CN
Inventors: 松木清悟
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-08-27
Filing date: 2005-08-26
Publication date: 2006-04-26
Anticipated expiration: 2025-08-26
Also published as: CN100354212C; JP4085084B2; TW200607766A; KR20060048764A; JP2006061840A; KR100786934B1

Abstract

The present invention provides an apparatus for producing reductive water that is produced in a condition that the residual amounts of a chlorine ion, a hypochlorite ion and a chlorine molecule are lowered and the elution of a base stock of an electrode in water is decreased by adjusting the time to impress positive (+) AC voltage and the time to impress negative (-) AC voltage. A carbon electrode 1 is selected as each of the electrodes of this apparatus for producing reduced water. The residual concentration of the chlorine ion or the like is lowered. Length of the time to impress negative (-) voltage to the carbon electrode 1 from an AC power source 3 is set so that a scale film having such a thickness that the electrical conductivity to water is not hindered is formed on the surface of the carbon electrode 1. Length of the time to impress positive (+) voltage is set to a degree that the formed scale film is dissolved and the impression of the positive (+) voltage ends before a carbon particle is eluted in water from the surface of the carbon electrode. As a result, the elution of the carbon particle in water can be decreased.

Description

The reductive water generating apparatus

Technical field

The present invention relates to a kind of by applying the device that voltage of alternating current generates reductive water.

Background technology

Advocated by applying the device that high-frequency ac voltage generates reductive water.

Usually, as the redox potential of water, as intermediate value, the water that current potential is lower than this intermediate value is called reductive water when using value (ORP value) demonstration+200mV of the redox potential that silver-silver chloride electrode determines.

In the existing reductive water generating apparatus that has adopted high-frequency alternating current, in most of the cases, employing applies high-frequency ac voltage to pair of electrodes, or except that this pair of electrodes, also use the 3rd ground-electrode (current potential be zero electrode), and between this pair of electrodes, apply volts DS etc., but the characteristic of reductive water generating apparatus is subjected to employed raw-material influence in this pair of electrodes.

For example, reductive water generating apparatus shown in the

patent documentation

1 and 2, adopt platinized titanium as pair of electrodes, but the water that contains chlorine with tap water etc. is under the situation of raw material, chlorion, hypochlorite ion and chlorine molecule residue in the reductive water, therefore, corollary is to be not suitable for very much (must be once more by gac etc. strainer purify) as tap water.

On the other hand, shown in patent documentation 3 like that, with the metal oxide be electrode use the reductive water generating apparatus of high-frequency alternating current, although this metal oxide stripping in water, can not prevent this stripping particularly.

[patent documentation 1] spy opens the 2000-84560 communique

[patent documentation 2] spy opens the 2002-45861 communique

[patent documentation 3] spy opens the 2002-273431 communique

Summary of the invention

Problem of the present invention is first: provide and can generate reductive water, second with the state of not residual chlorine ion, hypochlorite ion and chlorine molecule: provide and can reduce the starting material stripping that the constitutes electrode reductive water generating apparatus in the water.

In order to solve above-mentioned problem, basic comprising of the present invention is as follows:

(1) a kind of reductive water generating apparatus is to be equipped with pair of electrodes in the container that can adorn water, and is equipped with the reductive water generating apparatus to the AC power of this electrode application voltage, wherein, has selected carbon dioxide process carbon electrode as electrode.

(2) as above-mentioned (1) described reductive water generating apparatus, it is characterized in that, AC power is set at the degree that can form oxide scale film on the surface of this carbon dioxide process carbon electrode to the length that each carbon dioxide process carbon electrode applies the time of negative (-) voltage, and described oxide scale film is the degree that does not influence the electroconductibility of electrode and water; AC power is just applied the length of the time of (+) voltage to each carbon dioxide process carbon electrode is set at the established oxide scale film of dissolving, and carbon particles from the electrode surface stripping to water before the degree that just finishes.

In the present invention based on the formation of above-mentioned (1), can generate reductive water with the few state of chlorion, hypochlorite ion and chlorine molecule, particularly in the formation of above-mentioned (2), can reduce carbon particles stripping in the carbon dioxide process carbon electrode in water.

Description of drawings

Fig. 1 is the sectional side view that shows the basic comprising of the device that the present invention relates to, and (a) shows the situation that two electrode design is become basic sustained height, (b) shows the situation that two electrode design is become different heights.

Fig. 2 (a) shows the different situation of application time, (b) the different situation of peak value display for showing the figure of the state that utilizes the sinusoidal wave asymmetric voltage of alternating current that forms.

Fig. 3 (a) shows the symmetric alternating current voltage condition for showing the situation of the voltage of alternating current that applies the square wave pulse formation, (b) shows the situation of the asymmetric voltage of alternating current that application time is different, (c) situation of the asymmetric voltage of alternating current that peak value display is different

The explanation of symbol

1. carbon dioxide process carbon electrode

2. container

3. AC power

Embodiment

In the present invention, as shown in Figure 1, be provided with a pair of carbon dioxide process carbon electrode 1 in the container 2 that can adorn water, and be provided with ac voltage power supply, this ac voltage power supply can alternately apply just (+) voltage and negative (-) voltage between a pair of carbon dioxide process carbon electrode 1.

As the configuration of pair of electrodes, for example, can be shown in Fig. 1 (a) like that, design is at basic sustained height, can be designed to make a lateral electrode to be positioned at the position that is higher than the opposite side electrode shown in Fig. 1 (b) like that, two interelectrode distributing styles be not must be specific yet.

But, under the situation that adopts asymmetric voltage of alternating current described later, the distributing style of preferred Fig. 1 (b), its reason illustrates in the specification sheets of back.

In the present invention, the embodiment shown in Fig. 1 (a) and (b) is such, can only utilize a pair of carbon dioxide process carbon electrode to generate reductive water, but the same with the situation of existing reductive water generating apparatus, does not get rid of the formation that ground-electrode is set in addition especially.

Under the situation that is carbon dioxide process carbon electrode 1, owing between formation crystalline carbon particles, have the space, so can think that chlorion, hypochlorite ion and chlorine molecule in the water are adsorbed between this space, consequently, compare with the situation of other electrode, the residual degree of the chlorion in the reductive water, hypochlorite ion and chlorine molecule reduces.

But under the situation that is carbon dioxide process carbon electrode 1, the carbon that constitutes carbon particles is dissolved in the water after ionization, and (the H that forms carbonic acid sometimes ₂CO ₃).

In the formation of above-mentioned (2) by carrying out following operation repeatedly, so that the stripping of carbon in water reduces, described operation is before carbon dissolution is in the water, each electrode becomes the stage of negative electrode, utilize the cation compound in the water to form oxide scale film with the degree that the electroconductibility that does not make electrode and water is lost at electrode surface, becoming the anodic stage, remove the oxide scale film that has formed gradually, after this is removed, in the carbon generation ionization that constitutes carbon particles, stripping in the water before, be varied to negative electrode once more and (according to the above description, should prevent the stripping of blocking in water in theory, but in fact, when forming oxide scale film, and then the stage after removing oxide scale film, the carbon stripping of trace is in water, can not prevent the stripping of blocking in water fully, thereby show as " minimizing " all the time).

Like this, in the basic comprising of above-mentioned (2), formation by carrying out oxide scale film repeatedly with and remove the alternative cycle that forms, different fully with the situation of the existing reductive water generating apparatus that has used high-frequency alternating current, be generally the long-time of great disparity.

The concrete time is along with the density that applies voltage and the carbon that constitutes employed carbon dioxide process carbon electrode 1 is different and different, but in the most carbon composite electrode that is adopted, be under the situation of alternating-current of 10V at the peak value of the voltage that makes two electrodes, as the semi-period of this alternating-current, be set at 50～200 seconds mostly.

In the formation of above-mentioned (1) and (2), under the situation that applies common voltage of alternating current, this voltage is as the situation of common alternating-current, the voltage waveform that forms by semi-period of semi-period of just (+) and negative (-) be with the zero potential be the center and symmetric (below, abbreviate " symmetric alternating current voltage " as), can obtain the ORP value and be about reductive water about 0mV.

Having applied under the symmetric alternating current voltage condition, around electrode, and then in container 2, though hydrogen ion (H ⁺) and hydroxide ion (OH ^-) distribute substantially equably, but such as mentioned above, can obtain reductive water can be interpreted as: because the hydrogen ion (H that generates in water ⁺) and hydroxide ion (OH ^-) in, molten in hydrogen ion and the water deposited oxygen and combine and newly form water, and be relative therewith, and hydroxide ion combines and forms hydrated hydroxide ion (hydroxium) (HO with the molten oxygen of depositing ₃ ^-) probability very low, thereby remain in the water.

But, adopting to apply under the situation of embodiment that following alternating-current is a feature, can further reduce the OPR value, described alternating-current is, in the formation of above-mentioned (1) and (2), by during just (+) and negative (-) during formed voltage waveform, not to be the symmetry status at center with the zero voltage, and, in a specific electrode, just the time integral value of (+) voltage is greater than the time integral value of negative (-) voltage, in another electrode, just the time integral value of (+) voltage is less than the time integral value of negative (-) voltage (below, such alternating-current is abbreviated as " asymmetric voltage of alternating current ").

Can to reduce the foundation of reduction potential not necessarily clear by applying asymmetric voltage of alternating current.

But, can think, based on asymmetric voltage of alternating current, in a lateral electrode that has applied more just (+) voltage, hydrogen ion (H ⁺) than hydroxide ion (OH ^-) densification more, relative therewith, in the electrode of the opposite side that has applied more negative (-) current potentials, hydroxide ion (OH ^-) than hydrogen ion (H ⁺) densification more, in a lateral electrode, compare hydrogen ion (H with the symmetric alternating current voltage condition ⁺) situation of newly-generated water is more by combining with the molten oxygen of depositing, and is relative therewith, in the opposite side electrode, compares with the symmetric alternating current voltage condition, intensive hydroxide ion (OH ^-), not with hydrogen ion (H ⁺) in conjunction with and remaining situation becomes many.

So, applying under the situation of asymmetric voltage of alternating current, at the distributing style that adopts Fig. 1 (b) and the electrode that is configured in downside is that the voltage that applied makes it just under the situation of time integral value greater than the time integral value of negative (-) voltage of (+) voltage, the hydrogen ion (H of the more amount that generates in this electrode ⁺) in, not with water in hydroxide ion (OH ^-) the bonded part, do not become hydrogen atom (H immediately ₂) and diffuse in the air, but can combine with the molten oxygen of depositing in the water, therefore applying under the situation of asymmetric voltage of alternating current, preferably behind the distributing style of selecting Fig. 1 (b), apply voltage as described above at the electrode of downside.

As the mode that applies of asymmetric voltage of alternating current, there are following two kinds of embodiments, that is, such embodiment shown in Fig. 2 (a), this mode is characterised in that just (+) voltage application time set is for being longer than negative (-) voltage application time; And then, such embodiment shown in Fig. 2 (b), this mode is characterised in that just the peak value of (+) voltage is set at the peak value greater than negative (-) voltage.

Therefore, in order to obtain the low reductive water of ORP value, preferably utilize the embodiment of asymmetric voltage of alternating current as described above.

The waveform of the voltage of alternating current that applies not is to be defined in the such sine wave of Fig. 2 (a) and (b), certainly, many times adopts square wave pulse as shown in Figure 3.

Fig. 3 (a) has shown the symmetric alternating current voltage of square wave pulse formation, Fig. 3 (b) has shown that the difference of utilizing peak value corresponding with Fig. 2 (a) forms the square wave pulse of asymmetric voltage of alternating current, Fig. 3 (c) has shown that the utilize temporal differences corresponding with Fig. 2 (b) forms the square wave pulse of asymmetric voltage of alternating current, but under the situation of square wave pulse, owing to can easily realizing the generation of asymmetric voltage of alternating current and applying, so generate the low reductive water of ORP value easily.

Experience according to inventors, apply in the embodiment of the different asymmetric voltage of alternating current square wave pulse of application time such shown in Fig. 3 (b), in the embodiment of the asymmetric voltage of alternating current square wave pulse different, can reduce the ORP value efficiently with applying peak value such shown in Fig. 3 (c).

Fig. 2 and voltage shown in Figure 3, demonstration be voltage between pair of electrodes, the current potential of two electrodes and nonessential demonstration Fig. 2, the such state of Fig. 3.

That is, can certainly adopt following design, promptly for the lateral electrode in the pair of electrodes, be set to the such current potential of Fig. 2, Fig. 3, the electrode that opposite side is set makes it become zero potential.

With under reductive water generating apparatus of the present invention and the situation that water purifier combines, can drink the residual chlorine ion and the residual chlorine molecule is few, and neutral or the weakly alkaline water that is cleaned.

Below, describe according to embodiment.

Embodiment 1

In embodiment 1, be characterised in that, behind the asymmetric voltage of alternating current that adopts the different square wave pulse formation of application time such shown in Fig. 3 (b), with respect to electrode of another electrode pair apply 30～60 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, this square wave pulse has the peak value of 8～20V, the time length of pulse is 2000～4000 microseconds, the timed interval with 100～150 microseconds produces pulse successively, and applying 60～120 seconds negative (-) voltage, this negative (-) voltage is by the square wave pulse formation that produces same square wave pulse with the same timed interval successively.

The asymmetric voltage of alternating current square wave pulse that such difference of utilizing application time is produced, under the situation of the voltage that adopts numerical definiteness scope as described above and each application time, can obtain the residual chlorine ion or the chlorine molecule is few, and the low reductive water of OPR value.

Below, describe according to test-results.

[test]

Apply 45 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, this square wave pulse has the peak value of 12V, the time length of pulse is 3000 microseconds, the timed interval with 125 microseconds produces pulse successively, then, apply 85 seconds negative (-) voltage, should bear (-) voltage by the square wave pulse formation that produces same square wave pulse with the same timed interval successively, behind the asymmetric voltage of alternating current of selecting such square wave pulse formation, concentration of residual chlorine and reduction potential under following three kinds of situations are measured, described situation is

(1) after making tap water pass through activated charcoal filter in advance, tap water is accommodated the electrode that only adopts a pair of platinized titanium and do not adopt in the reductive water generating apparatus of ground-electrode, apply the situation of asymmetric voltage of alternating current of the square wave pulse formation of above-mentioned selection,

(2) do not make tap water pass through activated charcoal filter in advance, tap water is accommodated in the reductive water generating apparatus with the pair of electrodes of utilizing the platinized titanium electrode and ground-electrode, apply the high frequency symmetric alternating current voltage condition of the frequency that had 40khz in 20 minutes, this high frequency symmetric alternating current voltage is formed by the square wave pulse of peak value by 26V

(3) after making tap water pass through activated charcoal filter in advance, tap water accommodated only adopt a pair of carbon composite electrode and do not adopt in the reductive water generating apparatus of ground-electrode, apply the situation of asymmetric voltage of alternating current of the square wave pulse formation of above-mentioned selection in 12 minutes.

The result is as shown in table 1.

[table 1]

Subjects		(1)		(2)		(3)
Subjects		(1)		(2)		(3)		The kind of test		The concentration ※ of residual chlorine (ppm)	ORP value (mV)	The concentration ※ of residual chlorine (ppm)	ORP value (mV)	The concentration ※ of residual chlorine (ppm)	ORP value (mV)
Sample	1	1.0	-127	0.8	-88	0.2	-140	The kind of test		The concentration ※ of residual chlorine (ppm)	ORP value (mV)	The concentration ※ of residual chlorine (ppm)	ORP value (mV)	The concentration ※ of residual chlorine (ppm)	ORP value (mV)
	1	1.0	-127	0.8	-88	0.2	-140	2	1.3	-138	0.6	-97	0.1	-139
	3	1.0	-139	0.8	-106	0.2	-148	2	1.3	-138	0.6	-97	0.1	-139
	3	1.0	-139	0.8	-106	0.2	-148	On average		1.1	-134.7	0.7	-97	0.17	-142

The above-mentioned concentration of residual chlorine of ※ comprise chlorion and chlorine molecule the two.

By above-mentioned experimental result as can be known, when adopting existing platinized titanium electrode, as as indicated in the contrast of above-mentioned (1) and (2), by not using ground-electrode and applying asymmetric voltage of alternating current, can reduce reduction potential, but compare with having applied the symmetric alternating current voltage condition, it aspect residual degree of chlorion and chlorine molecule is being non-constant.

On the other hand, as as indicated in the contrast of above-mentioned (1) and (3), under the situation that has applied the formed asymmetric voltage of alternating current of same square wave pulse, compare with the situation of the titanium electrode of conventional example, can distinguish, carbon dioxide process carbon electrode 1 as embodiments of the invention can obtain low a little ORP value, and aspect concentration of residual chlorine, carbon dioxide process carbon electrode 1 is obviously excellent simultaneously.

And then, as as indicated in the contrast of above-mentioned (2) and (3), compare with such employing titanium electrode of conventional example and the symmetric alternating current voltage condition that applies the square wave pulse formation, can distinguish, the situation that on carbon dioxide process carbon electrode 1, applies the asymmetric voltage of alternating current of square wave pulse formation that embodiments of the invention are such, aspect ORP value and concentration of residual chlorine any, can obtain very low value.

Embodiment 2

In embodiment 2, be characterised in that, behind the asymmetric voltage of alternating current that adopts the different square wave pulse formation of peak value such shown in Fig. 3 (c), with respect to another electrode and to an electrode apply 30～60 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, this square wave pulse has the peak value of 8～20V, the time length of pulse is 2000～4000 microseconds, the timed interval with 100～150 microseconds produces pulse successively, and apply 100～200 seconds negative (-) voltage, should bear (-) voltage by the square wave pulse formation, this square wave pulse has the peak value of 15～40V, the time length of pulse is 2000～4000 microseconds, the timed interval with 100～150 microseconds produces pulse successively.

In being applied with the electrode of (+) voltage just, the amount of the amount of the hydrogen ion (H+) that generates and the hydroxide ion (OH-) that in the electrode that is applied with negative (-) voltage, generates, proportional with the integrated value of each voltage, and, in embodiment 2, also can obtain action effect similarly to Example 1.

Particularly, situation according to the test of embodiment 1, apply 45 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, this square wave pulse has the peak value of 12V, the time length of pulse is 3000 microseconds, the timed interval with 125 microseconds produces pulse successively, then, apply 125 seconds negative (-) voltage, should bear (-) voltage by the square wave pulse formation, this square wave pulse has the peak value of 23V, the time length of pulse is 3000 microseconds, the timed interval with 125 microseconds produces pulse successively, after selecting so asymmetric voltage of alternating current, under the situation that a pair of carbon dioxide process carbon electrode of the present invention is pressurizeed, certainly infer out with the situation of the test of embodiment 1 equally, can obtain the residual chlorine ion or the chlorine molecule is few, and the reductive water that the ORP value is low.

The industry utilizability

Reduced water generation device of the present invention can be used for the generation of drinking water, the manufacturing of industrial reductive water etc.

Claims

1. a reductive water generating apparatus is to be equipped with pair of electrodes in the container that can adorn water, and is equipped with the reductive water generating apparatus to the AC power of this electrode application voltage, it is characterized in that, has selected carbon dioxide process carbon electrode as electrode.

2. reductive water generating apparatus as claimed in claim 1, it is characterized in that, AC power is set at the degree that can form oxide scale film on the surface of this carbon dioxide process carbon electrode to the length that each carbon dioxide process carbon electrode applies the time of negative (-) voltage, and described oxide scale film is the degree that does not influence the electroconductibility of electrode and water; AC power is just applied the length of the time of (+) voltage to each carbon dioxide process carbon electrode is set at the established oxide scale film of dissolving, and carbon particles from the electrode surface stripping to water before the degree that just finishes.

3. reductive water generating apparatus as claimed in claim 1 or 2, it is characterized in that, be set at a lateral electrode with respect to the opposite side electrode for the time integral value of (+) voltage just greater than time integral value for negative (-) voltage, and be set at the opposite side electrode with respect to this lateral electrode for the time integral value of (+) voltage just less than time integral value for negative (-) voltage.

4. reductive water generating apparatus as claimed in claim 3 is characterized in that, just (+) voltage application time set is for being longer than negative (-) voltage application time.

5. reductive water generating apparatus as claimed in claim 3 is characterized in that, just the peak value of (+) voltage is set at the peak value greater than negative (-) voltage.

6. as each described reductive water generating apparatus in the claim 1,2,3,4,5, it is characterized in that the current potential that makes an electrode in the pair of electrodes is a zero potential.

7. as each the described reductive water generating apparatus in the claim 1,2,3,4,5,6, it is characterized in that just (+) voltage and negative (-) voltage all are the aggregate of square wave pulse.

8. as claim 5,6,7 each described reductive water generating apparatus, it is characterized in that, with respect to electrode of another electrode pair apply 30～60 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, the time length that this square wave pulse has peak value, the pulse of 8～20V is 2000～4000 microseconds, produces pulse successively with timed interval of 100～150 microseconds, and applying 60～120 seconds negative (-) voltage, this negative (-) voltage is by the square wave pulse formation that produces same square wave pulse with the same timed interval successively.

9. reductive water generating apparatus as claimed in claim 8, it is characterized in that, apply 45 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, the time length that this square wave pulse has peak value, the pulse of 12V is 3000 microseconds, produces pulse successively with timed interval of 125 microseconds, then, apply 85 seconds negative (-) voltage, this negative (-) voltage is by the square wave pulse formation that produces same square wave pulse with the same timed interval successively.

10. as claim 5,6,7 each described reductive water generating apparatus, it is characterized in that, with respect to electrode of another electrode pair apply 30～60 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, this square wave pulse has the peak value of 8～20V, the time length of pulse is 2000～4000 microseconds, the timed interval with 100～150 microseconds produces pulse successively, and apply 100～200 seconds negative (-) voltage, should bear (-) voltage by the square wave pulse formation, this square wave pulse has the peak value of 15～40V, the time length of pulse is 2000～4000 microseconds, the timed interval with 100～150 microseconds produces pulse successively.

11. reductive water generating apparatus as claimed in claim 10, it is characterized in that, apply 45 seconds (+) voltage just, this just (+) voltage by the square wave pulse formation, the time length that this square wave pulse has peak value, the pulse of 12V is 3000 microseconds, produces pulse successively with timed interval of 125 microseconds, then, apply 125 seconds negative (-) voltage, should negative (-) voltage by the square wave pulse formation, the time length that this square wave pulse has peak value, the pulse of 23V is 3000 microseconds, produces pulse successively with timed interval of 125 microseconds.

12. as claim 1,2,3,4,5,6,7,8,9 each described reductive water generating apparatus, it is characterized in that, combine with water purifier.