Title of Invention	"ELECTRODEIONIZATION MODULE COMPRISING ONCE ION-EXCHANGE MEMBRANE"
Abstract	Electrodeiouizatiou (EDI) iuodule comprising at least one ion-exchange membrane deliiitiiig at least one desalting zone (I 1) aud at least one concentrating zone (12) sihiatecl between electrodes (13: 14). each zone being provided with ion-exchange means. characterized hi that, tlie ion- exchaiicge means present in a zone are comprised of either ion-exchange resin bea& (17) or at least one nun-wot7en or woven fabric (21. 22) made of ion- exchange fibers. the resin beatis and the fabric(s) being both present in the ED1 modtlle. Fig 1.

Title of Invention

"ELECTRODEIONIZATION MODULE COMPRISING ONCE ION-EXCHANGE MEMBRANE"

Abstract

Electrodeiouizatiou (EDI) iuodule comprising at least one ion-exchange membrane deliiitiiig at least one desalting zone (I 1) aud at least one concentrating zone (12) sihiatecl between electrodes (13: 14). each zone being provided with ion-exchange means. characterized hi that, tlie ion- exchaiicge means present in a zone are comprised of either ion-exchange resin bea& (17) or at least one nun-wot7en or woven fabric (21. 22) made of ion- exchange fibers. the resin beatis and the fabric(s) being both present in the ED1 modtlle. Fig 1.

Full Text	The Present invention relates to Electrodeionization module and apparatus comprising it. The present invention relates to an electrodeionization (EDS) module and apparatus adapted to transfer ions present in a liquid.under the influence of a polar field. Specifically, this invention relates to an EDI apparatus adapted to purify aqueous liquids for the production of high purity water or uitra-pure water. The purification of an aqueous liquid by reducing the concentration of ions and molecules in the liquid has been an area of substantial technological interest. Numerous techniques have been used to purify aqueous liquids, and the most well known processes include distillation, electrodialysis, reverse osmosis, liquid chromatography, membrane filtration and ion-exchange, as well as the technique known as EDI. The first known apparatus and method for treating liquids by EDI was described by Watler et al (c.f. W. R. Walters, D. W. Weister and L. J. Marek, Industrial and Engineering Chemistry, Vol. 47, No. 1, pp 61 - 67, 1955) in 1955. United States Patents Nos. 2,689,826 and 2,815,320 in the name of Kollsman were the first known patents describing an apparatus and process for removing ions from a liquid in a depleting chamber also known as a dilution, desalting or demineralization chamber, through a series of anionic and cationic membranes into an adjacent volume of liquid in a concentrating chamber under the influence of an electrical potential which causes the desired ions to migrate in a predetermined direction. The volume of the liquid being treated is depleted of ions while the volume of the adjacent liquid becomes enriched with transferred ions. The second of these patents describes the use . of ' SUBSTITUTE SHEET (RULE 26) macroporous beads formed of ion-exchange resins as a filler material positioned between the anionic and cationic membranes. These ion-exchange resins form a path for ion transfer and also serve as an increased conductivity bridge between the membranes for the movement of the ions. Generally, ion-exchange resins employed in EDI modules are in the form of polymer beads (polystyrene, etc.), that are commercially available from Dow Chemical Company, Sybron Chemicals, Purolite and Rohm-Haas, for example, are typically 0.4 to 0.6 mm in diameter and contain functional groups which allow these beads to have an anion or cation-exchange function depending on the functional gpoups attached. The functional groups generally used for cation-exchange resins are sulfonic acid groups, while for anion-exchange resins these groups are typically quaternary ammonium groups. These beads are packed in the desalting and the concentrate compartments of an EDKapparatus either in a separate bed or a mixed bed configuration. A separate bed arrangement comprises the physical packing of anion and cation ion-exchange beads alternating throughout the desalting and concentrate compartments, the desalting and concentrate compartments being separated from the adjacent compartments by an anion-exchange membrane and a cation-exchange membrane. A mixed bed arrangement comprises the physical packing of an appropriate and uniform mixture of anion and cation-exchange beads throughout the desalting and concentrate compartments, the desalting and concentrate compartments being separated from the adjacent compartments by an anionic membrane and a cationic membrane. Commercially successful EDI apparatuses and processes are described in particular in United States Patents Nos. 4,465,573; 4,632,745; 4,636,296; 4,687,561; 4,702,810; 5,026,465; 5,376,253; 5,954,935 and 5,503,729 and in International Patent Application No. WO-96/29133. Some of these apparatuses employed in particular desalting compartments containing an ion exchange composition and concentrating compartments which were free of ion-exchange solid material. The EDI apparatuses employed two terminal electrode chambers containing an anode and a cathode and were used to pass direct current transversely through the body of the apparatuses containing a plurality of desalting compartments and concentrating compartments. In the case of US Patent No. 5,376,253, the arrangement of the apparatus is of cylindrical form that contains the concentrate and desalting compartments within. In the case of US Patent No 5,954,935, the electrode compartments are formed by desalting compartments, the cathode compartment being filled with anion exchanger material forming an anion resin bed and the anode compartment being filled with a cation exchanger material forming a cation resin bed. The concentrate compartments of, the apparatuses disclosed in this document can optionally be filled with such ion exchange resins or with a net-like spacer. In operation of such apparatuses, the dissolved ionized salts of the liquid are transferred through the appropriate membrane from the desalting compartments to the concentrating compartments and these ions were directed to waste. However, the major limitation with these apparatuses are the formation of insoluble scale, in particular within the cathode electrode compartment, and with time they fail to operate correctly. In any membrane separation process where ions become concentrated, there is always the potential to exceed the solubility limits and form precipitates on membrane surfaces known commonly as scale. In particular, calcium carbonate (CaCOa) scale is formed when the levels of calcium and carbonate ions reach the solubility limit. The main source for the observed scale phenomena is the adsorption of carbon dioxide (CO2) in water that will react with hydroxide ions in the following way to form the calcium carbonate ion: The presence of calcium ions in a concentrate compartment will naturally have as a consequence that calcium carbonate will precipitate out of solution. It should be noted in this connection that calcium carbonate is only slightly soluble in water, since only 14 milligrams is the maximum amount that will dissolve in 1 liter of water. Therefore, the potential for forming scale increases with an increase in calcium ion concentration, pH, carbonate and bicarbonate ion concentrations in a concentrating compartment of an EDI apparatus. Reactions at the EDI electrodes and water splitting in the EDI process creates shifts in the pH of a concentrate compartment, and is the source of protons (H+) and hydroxyl ions (OH") that will contribute effectively to the formation of scale, in particular from the hydroxyl ions. The reactions occurring at the electrodes are shown below, whereby the anode reaction is (3) and the cathode reaction is (4): Water splitting occurring in the desalting compartments is an additional source of hydroxyl ions within the EDI module. In a concentrating compartment where the hydroxyl ions are entering through the anion-exchange membrane and especially along the surface of that anion-exchange membrane, the pH can become sufficiently high enough to generate the formation of scale. Consequently, the formation of scale within the EDI module will result in a very high electrical resistance and blocking of the flow channels leading to a rapid decline in the production of quality water. There are methods available for the pretreatment of the feed water prior to it entering the EDI apparatus, such as water softening and reverse osmosis, which will reduce the ion concentrations of Ca2+, HCO3" and CO32" and therefore reduce the incidence of scale formation. However, improper maintenance of these apparatuses has resulted in limited success in reducing the scale formation inside EDI apparatuses. Additional commercially successful EDI apparatuses were described in United States Patents Nos. 5,154,809; 5,308,466; 5,316,637 and 5,593,563. These apparatuses all utilize a plurality of desalting compartments containing an ion-exchange composition in the form of resin beads, and a plurality of concentrate compartments which also contain an ion-exchange composition in the form of resin beads. However, in the latter compartments the selectivity for anions and cations was lower. United States Patent No. 5,593,563 addressed the problem of the formation of scale in the cathode electrode compartment by including electrically conductive particles or beads in the cathode electrode compartment. These electrically conductive particles or beads are metallic or constituted by carbon. However, some of these apparatuses experienced internal movement of the ion-exchange compositions in both the desalting and concentrate compartments which resulted in internal blockages, due to the high operational feed pressures or flow rates, which made some apparatuses fail to operate over a period of time. Alternative ion-exchange compositions have been produced in the form of fabrics made of polymer fibers that contain anion-exchange and cation-exchange functional groups similar to those mentioned above and adapted to be used as ion-exchangers, namely quaternary ammonium groups and sulfonic acide groups, respectively. The basic material of these polymer fibers can be constituted by cellulose based material as well as more robust polymer materials such as polyolefins (c.f.:"S. Ezzahar, A. T. Cherif, J. Sandeaux, R. Sandeaux and C. Gavach, Desalination, Vol. 104, pp 227 - 233, 1996; E. Dejean, E. Laktionov, J. Sandeaux, R. Sandeaux, G. Pourcelly and C. Gavach, Desalination, Vol. 114, pp 165 - 173, 1997; . E. Dejean, J. Sandeaux, R. Sandeaux and C. Gavach, Separation Science and Technology, Vol. 33, No. 6, pp 801 - 818, 1998.; E. Laktionov, E. Dejean, J. Sandeaux, R. Sandeaux, C. Gavach and G. Pourcelly, Separation Science and Technology, Vol. 34, No. 1, pp 69 - 84, 1999"). The desired functional groups are grafted onto these fibers in order to create the ion-exchange behavior required for the purification of aqueous liquids. United States Patents Nos. 3,723,306; 5,152,896 and 5,885,453 and French Patent Applications Nos. 1487391; 1492522 and 1522387 give examples of grafting functional groups onto various materials, whereby ion-exchange fibers have been developed. An alternative technology to grafting the desired ion-exchange functional groups onto the surface of polyolefin type fibers, is the manufacture of heterogeneous ion-exchange materials similar to that described in US Patent^ Nos. 5,346,924 and 5,531,899. The heterogeneous ion-exchange fibers can be manufactured by mixing an appropriate amount of polyolefin binder with an apparopriate amount of anion and/or cation ion exchange material, mechanically crushing and mixing the components and thermally extruding or moulding the heterogeneous ion-exchange textile polymer fibers. Commercially successful EDI apparatuses employing ion-exchange polymer fibers have been commercialized by Ebara Corporation and are described in particular in United States Patents Nos. 5,308,467; 5,425,866; 5,738,775 and European Patent Application No. 1069079. The ion-exchange polymer fibers employed in these EDI apparatuses are in the form of anion-exchange woven or non-woven fabrics, cation-exchange woven or non-woven fabrics, anion conducting spacers and cation conducting spacers, these spacers or separation fibers being respectively provided with anion and cation-exchange groups and are located in particular between the aforementioned woven or non-woven fabrics. These EDI apparatuses utilize a plurality of desalting compartments containing the anion and cation-exchange woven or non-woven fabrics and the conducting spacers and a plurality of concentrate compartments which contain anion and cation conducting spacers only. The desalting and concentrate compartments are alternating and separated by anion-exchange and cation-exchange membranes. These apparatuses also employed two terminal electrode compartments containing an anode and a cathode. However, the major limitation with these EDI apparatuses is their susceptibility to the formation of scale with water containing high levels of dissolved CC-2 and their low power efficiency. The present invention is based on the surprising discovery that the implementation in the desalting and concentrating compartments of either resin ./ beads having ion-exchange functional groups or non-woven or woven fabrics made of ion-exchange fibers, with the resin beads and the fabrics being present together within the electrodeionization module makes it possible to achieve a substantially more effective implementation than those known in the state of the art, in particular with respect to the purity of the water and the maintenance of this purity overtime. The present invention thus relates to an electrodeionization (EDI) module comprising at least one ion-exchange membrane delimiting at least one desalting zone and at least one concentrating zone situated between electrodes, each zone being provided with ion-exchange means, characterized in that the ion-exchange means present in a zone are comprised of either ion-exchange resin beads or at least one non-woven or woven fabric made of ion-exchange fibers, the resin beads and the fabric(s) being both present in the EDI module. Each zone is preferably formed by a compartment and, in this case, the module contains either at least one desalting compartment separated from two adjacent concentrating compartments respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane or at least one concentrating compartment separated from two adjacent desalting compartments respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane. According to a preferred embodiment of the present invention, the EDI module comprises alternating desalting compartments and concentrating compartments between electrodes, wherein each desalting compartment is adjacent to two concentrating compartments and separated therefrom respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane, each compartment being provided with ion-exchange means, and is characterized in that the ion-exchange means present in the desalting compartments are comprised of ion-exchange resin beads while the ion-exchange means present in the concentrating compartments are comprised of at least one non-woven or woven fabric made of ion-exchange fibers. According to an alternative embodiment, the EDI module comprises alternating desalting compartments and concentrating compartments between electrodes, wherein each desalting compartment is adjacent to two concentrating compartments and separated therefrom respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane, each -compartment being provided with ion-exchange means, characterized in that the ion-exchange means present in the concentrating compartments are comprised of ion-exchange resin beads while the ion-exchange means present in the desalting compartments are comprised of at least one non-woven or woven fabric made of ion-exchange fibers. Furthermore, the arrangement according to the preferred embodiment of the invention lends itself advantageously to a development according to which the ion-exchange means comprised of at least one woven or non-woven fabric made of ion-exchange fibers form at least one assembly comprising a woven or non-woven fabric made of anion-exchange fibers and a woven or non-woven fabric made of cation-exchange fibers which are placed in a face to face relationship, and at least one ion conducting spacer which is able to perform ion-exchanges and is interposed between the anion and cation-exchange fabrics. Preferably, in this case, the or each assembly is arranged such that the woven or non-woven fabric which is at the anion selective ion-echange membrane end is a woven or non-woven fabric made of anion-exchange fibers and the woven or non-woven fabric which is at the cation selective ion-exchange membrane end is a woven or non-woven fabric made of cation-exchange fibers. Preferably too, an anion conducting spacer and a cation conducting spacer which are able to perform ion-exchanges are positioned between the anion and cation-exchange fabrics and are respectively situated next to the anion-exchange fabric and the cation-exchange fabric. A particularly effective implementation, can thus be obtained, as will be seen in more detail below. For reasons of efficacy, economy and/or ease of manufacture, it is also preferred that: - each spacer is in the form of a net-like spacer, preferably a diagonal net-like spacer; and/or - the fabrics and the spacer(s) are in intimate contact with each other and are, preferably, carried by a frame; and/or - the or each woven or non-woven fabric made of ion-exchange fibers comprises a substrate made of fibers into which ion-exchange functional groups have been introduced by grafting with monomers which have ion- exchange groups or grafting with monomers having a group which may be converted to ion-exchange group and then converting said group to the ion- exchange group, and the or each spacer, when present, comprises a substrate made of fibers or resins into which ion-exchange functional groups have been introduced by grafting with monomers which have ion-exchange groups or grafting with monomers having a group which may be converted to ion- exchange group and then converting said group to the ion-exchange group; and/or - the substrate is a cellulosic or polyolefinic material; and/or - the cation-exchange fibers and/or cation-conducting spacer(s) have sulfonic acid groups and the anion exchange fibers and/or anion- conducting spacer(s) have quaternary ammonium groups; and/or - the functional groups are introduced by grafting polymerization initiated by radiation (UV-rays, X-rays, y-rays, accelerated electrons, B-rays or a-rays), or by a chemical reagent, such as cerium ions; and/or - the or each woven or non-woven fabric made of ion-exchange fibers comprises a substrate made of heterogeneous fibers .comprised of a mixture of ion-exchange material and polyolefinic binder and the or each spacer, when present, comprises a substrate made of resins or heterogeneous fibers comprised of a mixture of ion-exchange material and polyoiefin'ic binder. Regarding the ion-exchange resin beads, they can be formed by anion-exchangers and cation-exchangers forming a mixed bed or separate beds, but preferably a mixed bed. In this case, the ion-exchange resin beads are preferably formed from polymers, such as polystyrene or styrene-divinyl benzene copolymers, having functional groups, preferably sulfonic acid groups for the cation-exchangers and quaternary ammonium groups for the anion-exchangers. The. arrangement according to the invention also lends itself to another development, which may advantageously be combined with the preceding one, according to which an electrode compartment is formed between each electrode and the ion-exchange membrane adjacent to the electrode. In this case the cathode compartment preferably contains electrically conductive particles, which are preferably carbon and/or metallic particles. This development enables the risk of scale formation to be minimized. According to an alternative development, the cathode compartment comprises at least one spacer in the form of a net-like spacer maintaining the flow between the cathode and the adjacent cation selective membrane. Preferably, in this case, the or each spacer in the cathode compartment has ion-exchange groups. The anode compartment also preferably comprises, in such a case, at least one spacer in the form of a net-like spacer maintaining the flow between the anode and the adjacent anion selective membrane, and which, advantageously, possesses ion-exchange groups. The electrode compartment may, moreover, be formed by the concentrating or desalting compartment adjacent to each electrode. The EDI module also preferably comprises a plurality of alternating desalting compartments and concentrating compartments and fluid communication to each of the desalting compartments and to each of the concentrating compartments are each provided in a serial or parallel arrangement. The present invention also relates to an EDI apparatus for water production of high purity or for production of ultra-pure water, comprising an EDI module as defined above. The features and advantages of the present invention will emerge furthermore from the following description, made by way of example with reference to the accompanying drawings, in which: - Figure 1 is a diagrammatic view of an electrodeionization module according to a preferred embodiment of the invention; and - Figure 2 is a graph of the performance of the electrodeionization module of Figure 1 and of known electrodeionization modules, at the 36th day of operation. /• In the embodiment shown in Figure 1, the electrodeionization module 10 according to the invention comprises, in a manner known per se, alternating desalting compartments 11 and concentrating compartments 12 arranged between two terminal electrodes, i.e. a cathode 13 and an anode 14. Each desalting compartment 11 is separated from two adjacent concentrating compartments 12, respectively by an anion selective ion-exchange membrane 15 and a cation selective ion-exchange membrane 16. In the embodiment shown, the selective membranes adjacent to the cathode 13 and the anode 14 are respectively constituted by a cation selective membrane 16 and an anion selective membrane 15. The compartments situated between these latter membranes and the respective electrodes 13, 14 are concentrating compartments 12 each forming an electrode compartment containing respectively the cathode 13 and the anode 14. According to the invention, these compartments 11 and 12 are filled in the following manner: 1) each desalting compartment 11 is filled with cation-exchange resin beads and anion-exchange resin beads forming a mixed bed. These ion- exchange resin beads are formed from polymers having functional groups, which are sulfonic acid groups for the cation-exchangers and quaternary ammonium groups for the anion-exchangers. 2) the concentrating compartment 12 forming a housing compartment for the cathode 13 is filled with electrically conductive beads 18, while the concentrating compartment 12 forming a housing compartment for the anode 14 comprises a spacer in the form of a net 19 maintaining the flow between the anode and the adjacent anion selective membrane 15. In practice, this spacer 19 is formed from a polyolefinic resin net on which have been grafted anion-exchange groups. More particularly, a polyethylene resin net is used on which quaternary ammonium groups have been grafted. Such a spacer is similar to those described in the European patent application EP 1 069 079 mentioned above. 3) Each of the remaining concentrating compartments 12 is filled with a sandwich structure 20 each comprising a sheet like non-woven fabric 21 made of anion-exchange fibers, a sheet like non-woven fabric 22 made of cation-exchange fibers, an anion conducting spacer 23 and a cation conducting spacer 24. The non-woven fabrics 21 and 22 are disposed in face to face relationship and the spacers 23 and 24 are interposed between these two fabrics and are situated on the side of the anion-exchange non-woven fabric 21 in the case of the anion conducting spacer 23 and on the side of the cation-exchange non-woven fabric 22 in the case of the cation conducting spacer 24. The spacers 23 and 24 are more particularly in the form of a diagonal net formed of polyolefins of high molecular weight on which the ion-exchange functional groups have been grafted, i.e. anion-exchange groups on the anion conducting spacer 23 and cation-exchange groups on the cation conducting spacer 24. The non-woven fabrics 21 and 22 have also been developed from polyolefinic fibers of high molecular weight, on which the functional groups have been grafted. These polyolefinic fibers are, here, fibers of polyethylene and polypropylene, the functional groups grafted on the fibers being sulfonic acid groups in the case of the cation-exchange fibers and quaternary ammonium groups in the case of the anion-exchange fibers. These grafted fibers have been obtained through grafting polymerization initiated with radiation, here y-rays. It should also be noted that the non-woven fabrics 21 and 22 and the ion conducting spacers 23 and 24 are placed in intimate contact with each other. Furthermore, the anion-exchange fabric 21 is arranged on the side of the anion selective membrane 15, while the cation-exchange fabric 22 is arranged on the side of the opposite cation selective membrane 16. It should also be noted that each sandwich structure 20 is carried by a frame (not shown on Figure 1) forming the corresponding compartments 12 and provided, for this purpose, with inlet and outlet passages communicating with the ion-exchange sandwich structure 20, and more particularly with the spacers 23 and 24. For more detail in relation to this, reference may also be made to the European patent application EP-1-069 079 mentioned above. In the embodiment shown, fluid communication is provided respectively between the desalting compartments 11 and concentrating compartments 12 according to a serial arrangement (arrows 25 in dotted lines for feeding the concentrating compartments 12 and arrows 26 in solid lines for feeding the desalting compartments 11). Thus the product coming out from the last desalting compartment 11 (arrow 27 in solid line) is demineralized water, while the product coming out from the last concentrating compartment 12 (arrow 28 in dotted line) is composed of water in which are concentrated the ions extracted from the water that has passed through the desalting compartments 11. Considering this in more detail, the ions to be eliminated are fixed on the mixed resin beads placed in the desalting compartments 11, out of which comes the demineralized water; by virtue of the application of an electric potential, the ions then migrate rapidly towards the concentrating compartments 12, where they are concentrated for elimination by the electrodeionization module 10. More details about, on the one hand, the preparation of the ion-exchange non-woven fabrics and ion conducting spacers and, on the other hand, the fabrication of the EDI module are given below. Preparation of ion-exchange non-woven fabrics Table 1 shows the specifications of the substrate non-woven fabric used in the experiments below to prepare and ion-exchange non-woven fabric. The substrate non-woven fabric was prepared by thermal fusion of composite fibers consisting of a polypropylene core and a polyethylene sheath. TABLE 1 Core/sheath Polypropylene/polyethylene Areal density 50 g/m2 Thickness 0.55 mm Fiber diameter 15-40 \|im Process Thermal fusion Porosity 91 % One sample of the non-woven fabric identification in Table 1 was irradiated with y-rays in a nitrogen atmosphere and then immersed in a solution of glycidyl methacrylate (GMA) for reaction. Graft ratio of 163 % was obtained. Thereafter, the grafted non-woven fabric was immersed in a liquid mixture of sodium sulfite, isopropyl alcohol and water for sulfonation. Measurement of the ion-exchange capacity of the thus treated non-woven fabric showed that it was a strong acidic cation-exchange non-woven fabric having a salt splitting capacity of 2.82 meg/g. Another sample of the same non-woven fabric was irradiated with y-rays in a nitrogen atmosphere and thereafter immersed in a solution of chloromethylstyrene (CMS) for reaction and graft ratio of 148 % was obtained. The grafted non-woven fabric was then immersed in an aqueous solution of 10 % trimethylamine to introduce quaternary ammonium groups. The product was a strong basic anion-exchange non-woven fabric having a salt splitting capacity-of 2.49 meg/g. Preparation of ion-conducting spacers Table 2 shows the specifications of the diagonal net used as the substrate for preparing an ion-conducting spacer used in the experiments below. TABLE 2 Constituent material Polyethylene Shape Diagonal net Thickness 0.8 mm Mesh opening 6 mm x 3 mm One sample of the diagonal net substrate identified in Table 2 was irradiated with y-rays in a N2 atmosphere and thereafter immersed in a liquid mixture of glycidyl methacrylate (GMA) and dimethylformamide (DMF) for reaction and graft ratio of 53 % was obtained. The grafted net was then immersed in a liquid mixture of sodium sulfite, isopropyl alcohol and water for sulfonation. The product was a strong acidic cation-conducting spacer having a salt splitting capacity of 0.62 meg/g. Another sample of the diagonal net substrate identified in Table 2 was irradiated under the same conditions as just mentioned above and immersed, in a liquid mixture of vinylbenzyltrimethyl ammonium chloride (VBTAC), dimethyl acrylamide (DMAA) and water for reaction, and graft ratio of 36 % was obtained. The product was a strong basic anion-conducting spacer having a salt splitting capacity of 0.44 meg/g. Fabrication of EDI modules The thus-prepared ion-exchange non-woven fabrics and ion-conducting spacers were mounted in the concentrating compartments of EDI modules (comprising four desalting compartments, three concentrating compartments, a cathode compartment and an anode compartment) of the type employed in Millipore's commercial ELIX® by system. The ion-exchange resin beads used therein are cation and anion exchange resin beads produced either by Rohm & Haas or Dow Chemical and sold under the respective trade names, AMBERLITE® AND DOWEX® (particle size = 590 + 50 urn). The carbon beads used therein as the electrically conductive beads are produced by Rohm & Haas and sold under the trade name, AMBERSORB® (particle size = 590 ± 50 jim). Each deionization compartment measured 220 x 35 mm with a thickness of 3 mm and each concentration compartment was 0.8 mm thick. Each anode compartment and cathode compartment measured 2,5 mm thick. The performances of the thus obtained electrodeionization modules (configurations A1 and A2 below) have been compared to conventional electrodeionization modules (configurations B1, B2 and C below). In configurations A1 and A2 (present invention), each of compartments was loaded as shown in Fig. 1 and explained above. Configurations B1 and B2 (conventional) were the same as A1 and A2, except that each concentrating compartment was filled with cation and anion exchange resin beads forming a mixed bed. Configuration C (conventional) was the same as A1 and A2, except that each desalting compartment was filled in the same manner as each concentrating compartment. Using these apparatuses, a water pass test was conducted using supply water under the conditions as shown below. The flow volume of the feeding water was 3 l/h and the operating current was a 70 mA constant current. The fluid communication to each of the desalting compartments, on the one hand, and to each of the anode compartment, concentrating compartments and cathode compartment, on the other hand, are each provided as show in Fig. 1 in a serial arrangement. The operating conditions of ultrapure water production apparatuses incorporating these electrodeionization modules are the following: Operating modes Characteristics of the supply water: 1) reverse osmosis (RO) water No. 1 [C02]=24 mg/i pH=5.5a5.7 temperature = 20 to 22°C conductivity = 21.0 jas.cm 2) reverse osmosis (RO) water No. 2 [C02]=32 mg/I pH=5.2 temperature = 18°C conductivity = 16.5 jis.cm [Ca2+]=2.0 to 3.0 mg/I as CaC03 EDI operating modes: . Operating mode 1: The ED] apparatuses have been subjected to continuous operation 24 hours a day, from the first day to the seventh day. . Operating mode 2: The EDI apparatuses have been subjected to an operating mode consisting alternately of 2 hours of operation and two hours stopped (in standby), from the seventh day to the sixteenth day. . Operating mode 3: The EDI apparatuses have been subjected to operation for the following times: 1:00-3:00; 5:00-7:00; 9:00-11:00 and 13:00-15:00. During the remaining period of time, the apparatuses were stopped (in standby) from the 16th day to the 31st day. . Operating mode 4: the EDI apparatuses have been subjected to operation for the following times: 8:00-10:00 ; 14:00-16:00 ; and 20:00-22:00. During the remaining period of time, the apparatuses were stopped (in standby) from the 31st day to the 57th day. The physical measurements carried out during these tests were measurements of voltage and current level (energy consumption and scale formation) and resistivity as a measure of the water quality produced by these EDI apparatuses. The measurement results are given in tables 1, 2 and 3 which follow and in the graph of Figure 2. Table 1: Comparison of the water qualities produced with the EDI apparatuses. (Table Removed) EDI apparatuses using RO water No. 2 Apparatus B2 using RO water No. 1 between days 1 and 21 Apparatus C using only RO water No. 1 Table 2: Comparison of energy consumption of the EDI apparatuses. (Table Removed) - EDI apparatuses using RO water No. 2 - Apparatus B2 using RO water No. 1 between days 1 and 21 - Apparatus C using only RO water No. 1 Table 3: Observed electrical impedance/resistance in ohms (Q.) profile of the preferred embodiments A1 and A2 with time (Table Removed) a : - EDI apparatuses using RO water No. 2 The electrical impedance (ohms) of a given EDI module is calculated from the applied operating current and the resulting voltage. It is normal to observe a steady increase in the impedance of a given EDI module with time. Whenever there is significant scale formation on the membranes (usually the anion) of a given EDI module, then this will be indicated by a rapid increase in the observed impedance (i.e. 50 % increase in 2 or 3 days), as a / result of scale precipitation on the membrane interrupting the flow of electrical charge or current through the EDI module. The data presented in the above table strongly indicates that there is no or negligible scale precipitation on the surface of the membranes of these EDI modules. It will be understood that the association of two different ion-exchange configurations respectively in the desalting and concentrating compartments of the electrodeionization modules, according to the present invention, provides the following advantages: 1) the production of ultrapure water, of a higher level of purity than that of known apparatuses, in a reliable manner over a longer period of time than with these known apparatuses in continuous operation or in cyclic operation (certain periods of operation and certain periods stopped) representing a much more realistic implementation in water purification installations existing in the world. The synergetic effect resulting from the association dealt with above will be particularly appreciated (c.f. table 1 and Figure 2). 2) the EDI apparatus comprising the electrodeionization module 10 can operate with supply water with greater quantities of carbon dioxide and of calcium ions than with known apparatuses without any adverse effect on the quality of purified water produced and without any effect on scale formation when calcium ions are present in the supply load at moderate concentrations (in practice less than 30 mg of Ca2+ per liter). 3) the compression of fibers in the concentrating compartments of the electrodeionization module 10 restricts the internal movement of the ion- exchange resin beads in mixed bed configuration in the desalting compartments, which enables the EDI apparatus with this to function at high operational pressures and flow rates of the supply load. 4) improved transport of the ions in the concentrating compartments due to the combined presence of the separate layers of ion- exchange materials in the concentrating compartments and of the ion- exchange resin beads in mixed bed configuration in the desalting compartments. 5) the energy consumption is low and stable. Naturally, the present invention is not limited to the form of the embodiment described and represented, but covers any variant form. We Claim: 1. Electrodeionization (EDI) module comprising at least one ion-exchange membrane delimiting at least one desalting zone (1 1) and at least one concentrating zone (12) situated between electrodes (13, 14), each zone being provided with ion-exchange means, characterized in that, the ion- exchange means present in a zone are comprised of either ion-exchange resin beads (17) or at least one non-woven or w,oven fabric (21, 22) made of ion- exchange fibers, the resin beads and the fabric(s) being both present in the ED1 module. 2. ED1 module as claimed in claim 1, wherein each zone is formed by a compartment and the module contains at least one desalting compartment (I 1) separated from two adjacent concentrating compartments respectively by an anion selective ion-exchange membrane (15) and a cation selective ion-exchange membrane (16). 3. ED1 module as claimed in claim 1, wherein each zone is formed by a compartment and the module contains at least one concentrating compartment separated from two adjacent desalting compartments respectively by an anion selective ion-exchange membrane (15) and a cation selective ion-exchange membrane (16). 4. ED1 module containing alternating desalting compartments and concentrating compartments between electrodes, wherein each desalting compartment ( I I) is adjacent to two 'concentrating compartments and separated therefrom respectively by an anion selective ion-exchange membrane (15) and a cation selective ion-exchange membrane (161, each compartment being provided with ion-exchange means, characterized in that, the ion-exchange means present in the desalting compartments and concentration compartments are comprised of ion-exchange resin beads (1 7) while the ion-exchange means present in the concentrating compartments are comprised of at least one nonwoven or woven fabric (2 1,22) made of ion-exchange fibers. 5. ED1 module as claimed in anyone of claims 2 to 4, wherein the ion-exchange means comprised of at least one woven or nonwoven fabric made of ion-exchange fibers form at least one assembly comprising a woven or non-woven fabric (21) made of anionexchange fibers and a woven or non- woven fabric (22) made of cation-exchange fibers which are placed in a face to face relationship, and at least one ion conducting spacer (23,24) which is able to perform ion-exchanges and is interposed between the anion and cation-exchange fibers. 6. ED1 module as claimed in claim 5, wherein each assembly is arranged such that the woven or non-woven fabric which is at the anion selective ion-exchange membrane (15) end is a woven or non-woven fabric made of anion-exchange fibers and the woven or non-woven fabric which is at the cation selective ion-exchange membrane (16) end is a woven or non-woven fabric made of cation-exchange fibers. 7. ED1 module as claimed in claim 5 or 6, wherein an anion conducting spacer and a cation conducting spacer which are able to perform ion-exchanges are positioned between the anion and cation-exchange fabrics and are respectively situated next to the anionexchange fabric and the cation-exchange fabric. 8. ED1 module as claimed in anyone of claims 5 to 7, wherein each spacer is in the form of net-like spacer, preferably a diagonal net-like spacer. 9. ED1 module as claimed in anyone of claims 5 to 8, wherein the fabrics and the spacer(s) of an assembly are in intimate contact with each other and are, preferably, carried by a frame. 10. ED1 module as claimed in any of the claims 1 to 9, wherein each woven or non-woven fabric (21, 22) made of ion-exchange fibers comprises a substrate made of fibers into which ion-exchange functional groups have been introduced by grafting with monomers which have ion-exchange groups or grafting with monomers having a group which may be converted to ion- exchange group and then converting said group to the ion-exchange group, a d each spacer, when present, comprises a substrate made of fibers or resins into which ion-exchange functional group have been introduced by grafting with monomers which have ion-exchange groups or grafting with monomers having a group which may be converted to ion-exchange group and then converting said group to the ion-exchange group. 11. EDI module as claimed in claim 10, wherein the substrate is a ceIlulosic or polyolefinic material. 12. ED1 module as claimed in claim 10 or 11, wherein the functional groups are introduced by grafting polymerization initiated by radiation or a chemical reagent.. 13. ED1 module as claimed in claim 12, wherein the radiation source is ionizing radiation, such. as UV-rays, X-rays, y-rays, accelerated electrons, P-rays or a-rays. 14. ED1 module as claimed in claim 12, wherein the chemical reagent comprises ceriumions. 15. ED1 module as claimed in anyone of claims 5 to 14, wherein the cation-exchange fibers andlor cation-conducting spacer(s) have sulfonic acid groups and the anion exchange fibers and/or anion-conducting spacer(s) have quaternary ammonium groups. 16. ED1 module as claimed in anyone of claims T to 8, wherein each woven or non-woven (21,22) fabric made of ion-exchange fibers comprises a substrate made of heterogeneous fibers comprised of a mixture of ion-exchange material and polyolefinic binder and the or each spacer, when present, comprises a substrate made of resins or heterogeneous fibers comprised of a mixture of ion-exchange material and polyolefinic binder. 17. ED1 module as claimed in anyone of claims 1 to 16, wherein the ion-exchange resin beads (1 7) are formed by anion-exchangers and cation-exchangers forming a mixed bed or separate beds, preferably a mixed bed. 18. ED1 module as claimed in claim 17, wherein the ion-exchange resin beads (17) are formed from polymers, such as polystyrene or styrene-divinylbenzene copolymers, having functional groups, preferably sulfonic acid groups for the cation-exchangers and quaternary ammonium groups for the anion-exchangers. 19. ED1 module as claimed in anyone of claims 2 to 18, wherein an electrode compartment is formed between each electrode and the ion- exchange membrane adjacent to the 1 electrode. 20. ED1 module as claimed in claim 19, wherein the cathode compartment contains electrically conductive particles, which are preferably carbon andlor metallic particles. 21. ED1 module as claimed in claim 19, wherein the cathode compartment comprises at least one spacer in the form of a net-like spacer maintaining the flow between the cathode and the adjacent cation selective membrane. 22. ED1 module as claimed in claim 21, wherein each spacer in the cathode compartment has ion-exchange groups. 23. ED1 module as claimed in anyone of claims 19 to 22, wherein the anode compartment comprises at least one spacer in the form of a net-like spacer maintaining the flow between the anode and the adjacent anion selective membrane. 24. ED1 module as claimed in claim 23, wherein each spacer in the anode compartment has ion-exchange groups. 25. ED1 module as claimed in anyone of claims 19 to 24, wherein the concentrating or desalting compartment adjacent to each electrode forms the electrode compartment. 26. ED1 module as claimed in anyone of claims 2 to 25, wherein a plurality of alternating desalting compartments (11) and concentrating compartments and wherein fluid communication to each of the desalting compartments (11) and to each of the concentrating compartments are each provided in a serial or parallel arrangement 27. ED1 module as claimed in any of the previous claims, which is incorporated in an ED1 apparatus for water production of high purity or for production of ultra-pure water.

Full Text

The Present invention relates to Electrodeionization module and apparatus comprising it.
The present invention relates to an electrodeionization (EDS) module and apparatus adapted to transfer ions present in a liquid.under the influence of a polar field. Specifically, this invention relates to an EDI apparatus adapted to purify aqueous liquids for the production of high purity water or uitra-pure water.
The purification of an aqueous liquid by reducing the concentration of ions and molecules in the liquid has been an area of substantial technological interest. Numerous techniques have been used to purify aqueous liquids, and the most well known processes include distillation, electrodialysis, reverse osmosis, liquid chromatography, membrane filtration and ion-exchange, as well as the technique known as EDI.
The first known apparatus and method for treating liquids by EDI was described by Watler et al (c.f. W. R. Walters, D. W. Weister and L. J. Marek, Industrial and Engineering Chemistry, Vol. 47, No. 1, pp 61 - 67, 1955) in 1955. United States Patents Nos. 2,689,826 and 2,815,320 in the name of Kollsman were the first known patents describing an apparatus and process for removing ions from a liquid in a depleting chamber also known as a dilution, desalting or demineralization chamber, through a series of anionic and cationic membranes into an adjacent volume of liquid in a concentrating chamber under the influence of an electrical potential which causes the desired ions to migrate in a predetermined direction. The volume of the liquid being treated is depleted of ions while the volume of the adjacent liquid becomes enriched with transferred ions. The second of these patents describes the use . of '
SUBSTITUTE SHEET (RULE 26)
macroporous beads formed of ion-exchange resins as a filler material positioned between the anionic and cationic membranes.
These ion-exchange resins form a path for ion transfer and also serve as an increased conductivity bridge between the membranes for the movement of the ions.
Generally, ion-exchange resins employed in EDI modules are in the form of polymer beads (polystyrene, etc.), that are commercially available from Dow Chemical Company, Sybron Chemicals, Purolite and Rohm-Haas, for example, are typically 0.4 to 0.6 mm in diameter and contain functional groups which allow these beads to have an anion or cation-exchange function depending on the functional gpoups attached. The functional groups generally used for cation-exchange resins are sulfonic acid groups, while for anion-exchange resins these groups are typically quaternary ammonium groups. These beads are packed in the desalting and the concentrate compartments of an EDKapparatus either in a separate bed or a mixed bed configuration. A separate bed arrangement comprises the physical packing of anion and cation ion-exchange beads alternating throughout the desalting and concentrate compartments, the desalting and concentrate compartments being separated from the adjacent compartments by an anion-exchange membrane and a cation-exchange membrane. A mixed bed arrangement comprises the physical packing of an appropriate and uniform mixture of anion and cation-exchange beads throughout the desalting and concentrate compartments, the desalting and concentrate compartments being separated from the adjacent compartments by an anionic membrane and a cationic membrane.
Commercially successful EDI apparatuses and processes are described in particular in United States Patents Nos. 4,465,573; 4,632,745; 4,636,296; 4,687,561; 4,702,810; 5,026,465; 5,376,253; 5,954,935 and 5,503,729 and in International Patent Application No. WO-96/29133. Some of these apparatuses employed in particular desalting compartments containing an ion exchange composition and concentrating compartments which were free of ion-exchange solid material. The EDI apparatuses employed two terminal electrode chambers containing an anode and a cathode and were used to pass
direct current transversely through the body of the apparatuses containing a plurality of desalting compartments and concentrating compartments. In the case of US Patent No. 5,376,253, the arrangement of the apparatus is of cylindrical form that contains the concentrate and desalting compartments within. In the case of US Patent No 5,954,935, the electrode compartments are formed by desalting compartments, the cathode compartment being filled with anion exchanger material forming an anion resin bed and the anode compartment being filled with a cation exchanger material forming a cation resin bed. The concentrate compartments of, the apparatuses disclosed in this document can optionally be filled with such ion exchange resins or with a net-like spacer. In operation of such apparatuses, the dissolved ionized salts of the liquid are transferred through the appropriate membrane from the desalting compartments to the concentrating compartments and these ions were directed to waste. However, the major limitation with these apparatuses are the formation of insoluble scale, in particular within the cathode electrode compartment, and with time they fail to operate correctly.
In any membrane separation process where ions become concentrated, there is always the potential to exceed the solubility limits and form precipitates on membrane surfaces known commonly as scale. In particular, calcium carbonate (CaCOa) scale is formed when the levels of calcium and carbonate ions reach the solubility limit. The main source for the observed scale phenomena is the adsorption of carbon dioxide (CO2) in water that will react with hydroxide ions in the following way to form the calcium carbonate ion:
The presence of calcium ions in a concentrate compartment will naturally have as a consequence that calcium carbonate will precipitate out of solution. It should be noted in this connection that calcium carbonate is only slightly soluble in water, since only 14 milligrams is the maximum amount that
will dissolve in 1 liter of water. Therefore, the potential for forming scale increases with an increase in calcium ion concentration, pH, carbonate and bicarbonate ion concentrations in a concentrating compartment of an EDI apparatus.
Reactions at the EDI electrodes and water splitting in the EDI process creates shifts in the pH of a concentrate compartment, and is the source of protons (H+) and hydroxyl ions (OH") that will contribute effectively to the formation of scale, in particular from the hydroxyl ions. The reactions occurring at the electrodes are shown below, whereby the anode reaction is (3) and the cathode reaction is (4):
Water splitting occurring in the desalting compartments is an additional source of hydroxyl ions within the EDI module. In a concentrating compartment where the hydroxyl ions are entering through the anion-exchange membrane and especially along the surface of that anion-exchange membrane, the pH can become sufficiently high enough to generate the formation of scale. Consequently, the formation of scale within the EDI module will result in a very high electrical resistance and blocking of the flow channels leading to a rapid decline in the production of quality water.
There are methods available for the pretreatment of the feed water prior to it entering the EDI apparatus, such as water softening and reverse osmosis, which will reduce the ion concentrations of Ca2+, HCO3" and CO32" and therefore reduce the incidence of scale formation. However, improper maintenance of these apparatuses has resulted in limited success in reducing the scale formation inside EDI apparatuses.
Additional commercially successful EDI apparatuses were described in United States Patents Nos. 5,154,809; 5,308,466; 5,316,637 and 5,593,563. These apparatuses all utilize a plurality of desalting compartments containing an ion-exchange composition in the form of resin beads, and a
plurality of concentrate compartments which also contain an ion-exchange composition in the form of resin beads. However, in the latter compartments the selectivity for anions and cations was lower. United States Patent No. 5,593,563 addressed the problem of the formation of scale in the cathode electrode compartment by including electrically conductive particles or beads in the cathode electrode compartment. These electrically conductive particles or beads are metallic or constituted by carbon. However, some of these apparatuses experienced internal movement of the ion-exchange compositions in both the desalting and concentrate compartments which resulted in internal blockages, due to the high operational feed pressures or flow rates, which made some apparatuses fail to operate over a period of time.
Alternative ion-exchange compositions have been produced in the form of fabrics made of polymer fibers that contain anion-exchange and cation-exchange functional groups similar to those mentioned above and adapted to be used as ion-exchangers, namely quaternary ammonium groups and sulfonic acide groups, respectively. The basic material of these polymer fibers can be constituted by cellulose based material as well as more robust polymer materials such as polyolefins (c.f.:"S. Ezzahar, A. T. Cherif, J. Sandeaux, R. Sandeaux and C. Gavach, Desalination, Vol. 104, pp 227 - 233, 1996; E. Dejean, E. Laktionov, J. Sandeaux, R. Sandeaux, G. Pourcelly and C. Gavach, Desalination, Vol. 114, pp 165 - 173, 1997; . E. Dejean, J. Sandeaux, R. Sandeaux and C. Gavach, Separation Science and Technology, Vol. 33, No. 6, pp 801 - 818, 1998.; E. Laktionov, E. Dejean, J. Sandeaux, R. Sandeaux, C. Gavach and G. Pourcelly, Separation Science and Technology, Vol. 34, No. 1, pp 69 - 84, 1999"). The desired functional groups are grafted onto these fibers in order to create the ion-exchange behavior required for the purification of aqueous liquids. United States Patents Nos. 3,723,306; 5,152,896 and 5,885,453 and French Patent Applications Nos. 1487391; 1492522 and 1522387 give examples of grafting functional groups onto various materials, whereby ion-exchange fibers have been developed.
An alternative technology to grafting the desired ion-exchange functional groups onto the surface of polyolefin type fibers, is the manufacture
of heterogeneous ion-exchange materials similar to that described in US Patent^ Nos. 5,346,924 and 5,531,899. The heterogeneous ion-exchange fibers can be manufactured by mixing an appropriate amount of polyolefin binder with an apparopriate amount of anion and/or cation ion exchange material, mechanically crushing and mixing the components and thermally extruding or moulding the heterogeneous ion-exchange textile polymer fibers.
Commercially successful EDI apparatuses employing ion-exchange polymer fibers have been commercialized by Ebara Corporation and are described in particular in United States Patents Nos. 5,308,467; 5,425,866; 5,738,775 and European Patent Application No. 1069079. The ion-exchange polymer fibers employed in these EDI apparatuses are in the form of anion-exchange woven or non-woven fabrics, cation-exchange woven or non-woven fabrics, anion conducting spacers and cation conducting spacers, these spacers or separation fibers being respectively provided with anion and cation-exchange groups and are located in particular between the aforementioned woven or non-woven fabrics. These EDI apparatuses utilize a plurality of desalting compartments containing the anion and cation-exchange woven or non-woven fabrics and the conducting spacers and a plurality of concentrate compartments which contain anion and cation conducting spacers only. The desalting and concentrate compartments are alternating and separated by anion-exchange and cation-exchange membranes. These apparatuses also employed two terminal electrode compartments containing an anode and a cathode. However, the major limitation with these EDI apparatuses is their susceptibility to the formation of scale with water containing high levels of dissolved CC-2 and their low power efficiency.
The present invention is based on the surprising discovery that the
implementation in the desalting and concentrating compartments of either resin
./ beads having ion-exchange functional groups or non-woven or woven fabrics
made of ion-exchange fibers, with the resin beads and the fabrics being present together within the electrodeionization module makes it possible to achieve a substantially more effective implementation than those known in the state of the
art, in particular with respect to the purity of the water and the maintenance of this purity overtime.
The present invention thus relates to an electrodeionization (EDI) module comprising at least one ion-exchange membrane delimiting at least one desalting zone and at least one concentrating zone situated between electrodes, each zone being provided with ion-exchange means, characterized in that the ion-exchange means present in a zone are comprised of either ion-exchange resin beads or at least one non-woven or woven fabric made of ion-exchange fibers, the resin beads and the fabric(s) being both present in the EDI module.
Each zone is preferably formed by a compartment and, in this case, the module contains either at least one desalting compartment separated from two adjacent concentrating compartments respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane or at least one concentrating compartment separated from two adjacent desalting compartments respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane.
According to a preferred embodiment of the present invention, the EDI module comprises alternating desalting compartments and concentrating compartments between electrodes, wherein each desalting compartment is adjacent to two concentrating compartments and separated therefrom respectively by an anion selective ion-exchange membrane and a cation selective ion-exchange membrane, each compartment being provided with ion-exchange means, and is characterized in that the ion-exchange means present in the desalting compartments are comprised of ion-exchange resin beads while the ion-exchange means present in the concentrating compartments are comprised of at least one non-woven or woven fabric made of ion-exchange fibers.
According to an alternative embodiment, the EDI module comprises alternating desalting compartments and concentrating compartments between electrodes, wherein each desalting compartment is adjacent to two concentrating compartments and separated therefrom respectively by an anion
selective ion-exchange membrane and a cation selective ion-exchange membrane, each -compartment being provided with ion-exchange means, characterized in that the ion-exchange means present in the concentrating compartments are comprised of ion-exchange resin beads while the ion-exchange means present in the desalting compartments are comprised of at least one non-woven or woven fabric made of ion-exchange fibers.
Furthermore, the arrangement according to the preferred embodiment of the invention lends itself advantageously to a development according to which the ion-exchange means comprised of at least one woven or non-woven fabric made of ion-exchange fibers form at least one assembly comprising a woven or non-woven fabric made of anion-exchange fibers and a woven or non-woven fabric made of cation-exchange fibers which are placed in a face to face relationship, and at least one ion conducting spacer which is able to perform ion-exchanges and is interposed between the anion and cation-exchange fabrics.
Preferably, in this case, the or each assembly is arranged such that the woven or non-woven fabric which is at the anion selective ion-echange membrane end is a woven or non-woven fabric made of anion-exchange fibers and the woven or non-woven fabric which is at the cation selective ion-exchange membrane end is a woven or non-woven fabric made of cation-exchange fibers.
Preferably too, an anion conducting spacer and a cation conducting spacer which are able to perform ion-exchanges are positioned between the anion and cation-exchange fabrics and are respectively situated next to the anion-exchange fabric and the cation-exchange fabric.
A particularly effective implementation, can thus be obtained, as will be seen in more detail below.
For reasons of efficacy, economy and/or ease of manufacture, it is also preferred that:
- each spacer is in the form of a net-like spacer, preferably a diagonal net-like spacer; and/or
- the fabrics and the spacer(s) are in intimate contact with each
other and are, preferably, carried by a frame; and/or
- the or each woven or non-woven fabric made of ion-exchange
fibers comprises a substrate made of fibers into which ion-exchange functional
groups have been introduced by grafting with monomers which have ion-
exchange groups or grafting with monomers having a group which may be
converted to ion-exchange group and then converting said group to the ion-
exchange group, and the or each spacer, when present, comprises a substrate
made of fibers or resins into which ion-exchange functional groups have been
introduced by grafting with monomers which have ion-exchange groups or
grafting with monomers having a group which may be converted to ion-
exchange group and then converting said group to the ion-exchange group;
and/or
- the substrate is a cellulosic or polyolefinic material; and/or
- the cation-exchange fibers and/or cation-conducting spacer(s)
have sulfonic acid groups and the anion exchange fibers and/or anion-
conducting spacer(s) have quaternary ammonium groups; and/or
- the functional groups are introduced by grafting polymerization
initiated by radiation (UV-rays, X-rays, y-rays, accelerated electrons, B-rays or
a-rays), or by a chemical reagent, such as cerium ions; and/or
- the or each woven or non-woven fabric made of ion-exchange
fibers comprises a substrate made of heterogeneous fibers .comprised of a
mixture of ion-exchange material and polyolefinic binder and the or each
spacer, when present, comprises a substrate made of resins or heterogeneous
fibers comprised of a mixture of ion-exchange material and polyoiefin'ic binder.
Regarding the ion-exchange resin beads, they can be formed by anion-exchangers and cation-exchangers forming a mixed bed or separate beds, but preferably a mixed bed. In this case, the ion-exchange resin beads are preferably formed from polymers, such as polystyrene or styrene-divinyl benzene copolymers, having functional groups, preferably sulfonic acid groups for the cation-exchangers and quaternary ammonium groups for the anion-exchangers.
The. arrangement according to the invention also lends itself to another development, which may advantageously be combined with the preceding one, according to which an electrode compartment is formed between each electrode and the ion-exchange membrane adjacent to the electrode. In this case the cathode compartment preferably contains electrically conductive particles, which are preferably carbon and/or metallic particles.
This development enables the risk of scale formation to be minimized.
According to an alternative development, the cathode compartment comprises at least one spacer in the form of a net-like spacer maintaining the flow between the cathode and the adjacent cation selective membrane.
Preferably, in this case, the or each spacer in the cathode compartment has ion-exchange groups.
The anode compartment also preferably comprises, in such a case, at least one spacer in the form of a net-like spacer maintaining the flow between the anode and the adjacent anion selective membrane, and which, advantageously, possesses ion-exchange groups.
The electrode compartment may, moreover, be formed by the concentrating or desalting compartment adjacent to each electrode.
The EDI module also preferably comprises a plurality of alternating desalting compartments and concentrating compartments and fluid communication to each of the desalting compartments and to each of the concentrating compartments are each provided in a serial or parallel arrangement.
The present invention also relates to an EDI apparatus for water production of high purity or for production of ultra-pure water, comprising an EDI module as defined above.
The features and advantages of the present invention will emerge furthermore from the following description, made by way of example with reference to the accompanying drawings, in which:
- Figure 1 is a diagrammatic view of an electrodeionization module
according to a preferred embodiment of the invention; and
- Figure 2 is a graph of the performance of the electrodeionization
module of Figure 1 and of known electrodeionization modules, at the 36th day of
operation.
/•
In the embodiment shown in Figure 1, the electrodeionization module 10 according to the invention comprises, in a manner known per se, alternating desalting compartments 11 and concentrating compartments 12 arranged between two terminal electrodes, i.e. a cathode 13 and an anode 14.
Each desalting compartment 11 is separated from two adjacent concentrating compartments 12, respectively by an anion selective ion-exchange membrane 15 and a cation selective ion-exchange membrane 16.
In the embodiment shown, the selective membranes adjacent to the cathode 13 and the anode 14 are respectively constituted by a cation selective membrane 16 and an anion selective membrane 15. The compartments situated between these latter membranes and the respective electrodes 13, 14 are concentrating compartments 12 each forming an electrode compartment containing respectively the cathode 13 and the anode 14.
According to the invention, these compartments 11 and 12 are filled in the following manner:
1) each desalting compartment 11 is filled with cation-exchange
resin beads and anion-exchange resin beads forming a mixed bed. These ion-
exchange resin beads are formed from polymers having functional groups,
which are sulfonic acid groups for the cation-exchangers and quaternary
ammonium groups for the anion-exchangers.
2) the concentrating compartment 12 forming a housing
compartment for the cathode 13 is filled with electrically conductive beads 18,
while the concentrating compartment 12 forming a housing compartment for the
anode 14 comprises a spacer in the form of a net 19 maintaining the flow
between the anode and the adjacent anion selective membrane 15. In practice,
this spacer 19 is formed from a polyolefinic resin net on which have been
grafted anion-exchange groups. More particularly, a polyethylene resin net is used on which quaternary ammonium groups have been grafted.
Such a spacer is similar to those described in the European patent application EP 1 069 079 mentioned above.
3) Each of the remaining concentrating compartments 12 is filled with a sandwich structure 20 each comprising a sheet like non-woven fabric 21 made of anion-exchange fibers, a sheet like non-woven fabric 22 made of cation-exchange fibers, an anion conducting spacer 23 and a cation conducting spacer 24.
The non-woven fabrics 21 and 22 are disposed in face to face relationship and the spacers 23 and 24 are interposed between these two fabrics and are situated on the side of the anion-exchange non-woven fabric 21 in the case of the anion conducting spacer 23 and on the side of the cation-exchange non-woven fabric 22 in the case of the cation conducting spacer 24.
The spacers 23 and 24 are more particularly in the form of a diagonal net formed of polyolefins of high molecular weight on which the ion-exchange functional groups have been grafted, i.e. anion-exchange groups on the anion conducting spacer 23 and cation-exchange groups on the cation conducting spacer 24.
The non-woven fabrics 21 and 22 have also been developed from polyolefinic fibers of high molecular weight, on which the functional groups have been grafted. These polyolefinic fibers are, here, fibers of polyethylene and polypropylene, the functional groups grafted on the fibers being sulfonic acid groups in the case of the cation-exchange fibers and quaternary ammonium groups in the case of the anion-exchange fibers.
These grafted fibers have been obtained through grafting polymerization initiated with radiation, here y-rays.
It should also be noted that the non-woven fabrics 21 and 22 and the ion conducting spacers 23 and 24 are placed in intimate contact with each other.
Furthermore, the anion-exchange fabric 21 is arranged on the side of the anion selective membrane 15, while the cation-exchange fabric 22 is arranged on the side of the opposite cation selective membrane 16.
It should also be noted that each sandwich structure 20 is carried by a frame (not shown on Figure 1) forming the corresponding compartments 12 and provided, for this purpose, with inlet and outlet passages communicating with the ion-exchange sandwich structure 20, and more particularly with the spacers 23 and 24.
For more detail in relation to this, reference may also be made to the European patent application EP-1-069 079 mentioned above.
In the embodiment shown, fluid communication is provided respectively between the desalting compartments 11 and concentrating compartments 12 according to a serial arrangement (arrows 25 in dotted lines for feeding the concentrating compartments 12 and arrows 26 in solid lines for feeding the desalting compartments 11).
Thus the product coming out from the last desalting compartment 11 (arrow 27 in solid line) is demineralized water, while the product coming out from the last concentrating compartment 12 (arrow 28 in dotted line) is composed of water in which are concentrated the ions extracted from the water that has passed through the desalting compartments 11.
Considering this in more detail, the ions to be eliminated are fixed on the mixed resin beads placed in the desalting compartments 11, out of which comes the demineralized water; by virtue of the application of an electric potential, the ions then migrate rapidly towards the concentrating compartments 12, where they are concentrated for elimination by the electrodeionization module 10.
More details about, on the one hand, the preparation of the ion-exchange non-woven fabrics and ion conducting spacers and, on the other hand, the fabrication of the EDI module are given below.
Preparation of ion-exchange non-woven fabrics
Table 1 shows the specifications of the substrate non-woven fabric used in the experiments below to prepare and ion-exchange non-woven fabric. The substrate non-woven fabric was prepared by thermal fusion of composite fibers consisting of a polypropylene core and a polyethylene sheath.
TABLE 1
Core/sheath Polypropylene/polyethylene
Areal density 50 g/m2
Thickness 0.55 mm
Fiber diameter 15-40 |im
Process Thermal fusion
Porosity 91 %
One sample of the non-woven fabric identification in Table 1 was irradiated with y-rays in a nitrogen atmosphere and then immersed in a solution of glycidyl methacrylate (GMA) for reaction. Graft ratio of 163 % was obtained. Thereafter, the grafted non-woven fabric was immersed in a liquid mixture of sodium sulfite, isopropyl alcohol and water for sulfonation. Measurement of the ion-exchange capacity of the thus treated non-woven fabric showed that it was a strong acidic cation-exchange non-woven fabric having a salt splitting capacity of 2.82 meg/g.
Another sample of the same non-woven fabric was irradiated with y-rays in a nitrogen atmosphere and thereafter immersed in a solution of chloromethylstyrene (CMS) for reaction and graft ratio of 148 % was obtained. The grafted non-woven fabric was then immersed in an aqueous solution of 10 % trimethylamine to introduce quaternary ammonium groups. The product was a strong basic anion-exchange non-woven fabric having a salt splitting capacity-of 2.49 meg/g.
Preparation of ion-conducting spacers
Table 2 shows the specifications of the diagonal net used as the substrate for preparing an ion-conducting spacer used in the experiments below.

TABLE 2
Constituent material Polyethylene
Shape Diagonal net
Thickness 0.8 mm
Mesh opening 6 mm x 3 mm
One sample of the diagonal net substrate identified in Table 2 was irradiated with y-rays in a N2 atmosphere and thereafter immersed in a liquid mixture of glycidyl methacrylate (GMA) and dimethylformamide (DMF) for reaction and graft ratio of 53 % was obtained. The grafted net was then immersed in a liquid mixture of sodium sulfite, isopropyl alcohol and water for sulfonation. The product was a strong acidic cation-conducting spacer having a salt splitting capacity of 0.62 meg/g.
Another sample of the diagonal net substrate identified in Table 2 was irradiated under the same conditions as just mentioned above and immersed, in a liquid mixture of vinylbenzyltrimethyl ammonium chloride (VBTAC), dimethyl acrylamide (DMAA) and water for reaction, and graft ratio of 36 % was obtained. The product was a strong basic anion-conducting spacer
having a salt splitting capacity of 0.44 meg/g.
Fabrication of EDI modules
The thus-prepared ion-exchange non-woven fabrics and ion-conducting spacers were mounted in the concentrating compartments of EDI modules (comprising four desalting compartments, three concentrating compartments, a cathode compartment and an anode compartment) of the type employed in Millipore's commercial ELIX® by system.
The ion-exchange resin beads used therein are cation and anion exchange resin beads produced either by Rohm & Haas or Dow Chemical and sold under the respective trade names, AMBERLITE® AND DOWEX® (particle size = 590 + 50 urn). The carbon beads used therein as the electrically conductive beads are produced by Rohm & Haas and sold under the trade name, AMBERSORB® (particle size = 590 ± 50 jim). Each deionization compartment measured 220 x 35 mm with a thickness of 3 mm and each

concentration compartment was 0.8 mm thick. Each anode compartment and cathode compartment measured 2,5 mm thick.
The performances of the thus obtained electrodeionization modules (configurations A1 and A2 below) have been compared to conventional electrodeionization modules (configurations B1, B2 and C below). In configurations A1 and A2 (present invention), each of compartments was loaded as shown in Fig. 1 and explained above. Configurations B1 and B2 (conventional) were the same as A1 and A2, except that each concentrating compartment was filled with cation and anion exchange resin beads forming a mixed bed. Configuration C (conventional) was the same as A1 and A2, except that each desalting compartment was filled in the same manner as each concentrating compartment.
Using these apparatuses, a water pass test was conducted using supply water under the conditions as shown below. The flow volume of the feeding water was 3 l/h and the operating current was a 70 mA constant current. The fluid communication to each of the desalting compartments, on the one hand, and to each of the anode compartment, concentrating compartments and cathode compartment, on the other hand, are each provided as show in Fig. 1 in a serial arrangement.
The operating conditions of ultrapure water production apparatuses incorporating these electrodeionization modules are the following:
Operating modes
Characteristics of the supply water:
1) reverse osmosis (RO) water No. 1 [C02]=24 mg/i pH=5.5a5.7 temperature = 20 to 22°C conductivity = 21.0 jas.cm
2) reverse osmosis (RO) water No. 2 [C02]=32 mg/I pH=5.2
temperature = 18°C conductivity = 16.5 jis.cm [Ca2+]=2.0 to 3.0 mg/I as CaC03
EDI operating modes:
. Operating mode 1: The ED] apparatuses have been subjected to continuous operation 24 hours a day, from the first day to the seventh day.
. Operating mode 2: The EDI apparatuses have been subjected to an operating mode consisting alternately of 2 hours of operation and two hours stopped (in standby), from the seventh day to the sixteenth day.
. Operating mode 3: The EDI apparatuses have been subjected to operation for the following times: 1:00-3:00; 5:00-7:00; 9:00-11:00 and 13:00-15:00. During the remaining period of time, the apparatuses were stopped (in standby) from the 16th day to the 31st day.
. Operating mode 4: the EDI apparatuses have been subjected to operation for the following times: 8:00-10:00 ; 14:00-16:00 ; and 20:00-22:00. During the remaining period of time, the apparatuses were stopped (in standby) from the 31st day to the 57th day.
The physical measurements carried out during these tests were measurements of voltage and current level (energy consumption and scale formation) and resistivity as a measure of the water quality produced by these EDI apparatuses.
The measurement results are given in tables 1, 2 and 3 which follow and in the graph of Figure 2.
Table 1: Comparison of the water qualities produced with the EDI apparatuses.

(Table Removed)
EDI apparatuses using RO water No. 2
Apparatus B2 using RO water No. 1 between days 1 and 21
Apparatus C using only RO water No. 1

Table 2: Comparison of energy consumption of the EDI apparatuses.
(Table Removed)
- EDI apparatuses using RO water No. 2
- Apparatus B2 using RO water No. 1 between days 1 and 21
- Apparatus C using only RO water No. 1
Table 3: Observed electrical impedance/resistance in ohms (Q.) profile of the preferred embodiments A1 and A2 with time

(Table Removed)
a : - EDI apparatuses using RO water No. 2
The electrical impedance (ohms) of a given EDI module is calculated from the applied operating current and the resulting voltage. It is normal to observe a steady increase in the impedance of a given EDI module with time. Whenever there is significant scale formation on the membranes (usually the anion) of a given EDI module, then this will be indicated by a rapid
increase in the observed impedance (i.e. 50 % increase in 2 or 3 days), as a
/ result of scale precipitation on the membrane interrupting the flow of electrical
charge or current through the EDI module. The data presented in the above table strongly indicates that there is no or negligible scale precipitation on the surface of the membranes of these EDI modules.
It will be understood that the association of two different ion-exchange configurations respectively in the desalting and concentrating compartments of the electrodeionization modules, according to the present invention, provides the following advantages:
1) the production of ultrapure water, of a higher level of purity than
that of known apparatuses, in a reliable manner over a longer period of time
than with these known apparatuses in continuous operation or in cyclic
operation (certain periods of operation and certain periods stopped)
representing a much more realistic implementation in water purification
installations existing in the world. The synergetic effect resulting from the
association dealt with above will be particularly appreciated (c.f. table 1 and
Figure 2).
2) the EDI apparatus comprising the electrodeionization module
10 can operate with supply water with greater quantities of carbon dioxide and
of calcium ions than with known apparatuses without any adverse effect on the
quality of purified water produced and without any effect on scale formation
when calcium ions are present in the supply load at moderate concentrations
(in practice less than 30 mg of Ca2+ per liter).
3) the compression of fibers in the concentrating compartments of
the electrodeionization module 10 restricts the internal movement of the ion-
exchange resin beads in mixed bed configuration in the desalting
compartments, which enables the EDI apparatus with this to function at high operational pressures and flow rates of the supply load.
4) improved transport of the ions in the concentrating
compartments due to the combined presence of the separate layers of ion-
exchange materials in the concentrating compartments and of the ion-
exchange resin beads in mixed bed configuration in the desalting
compartments.
5) the energy consumption is low and stable.
Naturally, the present invention is not limited to the form of the embodiment described and represented, but covers any variant form.

We Claim:
1. Electrodeionization (EDI) module comprising at least one ion-exchange membrane
delimiting at least one desalting zone (1 1) and at least one concentrating zone (12)
situated between electrodes (13, 14), each zone being provided with ion-exchange
means, characterized in that, the ion- exchange means present in a zone are comprised of
either ion-exchange resin beads (17) or at least one non-woven or w,oven fabric (21, 22)
made of ion- exchange fibers, the resin beads and the fabric(s) being both present in the
ED1 module.
2. ED1 module as claimed in claim 1, wherein each zone is formed by a compartment and
the module contains at least one desalting compartment (I 1) separated from two adjacent
concentrating compartments respectively by an anion selective ion-exchange membrane
(15) and a cation selective ion-exchange membrane (16).
3. ED1 module as claimed in claim 1, wherein each zone is formed by a compartment and
the module contains at least one concentrating compartment separated from two adjacent
desalting compartments respectively by an anion selective ion-exchange membrane (15)
and a cation selective ion-exchange membrane (16).
4. ED1 module containing alternating desalting compartments and concentrating
compartments between electrodes, wherein each desalting compartment ( I I) is adjacent
to two 'concentrating compartments and separated therefrom respectively by an anion
selective ion-exchange membrane (15) and a cation selective ion-exchange membrane
(161, each compartment being provided with ion-exchange means, characterized in that,
the ion-exchange means present in the desalting compartments and concentration
compartments are comprised of ion-exchange resin beads (1 7) while the ion-exchange
means present in the concentrating compartments are comprised of at least one nonwoven
or woven fabric (2 1,22) made of ion-exchange fibers.
5. ED1 module as claimed in anyone of claims 2 to 4, wherein the ion-exchange means
comprised of at least one woven or nonwoven fabric made of ion-exchange fibers form
at least one assembly comprising a woven or non-woven fabric (21) made of anionexchange
fibers and a woven or non- woven fabric (22) made of cation-exchange fibers
which are placed in a face to face relationship, and at least one ion conducting spacer
(23,24) which is able to perform ion-exchanges and is interposed between the anion and
cation-exchange fibers.
6. ED1 module as claimed in claim 5, wherein each assembly is arranged such that the
woven or non-woven fabric which is at the anion selective ion-exchange membrane (15)
end is a woven or non-woven fabric made of anion-exchange fibers and the woven or
non-woven fabric which is at the cation selective ion-exchange membrane (16) end is a
woven or non-woven fabric made of cation-exchange fibers.
7. ED1 module as claimed in claim 5 or 6, wherein an anion conducting spacer and a cation
conducting spacer which are able to perform ion-exchanges are positioned between the
anion and cation-exchange fabrics and are respectively situated next to the anionexchange
fabric and the cation-exchange fabric.
8. ED1 module as claimed in anyone of claims 5 to 7, wherein each spacer is in the form of
net-like spacer, preferably a diagonal net-like spacer.
9. ED1 module as claimed in anyone of claims 5 to 8, wherein the fabrics and the spacer(s)
of an assembly are in intimate contact with each other and are, preferably, carried by a
frame.
10. ED1 module as claimed in any of the claims 1 to 9, wherein each woven or non-woven
fabric (21, 22) made of ion-exchange fibers comprises a substrate made of fibers into
which ion-exchange functional groups have been introduced by grafting with monomers
which have ion-exchange groups or grafting with monomers having a group which may
be converted to ion- exchange group and then converting said group to the ion-exchange
group, a d each spacer, when present, comprises a substrate made of fibers or resins into
which ion-exchange functional group have been introduced by grafting with monomers
which have ion-exchange groups or grafting with monomers having a group which may
be converted to ion-exchange group and then converting said group to the ion-exchange
group.
11. EDI module as claimed in claim 10, wherein the substrate is a ceIlulosic or polyolefinic
material.
12. ED1 module as claimed in claim 10 or 11, wherein the functional groups are introduced
by grafting polymerization initiated by radiation or a chemical reagent..
13. ED1 module as claimed in claim 12, wherein the radiation source is ionizing radiation,
such. as UV-rays, X-rays, y-rays, accelerated electrons, P-rays or a-rays.
14. ED1 module as claimed in claim 12, wherein the chemical reagent comprises ceriumions.
15. ED1 module as claimed in anyone of claims 5 to 14, wherein the cation-exchange fibers
andlor cation-conducting spacer(s) have sulfonic acid groups and the anion exchange
fibers and/or anion-conducting spacer(s) have quaternary ammonium groups.
16. ED1 module as claimed in anyone of claims T to 8, wherein each woven or non-woven
(21,22) fabric made of ion-exchange fibers comprises a substrate made of heterogeneous
fibers comprised of a mixture of ion-exchange material and polyolefinic binder and the
or each spacer, when present, comprises a substrate made of resins or heterogeneous
fibers comprised of a mixture of ion-exchange material and polyolefinic binder.
17. ED1 module as claimed in anyone of claims 1 to 16, wherein the ion-exchange resin
beads (1 7) are formed by anion-exchangers and cation-exchangers forming a mixed bed
or separate beds, preferably a mixed bed.
18. ED1 module as claimed in claim 17, wherein the ion-exchange resin beads (17) are
formed from polymers, such as polystyrene or styrene-divinylbenzene copolymers,
having functional groups, preferably sulfonic acid groups for the cation-exchangers and
quaternary ammonium groups for the anion-exchangers.
19. ED1 module as claimed in anyone of claims 2 to 18, wherein an electrode compartment
is formed between each electrode and the ion- exchange membrane adjacent to the 1
electrode.
20. ED1 module as claimed in claim 19, wherein the cathode compartment contains
electrically conductive particles, which are preferably carbon andlor metallic particles.
21. ED1 module as claimed in claim 19, wherein the cathode compartment comprises at least
one spacer in the form of a net-like spacer maintaining the flow between the cathode and
the adjacent cation selective membrane.
22. ED1 module as claimed in claim 21, wherein each spacer in the cathode compartment has
ion-exchange groups.
23. ED1 module as claimed in anyone of claims 19 to 22, wherein the anode compartment
comprises at least one spacer in the form of a net-like spacer maintaining the flow
between the anode and the adjacent anion selective membrane.
24. ED1 module as claimed in claim 23, wherein each spacer in the anode compartment has
ion-exchange groups.
25. ED1 module as claimed in anyone of claims 19 to 24, wherein the concentrating or
desalting compartment adjacent to each electrode forms the electrode compartment.
26. ED1 module as claimed in anyone of claims 2 to 25, wherein a plurality of alternating
desalting compartments (11) and concentrating compartments and wherein fluid
communication to each of the desalting compartments (11) and to each of the
concentrating compartments are each provided in a serial or parallel arrangement
27. ED1 module as claimed in any of the previous claims, which is incorporated in an ED1
apparatus for water production of high purity or for production of ultra-pure water.

Documents:

73-delnp-2006-Abstract-(12-07-2013).pdf

73-DELNP-2006-Abstract-(18-05-2012).pdf

73-delnp-2006-abstract.pdf

73-DELNP-2006-Assignment-(03-02-2012).pdf

73-delnp-2006-Claims-(12-07-2013).pdf

73-DELNP-2006-Claims-(18-05-2012).pdf

73-delnp-2006-claims.pdf

73-DELNP-2006-Correspondence Others-(03-02-2012).pdf

73-delnp-2006-Correspondence Others-(03-12-2012).pdf

73-delnp-2006-Correspondence Others-(12-07-2013).pdf

73-DELNP-2006-Correspondence Others-(18-05-2012).pdf

73-delnp-2006-Correspondence Others-(21-12-2012).pdf

73-delnp-2006-correspondence-others-1.pdf

73-delnp-2006-correspondence-others.pdf

73-DELNP-2006-Description (Complete)-(18-05-2012).pdf

73-delnp-2006-description (complete).pdf

73-DELNP-2006-Drawings-(18-05-2012).pdf

73-delnp-2006-drawings.pdf

73-delnp-2006-Form-1-(12-07-2013).pdf

73-DELNP-2006-Form-1-(18-05-2012).pdf

73-delnp-2006-form-1.pdf

73-delnp-2006-form-18.pdf

73-delnp-2006-Form-2-(12-07-2013).pdf

73-DELNP-2006-Form-2-(18-05-2012).pdf

73-delnp-2006-form-2.pdf

73-DELNP-2006-Form-3-(18-05-2012).pdf

73-delnp-2006-form-3.pdf

73-delnp-2006-form-5.pdf

73-DELNP-2006-GPA-(18-05-2012).pdf

73-delnp-2006-gpa.pdf

73-delnp-2006-pct-210.pdf

73-DELNP-2006-Petition-137-(18-05-2012).pdf

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Patent Number

257886

Indian Patent Application Number

73/DELNP/2006

PG Journal Number

47/2013

Publication Date

22-Nov-2013

Grant Date

14-Nov-2013

Date of Filing

04-Jan-2006

Name of Patentee

MILLIPORE CORPORATION

Applicant Address

290 CONCORD ROAD, BILLERICA, MASSACHUSETTS 01821, USA.

Inventors:

#	Inventor's Name	Inventor's Address
1	JACQUES MOULIN	12, RUE EDOUARD MANET, DOMAINE DE GATINES, F-78370 PLAISIR, FRANCE
2	KUNIO FUJIWARA	35-4, TORIGAOKA, TOTSUKA-KU, YOKOHAMA, JAPAN.

PCT International Classification Number

B01D 61/44

PCT International Application Number

PCT/IB2003/004112

PCT International Filing date

2003-08-05

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	PCT/IB03/004112	2003-08-05	PCT