WO2006127633A2

WO2006127633A2 - Acidic electrolyzed water production system and protection membrane

Info

Publication number: WO2006127633A2
Application number: PCT/US2006/019793
Authority: WO
Inventors: Yoichi Sano; Barry R. Taylor
Original assignee: Electrolyzer Corp.
Priority date: 2005-05-20
Filing date: 2006-05-22
Publication date: 2006-11-30
Also published as: WO2006127633A3; US7967958B2; US8858765B2; US20060260954A1; US20060260931A1; EP1926842A2

Abstract

An improved device and method for the creation of acidic electrolyzed water is described. The device has an flow-through anode chamber and a static cathode chamber. The static cathode chamber contains a fixed amount of salt-containing electrolyte, which is renewed as needed. The flow rate of water through the anode is restricted to a range of about 5 to 40 ml per ampere of current passed through the electrode. Electrolyzed water flowing from the anode is diluted to obtain the desired concentration of hypochlorous acid, and is collected in a tank or other vessel. The electrolysis reaction is terminated when a preset amount of current has passed through the anode. Water circulation may be one pass or recycling. In a preferred embodiment, the membrane is anion-selective. Preferably, the membrane and the electrodes are integrated into a preassembled format that can be attached to the anode and cathode compartments via flanges or similar devices allowing quick replacement of an electrode assembly in an electrolyzer. The anion-permeable membrane can be protected by a protection membrane, in which are provided slits or other discontinuities to allow venting of gas.

Description

Acidic Electrolyzed Water Production System and Protection Membrane

PRIORITY

This application is a continuation-in-part of, and claims priority to, co-pending Japanese applications JP 2005- 175654 and JP 2005-147,482, each filed May 20, 2005, and each of which is hereby incorporated by reference in its entirety where permitted.

FIELD OF THE INVENTION

This invention relates to a method for the production of hypochlorous acid-bearing acidic electrolyzed water, to an apparatus for such production, and to a control method for said production; and to a protective membrane for an ion exchange membrane in such a device.

BACKGROUND

Batch type production formats are known that generate hypochlorous acid-bearing acidic electrolyzed water, using raw water that has been stored in a vessel having a fixed capacity. These formats use an electrolysis tank in which the positive electrode chamber and the negative electrode chamber have been divided by a separation membrane. The electrolysis is done in the positive electrode chamber and the negative electrode chamber, using water for electrolytic processing that has had a small amount of a chloride-containing salt added to it to form the electrolyte. Typically, flow through an anode compartment generates acid electrolyzed water, and flow through a cathode compartment generates alkaline electrolyzed water.

However, there are many problems with this approach. In particular, although acidic electrolyzed water possesses strong bactericidal power, and is a desirable water that causes little contamination of people or the environment, the production systems of the past have weaknesses such as the fact that the resulting acidic water contains salt, has a strong smell of chlorine, and easily corrodes metals. In addition, from the standpoint of the production process, there are troublesome cases in which the generation of alkaline water creates problems. In the marketplace, devices that generate salt-free acidic electrolyzed water without generating alkaline water are not readily available. Finally, in some production systems that employ a cation exchange membrane, the presence of some cations in the salt can foul the ion- selective membrane. Consequently, restrictions are placed on the purity of the electrolyte salt that limit the possible grades of salt that can be used in such systems. A system is desired with which stable, reproducible generation of acidic electrolyzed water can be done, where the generation of alkaline water can be avoided or minimized, and where limits on the impurity content of the electrolyte salt can be relaxed.

In another aspect, electrolyzers rely on separation membranes to function efficiently, so that chloride ions can pass to an anode. These membranes are preferably anion selective when acid electrolyzed water is produced. The chlorine generated can damage these membranes, shortening their lifetimes or preventing efficient production of chlorine. Such problems are common to many methods of operating an electrolyzer , beyond the improved apparatus to be described. For example, two other methods are known in the art for electrolyzing water to produce acidic electrolyzed water that contains available chlorine and has sterilization capability: (I) a method of generating acidic electrolyzed water that contains available active. chlorine in the positive electrode chamber, by flowing tap water, into which a small amount of electrolyte containing chloride ions has been added, through both chambers of a two-chamber electrolysis apparatus which has a positive electrode chamber and a negative electrode . chamber, separated by a permeable membrane to perform the electrolysis; and (2) a method of generating acidic electrolyzed water by placing a liquid containing chloride ions in the center chamber of a three-chamber electrolysis apparatus, which is made up of a positive electrode chamber, a negative electrode chamber and a center chamber where, by passing tap water through both the positive electrode chamber and the negative electrode chamber, and applying a DC voltage to the positive electrode and negative electrode, the chloride ions in a chloride-containing electrolyte in the center chamber are caused to migrate to the positive electrode chamber, through the principle of electro-dialysis, generating acidic electrolyzed water that includes available active chlorine by the electrolysis reaction in the positive electrode chamber. Other methods are known, including an improved method described in JP 2005- 175,654.

The electrolytic reactions that occur on the surface of or near the positive electrode surface include both a desired reaction that generates chlorine gas from chloride ions, and the competing reaction of water that generates hydrogen ions and oxygen gas. Suppression of the reaction of water is important for increasing the production rate of chlorine gas needed to enhance the generation efficiency of available chlorine. Methods for performing this suppression of oxygen generation include

(1) placing the positive electrode plate and permeable membrane in close proximity to one another and generating effective electrolysis prior to the transmission of the chloride ion through the permeable membrane and its dispersal in a large amount of water; and

(2) restricting the amount of tap water for electrolysis passed through the positive electrode chamber with respect to the current applied, in order to increase the concentration of chloride ions in the positive electrode chamber and to increase the probability of the chlorine reacting. (These reactions are described in JP 3, 1 13,645).

In either of these methods the electrodes and the permeable membrane are placed as close together as possible to enhance the production efficiency of acidic electrolyzed water. However, with the permeable membrane and electrodes placed in close proximity in this manner, especially in the case where an ion exchange membrane is used as the permeable membrane, the ion exchange membrane and its supporting material deteriorate and break down more easily due to chlorination by chlorine gas generated at the electrode.

Problems of the Prior Art To Be Solved by the Invention

This invention relates to a method of generating electrolyzed water, in which acidic electrolyzed water is generated while generating little or no alkaline electrolyzed water, and in which no salt is contained in the generated water. Thereby, electrolyzed water is generated for which the chlorine smell is low. The electrolysis tank (electrolyzer) contains no cation exchange membrane, so impurity requirements for the electrolyte salt are relaxed. Moreover, the installation and removal of the electrodes is simple, and further, it is possible to generate, in a short period of time, acidic electrolyzed water that reproducibly exhibits targeted physical properties.

In Japanese patent JP 3, 1 13,645, by the inventor of the present invention, the chloride concentration in the water in the anode chamber is increased by limiting the flow rate of water through the positive electrode (anode) chamber to a rate of 5 to 40 cc per minute per ampere of current. This increases the efficiency of chlorine production on the surface of the positive electrode (anode). The conversion of chlorine to hypochlorous acid is promoted by mixing the electrolyzed water with additional water after the electrolyzed wate3r leaves the anode compartment. Consequently, the amount of chlorine that escapes from the generated water is reduced, and the smell of chlorine is made low.

A method that generates acidic electrolyzed water that does not include any salt content, and while generating very limited amounts of alkaline electrolyzed water, is described in Japanese Patent Number 3,551 ,288 by the inventor of the present invention for a system in which the acidic water is stagnant.

Summary of the Invention

The present invention is an improvement over the above art. In one improvement, as the means with which hypochlorous acid-bearing acidic electrolyzed water having a low chlorine smell is generated efficiently, means are provided in which an extremely limited amount of raw water is introduced, by a liquid distribution device, into the positive electrode chamber. Chloride ions are selectively introduced into the water in the positive electrode (anode) chamber in close proximity to the anode through an anion selective membrane. The limited amount of raw water is electrolyzed there, and then it is removed from the positive electrode chamber and mixed with non-electrolyzed water. For selecting the amount of raw water that is introduced into the positive electrode chamber to be treated, a flow rate of 5 to 40 cc per minute per ampere of current is preferred.

The positive electrode (anode) and negative electrode (cathode) chambers are separated by an anion selective membrane. The salt electrolyte is contained in the form of a solution in the negative electrode (cathode) chamber . The electrolyte is preferably highly concentrated, and may contain undissolved salt.

In addition, to make the attachment and removal of the electrodes simple, means are provided in which the positive and negative electrode plates and the separating membrane have been integrated into a single unit, that is held between flanges or other attachment means that have been attached to the negative electrode chamber and the positive electrode chamber. As described in JP 3,551 ,288 for a non-integrated membrane, the membrane in the integrated unit may be a non-ion selective membrane or an anion-selective membrane, and preferably is an anion-selective membrane, of any of the types known in the art.

Also, as a means with which the generated water that accurately exhibits the target physical properties can be produced in a short period of time, an embodiment is provided in which the end of the electrolysis process is determined by integrating the current over time, for example collecting values determined at fixed time intervals, such as each second, and then terminating the electrolysis when the total amount of electricity supplied to the cell reaches a selected value. The selected value will depend on various factors, including the desired final level of active chlorine (hypochlorous acid plus hypochlorite ion plus chlorine gas) or equivalent in the electrolyzed water, and the activity efficiency of the electrodes surfaces toward the various electrolysis reactions and their catalysts. In one embodiment, the selected value is in the range of 420 ±200 coulombs per liter of raw water that is processed. An alternative embodiment is a format for use in those cases where the current is stable to some degree, where a timer is used instead of integrating the current, and the time is regulated.

In another embodiment, the present invention is a batch type acidic electrolyzed water production system characterized in that the system uses an electrolyte cell having an easily removable electrode assembly with a unitary, integrated structure, in which the positive and negative electrode plates, and the separating membrane that is in between these plates, are arranged in a layered assembly, and connected, using a flange or the like, in between the positive electrode chamber and the negative electrode chamber.

Regarding a protection membrane, the invention uses a negative ion permeable membrane, preferably a negative ion exchange membrane, as the permeable membrane, and generates chlorine gas in the positive electrode chamber of an electrolysis apparatus, where the positive electrode and the permeable membrane are placed in close proximity to one another, thereby providing an improved method of producing acidic electrolyzed water containing available chlorine. The improvement is in providing a water electrolysis electrode that solves the difficulty of maintaining stable production, said difficulty being caused by deterioration of the negative ion exchange membrane from the chlorine gas generated on the positive electrode surface. This is accomplished by placing a porous fabric-like material between the electrode and the anion-permeably membrane. To prevent accumulation of gas, the protection membrane has discontinuities, such as slit-like openings or holes.

Brief Description of the Drawings

Fig. I is an overall flow diagram of the water electrolysis system for one embodiment of the two-chamber electrolyzer of the present invention. Fig. 2 is an oblique view drawing that shows the relationships among the components; and Fig. 3 is an exterior drawing of the batch type water electrolysis system of one embodiment of the present invention.

Figures 4 - 9 show the protective membrane in two types of electrolyzers. Figure 4: Assembly drawing of an example of an electrode used for water electrolysis of the present invention. Figure 5: Cross sectional drawing of an example of a protection membrane used in the present invention. Figure 6: A perspective drawing of another protection membrane used in the present invention. Figure 7: Perspective drawing that shows a usage example of an electrode used for water electrolysis of the present invention. Figure 8: Assembly drawing of another example of an electrode used for water electrolysis of the present invention. Figure 9: Perspective drawing of an example of an electrode used for water electrolysis of the present invention.

Detailed Description of the Invention

An example of the batch type water electrolysis system of the present invention is shown in Fig. I . Fig. I is a line diagram in which the water electrolysis system is shown. In this embodiment, the electrolysis system has an assembled electrolyzer assembly (V), which has been furnished with an electrolyte container (L) which is in fluid connection with the negative electrode chamber (cathode chamber) (X), which consists of the space inside frame (7) of integrated electrode assembly (J), and a space ( 12) cut into the face of flange ( N). (Y) is the positive electrode chamber, formed in the space inside frame (7) of integrated electrode assembly (J), and optionally in a space (not illustrated) cut into the positive electrode chamber bounding plate (K) . Flanges (M) and (N) are used to connect the two chambers (X) and (Y) and the electrode assembly (J), using fastener means such as bolts (see Fig. 2) to form the electrolyzer assembly (V). The direct current power source (D) is connected to said electrode assembly (J). (E) is a raw water tank, (F) is a circulation pump, (G) is a liquid distribution device, and (H) is a liquid mixing device. The water that has been delivered by the circulation pump (F) from the raw water tank (E) is distributed by the liquid distribution device (G) both to the water in the positive electrode chamber (Y), which is water that will be electrolyzed, and to liquid mixing device (H), which is water that will not be electrolyzed, but used to immediately dilute electrolyzed water that is leaving the electrolyzer assembly (V).

Both of the waters are mixed by the liquid mixing device (H) and, at the same time, the water and the chlorine gas that is generated in the positive electrode chamber are reacted, forming hypochlorous acid, and the mixture is returned once more to the raw water storage tank. A separate pump can be used for the distribution of water for electrolysis, instead of using a distribution device (G).

However, it should be noted that as a matter of convenience with regard to the layout of the piping, there are cases, which are not illustrated here, in which both of the waters are again returned to the raw water storage tank (E) without first mixing, i.e., in which there is no mixing device (H). There are other cases, not illustrated, in which the raw water storage tank is not the same as the tank that the electrolyzed water mixed with the non-electrolyzed water is stored in. It is not required that the raw water comes from a storage tank, such as tank (E); it could come from a continuous water source, and be regulated in amount by timing, weight or other means. The electrolysis time or charge is calculated, limited according to the result of the calculation, and the acidic electrolyzed water having the target effective chlorine concentration is thereby generated.

A salt for electrolysis, which is a chloride salt such as sodium chloride, potassium chloride or other chloride salt, is put into the electrolyte storage tank (L) of the negative electrode (cathode) (X). As the electrolysis of the electrolyte progresses, the chloride ions in the cathode move to the positive electrode (anode) chamber (Y) due to electrodialysis, and the chloride ions are replaced in the storage tank by hydroxyl ions, producing a hydroxide such as sodium hydroxide or the like. At some point, it is necessary to exchange the cathode solution with a fresh electrolyte solution before the chloride ions have disappeared, or before the alkalinity becomes excessive.

Fig. 2 shows a perspective drawing of a particular design of the electrolyzer assembly (V), which includes the negative electrode chamber (X), which may serve as the electrolyte storage tank, and the positive electrode chamber (Y) as well as the integrated electrode assembly (J), all of which are fastened together by the flanges (N) and (M) to form the electrolysis assembly (V). The integrated electrode assembly (J) is composed of a frame (47), a positive electrode (+), a membrane (46), a negative electrode(-) and a second frame (47). Other features of this embodiment are bolt holes 48, 49, 50, 51 in flanges M and N; and inlet (53) for raw water and outlet (54) for electrolyzed water in plate (K). The gaskets (Z) are not illustrated in this view.

Fig. 3 is an exterior view drawing of one version of a complete batch type acidic electrolyzed water production system. (E) is the raw water tank, (L) is a portion of the negative electrode chamber/ electrolyte storage tank shown in Fig. 2, (O) is a control box, also containing the pump (F) (not shown), (P) is the electrolysis control setting device or the timer, and (R) is the water supply orifice for placing water in the tank (E).

In a preferred embodiment, the electrolyte solution storage tank (L), connected to the cathode chamber (X), is a static system, in which the electrolyte solution is periodically replaced as its chlorine content is depleted. Electrolytes may include, but are not limited to, chlorides of alkali metals, such as sodium and potassium. Raw water is delivered from a raw water storage tank (E) that, in the illustrated embodiment, has a fixed capacity, by a pump (F). Then by means of a liquid distribution device (G), the raw water is distributed in part to the anode chamber (Y) as water that is electrolyzed and generates acidic electrolyzed water, and in part as other raw water not to be electrolyzed that is delivered so that it bypasses the anode. Only the amount of water that is electrolyzed in anode chamber (Y) is regulated at a flow rate of 5 to 40 cc per minute per ampere of current. After the electrolysis, the acidic electrolyzed water from the anode chamber (Y) is collected in a storage tank (E), which in this embodiment is the same as the supply tank . The acidic electrolyzed water may be diluted with other raw water after it leaves the anode the integrated electrode assembly (J), either by in-line dilution or by separate delivery of raw water to a storage tank. In one embodiment, the storage tank (E) for collection may be the same tank that originally contains the raw water for making the batch of acidic electrolyzed water. In this embodiment, some water passes through the anode chamber and is returned to the tank (E), and optionally other water is circulated by a pump, and returns to the tank without electrolysis, for example to promote efficient mixing. The electrolyzed and non-electrolyzed water may be mixed at any point after the acidic electrolyzed water has left the anode compartment, either directly in tank (E) or in a mixer (H).

It should be noted that while dilution of acid electrolyzed water after it leaves the anode compartment (Y) is possible and in some cases preferred, it is also possible to collect or use acid electrolyzed water without further dilution. One or both of the current and the residence time of water in the anode compartment has to be adjusted appropriately to provide the required final active chlorine concentration. (Active chlorine is the total chlorine present as any of hypochlorous acid, hypochlorite anion, and dimeric chlorine, all of which are in an equilibrium determined by pH and secondarily by other factors.)

In another embodiment, the present invention is a batch type acidic electrolyzed water production method, characterized by the use of a direct current power source (D) to provide electrical power to an electrolyzer, further characterized by the generation in an anode compartment (Y) of acidic electrolyzed water of known volume W liters, which may be contained in a tank, that is characterized by a known relationship between a target property in the volume W of acidic electrolyzed water, and the cumulative electric charge C (for example, in coulombs or ampere-seconds) required to achieve that property, and also characterized by the integration versus time of the electrical current passed through the electrolyzer assembly (V). When the integration value Q in the selected units is equal to the target value C, the generation of the acidic electrolyzed water is completed. The desired property is one that characterizes the usefulness of the acidic electrolyzed water. In one embodiment the property is the concentration of hypochlorous acid or of total active chlorine in the water in the collection tank, or in the stream of water leaving the anode compartment (Y). In another embodiment the property is the pH in the collection tank. The collection tank may be the same as the fixed volume supply tank (E), or may be a different tank (not illustrated.)

In another embodiment, the present invention is a batch type acidic electrolyzed water production method, characterized in that a direct current power source to provide a fixed current to an electrolysis tank. The processing time that is required for the time integral of the current that is passed through the electrolysis tank to reach a target value of C coulombs/liter (for the W liters in the storage tank having an active chloride level of U ppm) is calculated. The time is set with a timer, and the generation is terminated when the predetermined generation time is reached.

In one preferred embodiment, in which the target active chlorine level is about 30 ppm, the time required to apply about 420 ±200 coulombs per liter of water electrolyzed is calculated, the time is set with a timer, and the generation is terminated when the pre-selected value of total coulombs loaded is reached. The figure is derived from the multiplication of the desired level V of active chlorine (in parts per million) with a factor A. Factor A is in the range of about 8 to 20, in appropriate units, and is a measure of the efficiency of conversion of current flow through the membrane into production of hypochlorite from chloride. (In a perfectly efficient conversion, the value of A would be I). In effect, the time required T may be calculated as T + (AUW)/C

Also, in order to make it such that the physical properties of the generated water can be produced simply and accurately, two methods are described. In a first method, the value of the electrolyzing current is integrated and the point in time at which the coulomb value per liter has reached a predetermined value is made the end point of the generation reaction. In a second method, a power source that can supply a fixed current or voltage is used, the mean electrolyzing current is sought in advance, the time that is required for the coulomb amount to reach the predetermined value is calculated, and the time is set with a timer. An example of a predetermined value is a number lying in the range of 420 +/- 200 (i.e., the range 220 - 620) coulombs per liter of water, but other predetermined values may be set depending on the desired concentration of hypochlorous acid in the product, on the efficiency of the particular electrolyzer, and on local regulations affecting the selected value, for example regulating the pH. These methods are judged to have advanced qualities with regard to the fact that straightforward and logical formats with which the amount of electricity per liter of raw water is regulated to be held constant have been utilized as suitable methods for the simple production of acidic electrolyzed water having an effective chlorine concentration, which is the target, with a batch type acidic electrolyzed water production system.

An additional advantage of the preferred embodiment described is that the simplicity of changing the electrode. Since the electrode has been integrated as a single unit (]), and is attached to the positive and negative electrode chambers by simple systems such as flanges (M, N) bolted together, the amount of work required to change the electrodes is considerably reduced.

Thus, in one embodiment, the present invention is a batch type acidic electrolyzed water production system characterized in that the system uses an electrolyte cell having an easily removable structure with an electrode having an integrated structure, in which the positive and negative electrodes and the separating membrane that is between these are arranged in proper order, and are enclosed by frames. The integrated electrode assembly is placed between the positive electrode chamber and the negative electrode chamber, which latter also serves as the electrolyte solution storage tank, and raw water is delivered from a raw water storage tank that has a fixed capacity with a pump, and by means of a liquid distribution device, is distributed as water that is electrolyzed to generate acidic electrolyzed water, and water that is not electrolyzed, and the amount of water that is electrolyzed is 5 to 40 cc per ampere of current, and after the electrolysis, both of the waters are again mixed and circulated to the raw water storage tank. In another embodiment, a batch type acidic electrolyzed water production system is characterized in circulating water from a storage tank through an anode at limited flow rate, for example a flow rate of 5 to 40 ml per minute per coulomb of electricity applied to said anode, and the acidic electrolyzed water from the anode is diluted by its return to the storage tank and its mixture with the water contained in the storage tank.

In another embodiment, the storage tank is a detached container, for example a bottle, and water is removed from said bottle by a pump or equivalent connected to a first tube inserted into said bottle, and after electrolysis the acidic electrolyzed water is returned to said bottle by a second tube. When the designated time has passed, or a measured number of coulombs has been applied, then the tubes are removed and the bottle may be removed and closed.

In another embodiment, the raw water is supplied by a continuous source, preferably controlled by a valve, and the continuous raw water passes in a limited amount though the anode compartment, and optionally in another amount raw water bypasses the anode compartment and is mixed with the electrolyzed water after it leaves the anode compartment, either in line or in a receiving tank, which can be a fixed tank or an exchangeable tank.

In the batch-type electrolysis system, the salt solution in the cathode is generally changed in a batch type process, in which the salt solution is replaced after it has been used to generate a certain volume of acidic electrolyzed water having a target concentration of active chlorine, such as hypochlorous acid. The time before replacement could be extended, for example for the convenience of an operator, by circulating salt solution through the cathode compartment from a large tank, or from a tank containing undissolved salt, or both. In principle, electrolyte solution could be generated continuously by automatic means and circulated through the cathode compartment at a rate designed to maintain a particular chloride concentration in the electrolyte solution flowing out of the cathode compartment, in which case, if the anode compartment flow was also continuous, the system might not strictly speaking be a batch system.

In any of these embodiments the active chlorine concentration in the diluted electrolyzed water can be controlled by any practical combination of alteration of the ratio of diluting raw water to electrolyzed water, and altering the rate of flow of water (for example in ml/min) and/or the' rate of current flow (amperes) in the anode compartment. (In any calculation, the influence of changes in the chloride concentration and pH in the cathode compartment on the efficiency A of the system should be considered for the most accurate results.)

In addition, the invention comprises a batch type acidic electrolyzed water production method characterized in that in those cases where acidic electrolyzed water for which the effective target chlorine concentration is about 30 ppm ±20 is generated from the raw water of the raw water storage tank that has a fixed capacity (W liters), the current which is loaded is integrated each second and the generation is completed at the point in time where the integration value Q has reached the value that has been set, which may be a figure in the range of 420 ±200 coulombs per liter of water.

In addition, the invention comprises a batch type acidic electrolyzed water production method characterized in that a direct current power source is used to provide a fixed value for the current, or for the voltage with estimation of the current, and by means of the assumption in advance of the mean electrolytic current, the processing time that is required for the amount of the current that is loaded by one liter of raw water of the W liters to become 420 ±200 coulombs is calculated, the time is set with a timer, and the generation is completed.

In construction of the system of the invention, regulation of flow through the anode compartment is usually required. Any convenient known means of regulating flow can be used. Flow regulations means include, without limitation, valves, including needle valves, orifices, diaphragm pumps, piston pumps, other metering pumps, and capillary tubing.

In construction of the invention, any convenient means may be used to connect the flanges of the electrolyzer assembly. Besides bolts and nuts, as mentioned, clamps, screws, latches, snaps, straps, hook/loop closures, and other known fastening systems, and combinations of these, can be used.

In addition, the device of the invention may comprise means for determining when the salt solution in the cathode needs to be removed and replaced with a fresh salt solution. Any suitable determination means may be used. One means is by calculation, so that after a preset total number of coulombs of electricity are passed through the membrane, which corresponds to a total number of moles of chloride ion passed through the membrane when corrected for the efficiency, the device signals the operator that it is time to replace the salt solution. In an automated version, the device opens valves to remove the old salt solution and add fresh salt solution. In an alternative or supplementary mode of determination, a sensor is present in the cathode compartment and senses a value related to the level of chlorine. The value can be, among others, the pH, measuring the accumulation of hydroxy] ion, or it could be output from a chloride detector, or it could be a measurement of the redox potential of the cathode solution relative to a reference.

Likewise, for a batch operation, the time of termination of application of electric current to make acid electrolyzed water, and the time for termination of circulation of water through the anode, can be selected to occur upon the attainment of a criterion. Operation can also be contingent on the first of any of several criteria to be attained; or on a combination of criteria to be obtained, which may be weighted or otherwise mathematically interrelated. Criteria, which typically are the attainment of a value lower than, equal to, or greater than a selected value, can be any criterion of usefulness in selecting a particular level of antibiotic activity in the acid electrolyzed water. Preferred criteria include time of operation; integrated current during operation; pH; oxidation/reduction potential (ORP) (also called redox potential); concentration of active chlorine, for example by direct measurement, or a surrogate therefore; or change of color or other visible property of an indicator. "Water" as used herein means water of low salinity, and typically water of a grade useful and permissible for washing persons and animals, food items and other objects. Conventional additives can be added to water when such additives are electrochemically compatible with the presence of active chlorine in the final product. i

Water, as noted, is preferably provided in a batch, but may be continuously replenished in one of several ways. Likewise, the chloride in the electrolyte is gradually expended, and the chloride concentration is maintained by one or more means selected from replacement of the electrolyte and replenishment of the electrolyte. For example, and with out limitation, the electrolyte may be replenished by one or more of recirculating the electrolyte in the cathode from and to a much larger external saline reservoir, or periodically adding salt to the electrolyte in the cathode, or periodically interrupting operation, discharging the electrolyte in the cathode, and refilling the cathode compartment with fresh electrolyte, or pumping electrolyte through the cathode chamber in a single pass mode at a regulated rate from another reservoir. Combinations of these may also be used, and pH may be adjusted independently of or concurrently with the replenishment of chloride ion.

As part of the process of improving electrolyzers, a protection membrane system has been discovered which prolongs the life of an anion permeable membrane. Various methods were investigated for preventing deterioration and damage over time, due to chlorine gas, of the permeable membrane in the form of a negative ion exchange membrane. As a measure for preventing deterioration of the permeable membrane, the placing of a protection membrane between the permeable membrane and the positive electrode to prevent contact of the chlorine ions with the permeable membrane was considered. However, implementation of this two-layer type permeable membrane and protection membrane made continuation of electrolysis difficult. As a result of investigation, the cause was found to be the transfer or so- called infusion of ions accompanying the electrolysis reaction; when the ions accompanied by liquid and gas are transmitted through the permeable membrane, the gas and water are caught between the two layers of the membrane, i.e., between the protection membrane and the anion exchange membrane. It was learned that the gas and water that are caught between the two membranes exhibit very high electrical resistance and make it difficult to continue with electrolysis. After much investigation, a plurality of slit-shaped discontinuities and the like were formed in the protection membrane as an outlet for the liquid and gas. Thus, instead of being caught between the two membranes, gas and water are discharged through the slit-shaped discontinuities. This prevents an increase in electrical resistance, while also preventing direct contact of chlorine gas with the ion exchange membrane to avoid deterioration of the membrane.

The present invention is an electrode for water electrolysis used in water electrolysis equipment to produce acidic electrolyzed water containing available chlorine. This electrode is characterized by having a positive electrode (anode) plate that preferably has a plurality of holes, in combination with a protection membrane; and further by a protection membrane that has a plurality of slit-shaped discontinuities. In the preferred embodiments, the electrode is adjacent to a permeable membrane that is a negative ion (anion) exchange membrane, placed next to the protection membrane on the side facing the negative electrode. A negative electrode with a plurality of holes can be placed on the permeable membrane side of the water electrolysis electrode described above. Overlap construction of the slit-shaped discontinuities of the protection membrane described above is desirable. In one embodiment, the electrode for water electrolysis of the present invention uses a negative ion (i.e., anion) permeable ion exchange membrane as the permeable membrane. This electrode, that produces acidic eiectrolyzed water containing available chlorine, such as hypochlorous acid, by generation of chlorine gas in an electrolysis apparatus and the ensuing reaction of chlorine gas and water, has the effect that when the positive electrode and permeable membrane of the electrode for water electrolysis are placed in close proximity to one another, acidic eiectrolyzed water is produced efficiently.

Furthermore, using the water electrolysis electrode of the present invention, although the electrode and permeable membrane are placed in close proximity to one another, a protection membrane is placed between the electrode and the permeable membrane. This protection membrane prevents direct contact of chlorine gas with the ion exchange membrane, preventing deterioration of the negative ion exchange membrane due to chlorine gas and i enabling high efficient operation over a long period of time. In addition, this electrode is equipped with slit-shaped discontinuities, wherein during electrolysis the slit-shaped discontinuities discharge any chlorine gas generated at the positive electrode surface and water, before the chlorine gas is caught between the two membranes, thereby preventing an increase in electrical resistance.

Preferred Embodiments of the Invention

One example of the electrode for water electrolysis of the present invention is described in the Figures. Fig. 4 is an assembly drawing of an electrode for water electrolysis of the present invention. The symbol I is for a positive electrode plate, 2 is for an insulator, 3 is for a protection membrane, and 4 is for a permeable membrane that is a negative ion exchange membrane. The protection membrane 3 is overlaid onto the positive electrode plate I .

Insulation 2 is inserted as necessary. Next, the permeable membrane 4 that is a negative ion exchange membrane is overlaid onto the protection membrane 3. It is desirable to integrate the positive electrode plate I , the insulation 2 used as necessary, the protection membrane 3, and the permeable membrane 4 that is a negative ion exchange membrane, which are overlaid together. The electrode for water electrolysis with this structure is used as the positive electrode.

Preferably, as described in US 5,674,365, holes "a" are formed in the positive electrode I . The shape of the holes "a" is arbitrary. However, a circular shape is desirable. With the circular shape, a diameter of I to 5 mm is desirable. Titanium, gold, platinum, iron oxide, and graphite etc., can be used as the material for the positive electrode plate; however, use of titanium as a base material with a platinum-family coating is desirable. It is especially desirable to use platinum- family materials such as iridium oxide, palladium, or ruthenium as a catalyst for increasing the generation efficiency of the available chlorine. A suitable thickness for the metal used is 0.1 to 5 millimeters. Next, the insulator 2 is formed out of a non-electrical conducting material such as, for example, synthetic resin. The insulator 2 is used as needed.

The protection membrane 3 is made from a non-electrically conductive material that has a plurality of slit-shaped discontinuities b inserted in the surface. Fig. 5 is a cross-sectional diagram of the protection membrane 3 from Fig. 4 above. This protection membrane, as shown in Fig. 5 uses a plurality of pieces of non-woven fabric cut into strips. A strip of non-woven fabric is overlapped on the edge of another strip of non-woven fabric; another strip of non- woven fabric is overlapped onto the second strip of non-woven fabric and so on, repeating in this fashion. These strips are integrated into one piece. The integration can be performed for example by bonding the outside edges using an adhesive. A slit-shaped discontinuity is formed in the overlapped sections. The amount of overlap differs with the size of the protection membrane; however, one to five millimeters of overlap is desirable. The protection membrane of this shape is suitable primarily when the protection membrane surface is large. This maintains the openings in the slit-shaped discontinuities of the overlap portion when a nonuniform load is exerted on the protection membrane, causing distortion and when a pressure is exerted that causes swelling.

Fig. 6 is a perspective drawing of another example of a protection membrane of the present invention. This protection membrane is an example which retains the outer edges of the non- woven fabric permeable membrane and introduces a plurality of slit-shaped discontinuities (slits) "b". A width of I to 10 mm for these slits "b" is desirable and of 3 to 7 mm is even further desirable. This simplifies manufacture of the protection membrane; however, due to distortion caused by a non-uniform load or swelling caused by pressure, there is the possibility that chlorine gas can contact the ion exchange membrane directly through slight opening of the slits. It follows that this procedure is suitable for small electrodes where the change in shape of the membrane is minimal. The direction of the slit-shaped discontinuities of the protection membrane 3 can be up and down, side to side, or diagonal etc. In addition, a plurality of fine holes can also be formed. The spacing interval of the slit-shaped discontinuities is arbitrary; however, too narrow an interval increases the chances of the opening of the slit-shaped discontinuities allowing chlorine gas to contact the ion exchange membrane. On the other hand, if there are too few intervals, discharge of gas and liquid is insufficient and can lead to an increase in electrolytic voltage. In general, a spacing interval of one to seven millimeters is desirable. This protection membrane 3 prevents the chlorine gas generated on the surface of the positive electrode from contacting the ion exchange membrane. When a liquid or gas is caught between the protection membrane and the ion exchange membrane, the protection membrane functions by slightly changing shape and discharging this liquid or gas. Examples of suitable materials for the protection membrane 3 include, without limitation, asbestos, glass wool, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyester fibers, aromatic polyamide fibers or non-woven fabric made from any of these fibers, paper, or cellophane paper can be used as the material for this protection membrane 3. A non-woven fabric that provides favorable ion exchange is desirable.

Fig. 7 is a cross-sectional drawing of a three chamber electrolysis bath for which the electrode shown in Fig. 4 is used as the positive electrode. The electrolysis bath is made up of three chambers separated with an electrode and a permeable membrane. The symbol A is for the positive electrode chamber, B for the center chamber, and C is the negative electrode chamber. The positive electrode chamber A and center chamber B are separated by the positive electrode. This positive electrode is the positive electrode plate I with a plurality of holes, the protection membrane 3 that has slits and the permeable membrane 4 that is a negative ion exchange membrane are shown in Fig. 4 overlaid together. Furthermore, the center chamber B and negative electrode chamber C are separated by the negative electrode. The negative electrode is the permeable membrane 7 overlaid together with a negative electrode plate 8 with a plurality of holes. Electrolyte containing chloride ions is placed in the center chamber B, tap water flows through the positive electrode chamber A and the negative electrode chamber C, performing the electrolysis. The symbol D is for the inlet introducing tap water to the positive electrode chamber. The symbol E is for the outlet where the acidic electrolyzed water is discharged. The symbol F is for the inlet introducing tap water to the negative electrode chamber. The symbol G is for the outlet where the alkaline electrolyzed water is discharged. The symbol H is for the inlet used for the electrolytic water and the symbol I is the outlet for the electrolytic water. The electrolyte placed in the center chamber B is generally sodium chloride; however, other salts that contain chloride ion such as potassium chloride are suitable. Furthermore, another halogen ion can be used, in whole or in part, in place of the chloride ion.

Fig. 8 is an assembly drawing of an example of a water electrolysis electrode similar to the apparatus of Figure I , but incorporating a protection membrane. A negative electrode plate with a plurality of holes is overlaid onto the electrode (positive electrode) for water electrolysis described above on the permeable membrane side. The symbol I is for the positive electrode plate, 2 the insulator, 3 the protection membrane, and 4 for the permeable membrane, the same as noted previously. In addition, 5 is another insulator and is the same structure as the insulator 2. The symbol 6 is for the negative electrode plate. The negative electrode plate 6 has a plurality of holes of the same form as with the positive electrode plate I . The shape of the holes "a" is arbitrary; however, a circular shape is desirable. With a circular shape, a diameter of I to 5 mm is desirable. In addition, the material used for the negative electrode 6 can be the same as the material used for the positive electrode plate I ; however, as the solution is alkaline, materials that corrode easily in acid such as steel, stainless steel, tin, or copper can only be used for a short time.

Fig. 9 is a perspective drawing of the electrode shown in Fig. 8 with the positive electrode I , insulator 2, protection membrane 3, permeable membrane 4, insulator 5, and negative electrode 6 overlaid and placed in this order, integrated with a frame 47 on each side for holding in place around the edges. For integration of the electrode, use of adhesive near the frame on each of the parts and for integrating with the fixation frame 47 is preferable, forming integrated electrode assembly J. Here, a non-electrically conducting adhesive must be used to maintain insulation and prevent direct contact between the positive electrode plate and the negative electrode plate. The material used for the fixation frame 47 is a non-electrically conducting material that is a plastic such as polyvinyl electrode, polyethylene, or polypropylene or ceramic or glass.

Embodiment I :

In this embodiment, an electrode prepared as the positive electrode plate of the present invention is used with a three chamber electrolyzer apparatus for electrolysis of water. The electrode, shown in Fig. 7, is made up of a positive electrode plate I , protection membrane 3, and permeable membrane 4 (negative ion exchange membrane) is formed to a size of 9 cm wide and 15 cm tall and used as the positive electrode for the three chamber electrolyzer apparatus shown in Fig. 7. In other words, this positive electrode was used to separate the positive electrode chamber A from the center chamber B. Furthermore, a negative electrode made up of a negative electrode plate 8 and permeable membrane 7 (fluorine based positive ion exchange membrane) was placed to separate the center chamber B and negative electrode chamber C. A saturated sodium chloride aqueous solution was placed in the center chamber B. Electrolysis was performed using a load current of 6.5 amps.

A comparison of electrolysis using various forms of protection membrane is shown in Table I , where the pH and the concentration of available chlorine was measured, and the operating conditions were monitored. The results are shown in Table I . The screen butterfly net shown in Table I is one that is commercially available. A micro filter MF250B manufactured by Yuasa M&B was used as the non-woven fabric. The slit-shaped discontinuities based on overlapping were formed through overlapping strips of non-woven fabric 15 mm wide. In addition, the slit discontinuities were formed by slits with an interval width of 5 mm. In Table I , the Xs indicate the increase in voltage shortly after start of operation where continued operation was not feasible and the Os indicate tests where continued operation was possible. Aciplex A50 I (manufactured by Asahi Kasei) was used as the permeable membrane that is a negative ion exchange membrane.

Table I

Referring to Table I , for the case of using butterfly net screen as the protection membrane, the voltage rose slightly after start of operation, and the operation was no longer feasible. In addition, when non-woven fabric without slit-shaped discontinuities was used, operation was feasible for approximately 30 minutes, and acidic water was obtained; however, at this point, the voltage rose dramatically, and operation was no longer feasible. Moreover, when operating without a protection sheet, or operating with a non-woven sheet with slit-shaped discontinuities, continuation of the operation was feasible. However, in the case of operation without a protection sheet, after 1000 hours the negative ion exchange membrane became whitish and deteriorated. On the other hand, in the case where a non-woven fabric with slit- shaped discontinuities was used, there was virtually no change in the negative ion exchange membrane after 1000 hours of operation.

Embodiment 2:

This embodiment is equipped with a positive electrode and a negative electrode of the present invention. In other words, the electrode described previously for Fig. 9 is used, and electrolysis is performed using the electrolysis equipment shown in Fig. I and Fig. 2. This equipment is a two-chambered apparatus with a non-circulating cathode compartment, described above.) The protection membrane of the electrode J structure of Fig. 9 used for this embodiment is ten pieces of non-woven fabric (micron filter MF250B) with 5 mm slit intervals as the protection membrane, has an effective surface area of approximately 20 cm², and is mounted using an approximately 6 cm square frame. Fig. 2 is an assembly drawing of the electrolytic equipment with a positive electrode bounding plate K and an electrolysis apparatus V in which the integrated electrode plate J is mounted. Flanges M and N are joined to form a positive electrode bath and a negative electrode bath, and to assemble the electrolysis apparatus. Note that packing or gasketing was used to fix the electrode J against the flanges. Fig. I shows the flow of tap water when the electrolysis equipment of Fig. 2 and Fig. 3 is used to electrolyze water. The symbol O is the tap water storage tank, P the pump, Q the tap water distribution device, R the timer that controls the time electrolysis is performed.

Five liters of tap water stored in the tap water storage tank O were circulated through the positive electrode chamber by the pump P, and product water with a concentration of 30 ppm of available chlorine was produced. Here, the amount of tap water actually flowing through the positive electrode chamber Y (Fig. I) was maintained at or below 40 cc per minute per ampere, and the rest was returned to the storage tank using the bypass; this distribution was performed by the liquid distribution device Q. The generation efficiency of available chlorine concentration is favorable, and it was possible to hold the operating voltage down. The DC power supply voltage supplied for this embodiment was 5 Volts and current was 6 Amps. Furthermore, the amount of time needed to produce acidic electrolyzed water with 30 ppm available chlorine was 5.5 minutes.

Hence, in an apparatus for producing acidic electrolyzed water, the use of a protection membrane having slits allows the protection of a permeable membrane from chlorine generated by the electrolysis, together with a venting action of trapped gas and fluid through the slits which preserves the electrical conductivity of the membrane and electrode assembly. The protection membrane is useful both in three chambered electrolyzers and in two chambered electrolyzers. The preferred protection membrane has slits formed by overlapping strips of fabric or the like. The preferred fabric is a non-woven fabric.

The nature of the invention has been illustrated by description and examples to aid in its understanding, and several embodiments of the invention have been illustrated or described. Additional embodiments are contemplated in the invention, and the scope of the invention is not limited by the description of particular embodiments, but by the scope of the claims.

Claims

1. A device for producing acidic electrolyzed water, the device comprising: an apparatus comprising an anode in an anode compartment, a cathode in a cathode compartment, an anion-permeable membrane separating the anode and the cathode compartment, and a means for circulating water for electrolysis through the anode compartment; a chloride-containing electrolyte in said cathode compartment; means for applying a direct current voltage between the electrodes; means for regulating the rate of flow of water for electrolysis through the anode compartment; and means for deactivating the means for circulating water and the means for application of voltage across the membrane, when one or more criteria have attained pre- selected values.

2. The device of claim I , wherein the one or more criteria are selected from one or more of elapsed time of operation; integrated current during operation; pH; oxidation/reduction (redox) potential; concentration of active chloride; or change of color or other detectable property of an indicator.

3. The device of claim I , wherein the flow rate of the water for electrolysis through the anode compartment is between about 5 and about 40 ml/min per ampere of current passing between the electrodes.

4. The device of claim I where the amount of diluent non-electrolyzed water is selected to meet a criterion, wherein the criterion is selected from a pre-set concentration of active chlorine, a pre-set oxidation reduction potential, and a combination thereof.

5. The device of claim 4 wherein the criterion is an oxidation-reduction potential in excess of 650 mV.

6. The device of claim I wherein the water that is electrolyzed is provided from one or more of a tank, a detachable container, and a continuous source.

7. The device of claim I wherein the water that is electrolyzed is collected after electrolysis in one or more of a tank, a detachable container, and a pipe.

8. The device of claim 7 wherein the tank, container or pipe for collecting the diluted acidic electrolyzed water is connected to a device for dispensing acidic electrolyzed water.

9. The device of claim 7 wherein no additional diluting water is supplied as a flowing stream, and dilution is achieved by mixture of the electrolyzed water into water in a tank, which will become a combination of acidic electrolyzed water and non-electrolyzed water during the operation of the device.

10. The device of claim I wherein the anion-permeable membrane is an anion-selective ion exchange membrane.

1 1. The device of claim I wherein the chloride-containing electrolyte in the cathode compartment is periodically or continually replenished to maintain at least one of a minimum chloride concentration and a maximum pH.

12. The device of claim 1 1 wherein the chloride concentration is maintained by one or more means selected from recirculating the electrolyte in the cathode from and to a much larger external saline reservoir; periodically adding salt to the electrolyte in the cathode; periodically interrupting operation, discharging the electrolyte in the cathode, and refilling the cathode compartment with fresh electrolyte; and pumping electrolyte through the cathode chamber in a single pass mode at a regulated rate from another reservoir.

13. The device of claim I , characterized in that the membrane and the electrodes are formed in an integrated unit that is readily exchangeable.

14. A method for making acidic electrolyzed water, the method comprising: providing an electrolyzer apparatus comprising an anode in an anode compartment, a cathode in a cathode compartment, an anion-permeable membrane separating the anode and the cathode compartment, and a means for circulating water to be electrolyzed through the anode compartment; placing chloride-containing salt water in said cathode compartment; placing a voltage across the membrane between the electrodes; and circulating water to be electrolyzed through the anode compartment at a rate in the range of about 5 to about 40 milliliters per minute per ampere of current; thereby producing hypochlorous acid -contain ing acidic electrolyzed water.

15. The method of claim 14 wherein, in a batch system treating a fixed volume of water, the electrolysis is terminated after the passage of a selected number of coulombs per liter of product water.

16. The method of claim 14, characterized in that the water to be electrolyzed is diluted sufficiently to obtain a chlorine concentration in the range of about 30 +/- 20 parts per million in the diluted electrolyzed water.

17. The method of claim 14, wherein the anion-permeable membrane is an anion-selective ion exchange membrane.

18. The method of claim 14 wherein the water to be electrolyzed that is circulated through the anode is diluted with additional water that is not passed through the anode to obtain desired product water properties.

19. The method of claim 18 where the dilution occurs as the electrolyzed water leaves the anode compartment and before the electrolyzed water either returns to a collection tank or is used.

20. The method of claim 19 wherein the collection tank is the same as the storage tank.

21. An improved electrode assembly for the production of acidic electrolyzed water, wherein the anodic section of the assembly comprises a protection membrane (3), placed between a positive electrode (I), and an anion-permeable membrane (4), the protection membrane (3) functioning to protect the anion permeable membrane (4) from chlorine generated at the positive electrode.

22. The electrode assembly of claim 21 wherein the protection membrane (3) is provided with discontinuities (b) through which gas can escape from the space between the protection membrane and the anion permeable membrane.

23. The electrode assembly of claim 21 wherein the discontinuities (b) are selected from slit- shaped discontinuities and hole shaped discontinuities.

24. The electrode assembly of claim 21 wherein the discontinuities (b) are slit-shaped discontinuities.

25. The electrode assembly of claim 21 wherein the protection membrane is a fabric.

26. The electrode assembly of claim 25 wherein the protection membrane is a non-woven fabric.

27. The electrode assembly of claim 21 wherein the anion-permeable membrane is an anion- selective membrane.

28. The electrode assembly of claim 21 wherein the assembly optionally comprises a first insulator (2) between the protection membrane (3) and the positive electrode (I).

29. The electrode assembly of claim 21 wherein the electrode assembly further comprises a cathodic section comprising an optional second insulator (5) and a negative electrode (6).

30. The electrode assembly of claim 29 further comprising fixation frames (9).

31. The electrode assembly of claim 30 wherein the components (1 - 6) and the frames (9) are bonded together into an assembly (J).

32. The electrode assembly of claim 21 , wherein the electrode assembly further comprises a electrolyte-containing section comprising a central chamber (B), and a cathode chamber (C) containing a negative electrode (8), wherein the central chamber (B) is bounded by anion permeable membrane (4) between chamber (B) and chamber (A), and wherein central chamber (B) is further bounded by a permeable membrane (7) and a negative electrode (8) between central chamber (B) and cathode chamber (C).

33. A method for protecting an ion-selective membrane from chemical degradation, wherein the membrane is in an electrolyzer for production of acidic electrolyzed water, the method comprising: providing a protection membrane (3) between the electrode (I and the anion selective membrane (4); and providing discontinuities (b) in the protection membrane (3) to allow the escape of gas and fluid trapped between the protection membrane and the ion selective membrane; and operating the system for prolonged periods while maintaining the ion exchange membrane in a functional state.

34. The method of claim 33 wherein the electrolyzer is selected from a two chamber electrolyzer and a three chamber electrolyzer.

35. An improved system for producing acidic electrolyzed water, the system comprising: a positive electrode (I ), optionally with a first insulator (2; an anion-permeable membrane (4), a second electrode (6 or 8), optionally with a second insulator (5), and a protection membrane (3) functioning to protect the anion permeable membrane (4) from gas produced by the positive electrode ( I); wherein the protection membrane (3) has discontinuities (b) for venting gas and liquid.

36. The improved system of claim 35 wherein the discontinuities (b) are slit-like.

37. The improved system of claim 35 further comprising a center chamber (B) between the anion permeable membrane (4) and a permeable membrane (7), said permeable membrane (7) lying between chamber (B) and second electrode (8).

38. The improved system of claim 35 wherein the positive electrode (I ), optional insulator (2), protection membrane (3) with discontinuities (b), anion exchange membrane (4), optional second insulator (5) and negative electrode (6) are placed between fixation frames (9) and bonded together to form a unitary electrode (J).

39. The improved system of claim 38 wherein the electrode assembly (j) is interposed between a negative electrode chamber and electrolyte-containing bath (L) and a positive electrode chamber (K) and the system is closed by connecting flanges (M) and (N).

40. The improved system of claim 39 wherein water for electrolysis is circulated from a tank (O) by a pump (P), or is obtained from a continuous source, and at least a portion of the water for electrolysis passes through positive electrode chamber (K).

41. The device of any one of claims I through 12 further comprising a protection membrane according to claim 21.

42. The method of any one of claims 13 - 20 further comprising use of a protection membrane according to claim 33.

43. The system of claim 35 further comprising the device of claim I .