2) United States Patent ay a my 3) wo ey @y (86) (7) G0) Jul, 31, 2013 on} Manabe et al. ELECTROLYTIC ENRICHMENT METHOD FOR HEAVY WATER Applicant: INDUSTRIE DE NORA S.p.. Milan a Akiyoshi Manabe, Fujisawa (JP) Yoshinori Nishiki, Fujisawa (JP) Akira Kunimatsu, Fujisawa UP) Inventors INDUSTRIE DE NORA SP. ap Assignee: Milan Notice: Subject to any disclaimer, the term ofthis, patent is extended of adjusted under 33 USC. 1540) by 198 days, Appl. Nox 141902,363 PCT Filed: Jul 24, 2014 PCT No, $371 (€X0) (Q) Dae PCTIBP2014/065948 31, 2015 PCT Pub, Nos WO2015/014716 PCT Pub, Date: Feb. 8, 2018 Prior Publication Data US 201610368789 AL Dec. 22, 2016 Foreign Application Priority Data oe) 2013-158735 Im. cl, CORE 1146 CORE 1461 (200601) (2008.01) (Continued CORE 1/461 (2013.01): BOLD 59/40 (201301); CorB 52 (2013.01), COIB 1300207 (201301) (Continued) 'US009890062B2 US 9,890,062 B2 Feb. 13, 2018 (10) Patent No.: (4s) Date of Patent: (58) Fleld of Classification Search None See application file for complete search history 66) References Cited US. PATENT DOCUMENTS. 2080296167 AL* 122008 Davidion cast a908 PORPIGN PATENT DOCUMENTS ce ” 79si2 A 3/1985 soe A L196 (Continved) (OTHER PUBLICATIONS International Search Report base om latrntinal application No, PCTEP20L4065048, dated Sep. 17,2014. 3 popes) (Continved) Primary Evaminer— Arva $ Phase (14) Attorney, Agent, or Firm — Lucas & Mercaati, LLP on ABSTRACT An electrolytic enrichment method for heavy water includes enriching heavy water by electolysis using an alkaline water electrolysis cell inding an anode chamber that holds an anode, a cathode chamber that holds cathode, and 4 disphragm. Ia the method, an electrolyte prepared by ‘adding high-coneentration alkaline water to raw material ‘water containing heavy Water is circularly supplied t0 the ‘anode chamber aad the cathode chaenber from # circulation ‘tank; an anode-side gas-Tiguid separator and an anode-side wwaterscal device are connected tothe anode chamber, and 4 cathode-side gas-liquid separator and a cathode-side ‘water-seal deve are connected wo the eathode chaenber: and lectolysis is continued while the alkali concentration in the clecimlyte supplied to both electrolysis eharnbers is main- ‘ained ata constant concentration by circularly supplying, to the circulation tank, the clectmlyte from which the gas (Continsed)US 9,890,062 B2 Page 2 enerated from the anode-side gas-liquid separator and the ‘calhode-side gas-liquid separator is separated 9 Claims, 1 Drawing Sheet (1) Inte. BOLD 39/40 (2006.01) coun 302 (2006.01) Cs 104 (2006.01) cone 13/02 (2006.01) (2) US.C1. CPC. C258 10d 2013.01): CO2F 2001/4619 (2013.01), Co2F 2301/46185 (2013.01), YORE (60/366 (201301) 66) References Cited FOREIGN PATENT DOCUMENTS. wp Sams A 129% wo 96356 AL 1/1996 wo om137435 AL 122009, (OTHER PUBLICATIONS ‘Moranaka ot a “HlestolytieEnschment of Teo in Water Using PEF’, Feetolyis, 2012, Ch7, pp. 141-162 * cited by examinerU.S. Patent Feb. 13, 2018 US 9,890,062 B2US 9,890,062 B2 1 ELECTROLYTIC ENRICHMENT METHOD FOR HEAVY WATER This application is a US. national stage of PCT/EP2014/ (065948 filed on Jul, 24, 2014 which claims the benefit of priority fom Japanese Patent Application No. 2013-158735 Sled Jul, 31, 2013 the contents of each of which are incomporated herein by reference BACKGROUND OF THE INVENTION 1. Field of the Invention ‘The present invention relates to an eloctolytic enrichment method for heavy water, in which heavy’ water is enriched by ‘electrolysis with an alkaline water electrolysis cell 2, Description of the Related Art Heavy water is water containing, many isotopic water molecules with Jaye mass numbers and having higher specie gravity than general water Heavy water has pi ‘al and chemical properties slighly dlferet from those of ‘general water. General water is refered 0 as “Tight water” relative to heavy water. Heavy water contains hydrogen ‘isotopes sch as deuterium (D, 241) and tritam (T, 31, and ‘oxygen isotopes 170 and 180. Inthe field of determination of safety ofan atomie porser plant, prediction of crustal movement, measurement of a hot-spring groundwater system, or the like, analysis of deuterium (D, 241) and ttium (T, 3H) in natural water is becoming important. A tritium concentration is a very low Jevel, and thus electrolytic enrichment is generally con- ducted for improving measurement accuracy. A generally known electrolytic enrichment method for heavy water ‘nchides preparing a sample solution in which an electrolyte is dissolved, and eleetrolyzing the solution using flat plates disposed to face each other Water contained in an electolyte ‘contains HOD and HOT ia addition wo HO, and these are ‘decomposed into hydrogen and oxygen according to ustal ‘water electrolysis, but FH,O is decomposed in preference to decomposition of HOD and HOT by the isotope effect to ‘increase the concentrations of denterium and tet in the ‘lectrolyte, resulting in enrichment. In this electrolysis, nickel is used as an anode, and see, iron, of nickel is Used as a cathode, and these electrodes are washed and used for ‘electrolysis under current-carrying conditions in a lass ‘container which contains semple water prepared by adding sliluted sodium hydroxide as a support salt to an aqueous solution containing heavy water. Heavy water is generally ‘enriched by continuing electroysis with a current density of 1 t 10 Adm? until a Figuid amount becomes Yio or less “while the solution temperature is kept at S°C.oF less in order to prevent water evaporation die to the beat generated, That is, electrolytic enrichment uses the property that tritium water isles eletrolyzed than light hydrogen water A method for electrolysis using metal electrodes inserted nto an alkaline aqueous solution has already been fre- ‘quently studied and publicly standardized in a mamual as 3 Sandard method, This method inclndes one-stage enrich- ment of tritium concentrations. However, in practice, @ eneral method for electrolytic enrichment as some prob- Jems. The problems Tie in complicated experiment opers- tions, titium ensichment rate linited to the upper limit of an electrolyte concentration, a danger of explosion de to the ‘occurrence of mixed gas of hydrogen and oxygen, much time required for electrolysis, and unsuitablenoss for large- ‘capacity treatment ‘Since a technique is considered in view of one-step separation and eapture of dilute inclusion, the problems are 0 o 2 {due to rouble with handling an aqueous alkaline electrolyte solution, dillculty in separating gases generated on both clecimdes, dticulty in increasing an electrolysis erent due to the generation of bubbles on a metal surface, ete, which fare mainly caused in a general electroytie method of an ‘aqueous alkaline solution. ‘On the other hand, a Water electrolytic method revently atracting attention is a water eleetristic miethod (hereinaf- ter refered to a “SPE water electrolysis") using a solid polymer electrolyte (hereinafter refered to as “SPE™). Inthe ‘arly 1970s, US General Elecsie Company frst applied fuel fell technology to the SPE. water electrolysis in svch a nner that an electrolysis portion having a strctue include ‘@ SPE membrane held between poross metal electrodes s immerse in pure water and eleeteolysis i performed only by passing a curren, generating decomposed gas from the porous electrodes. The SPE is one type of cation exebange resins and has a polymer chain to which sulfone acid groups contributing to ionic conduction are chemically bonded ‘When a current is passed between both electrodes, water is decomposed, and oxygen gas is generated on an anode, ‘zencriting hydrogen ions. The hydrogen ions move trough the sulfonic acid groups in the SPE, reach the cathode, and receive electrons to generate hydrogen gas. The SPE is ‘appareatly maintained ia a solid. state without being hinged. When the SPE is used for ttium electrolytic enrichment, the advantages befow can be expected as com- pared with usual methods. 1) Distilled water can be directly decomposed. That is, dissolution, neutralization, and removal of an electrolyte ‘whieh are essential for an electrolytic method of an alkaline aqueous solution, are not required, and a volume reduction ‘actor of sample water is basically unlimited. 2) An electrode surface is not covered with bubbles, and thus electrolysis can be performed with a lange current, thereby shortening the electrolysis time. '3) Since hydrogen gas and oxygen gas are generated separately on both sides ofthe SPE membrane, the gases can be easily treated. This is far safer than a usual method including handling explosive mixed yas. Also, the applicant hs proposed an electrolytic enrich: sent method for heavy water by SPE water electolysis ia Japanese Unexamined Patent Application Publication Nos. 8.26708 (US, Pat, No, 3,406,390) and 8.323154 (U.S, Pat. No. 3.977.446) and Tritium Flectolytic Phrichment using Solid Polymer Electrolyte (RADIOISOTOPES, Vol. 45, No. 5, May 1996 (issued by Japan Radioisotope Association) However, the method proposed in these documents can be applied to an analysis apparatus and small-scale enrichment ‘eecument, but is unsuitable for large-scale treatment, No ‘current flows through the electrolyte because the electrolyte used is pure water, and thus the solid polymer membrane ‘used as a component must be strongly crimped with the nade and the cathode under surface pressure corresponding {© 20 to 30 Kplem’, Therefore, members of an electrolysis cell are required to have hiph strength, and in view of economy and operationaliy itis unrealistic to secure a large ection area of 1m” or more, thereby undesirably inereas- jing the equipment cost for electrolyte enrichment and fractionation of raw material water containing # large amount of heavy water, SUMMARY OF THE INVENTION Accordingly it isan abject of the present invention to resolve the problems of the related art and provide an cleciolyie enrichment method for heavy water capable ofUS 9,890,062 B2 3 electrolytic enrichment and fractionation of raw material Water containing a large amount of heavy water by aa alkaline water electrolytic method, and eapable of producing high-purity hydrogen gas andor high-purity oxygen gas, TInorder o achieve the object, ist resolving means ofthe present invention isto provide an electrolytic enrichment method for heavy water, the method including enriching heavy water by electrolysis with an alkaline water eleceoly- sis cell which includes an anode chamber that holds an anode, a cathode chamber that holds a cathode, and 2 ‘diaphragm that divides between the anode chamber and the ‘cathode chamber. Inthe elecirolytc enrichment method, an ‘electrolyte prepared by adding high-concentration alkaline Water 10 raiv material water containing heey’ water con- taining tritium is circularly supplied to both electrolysis ‘chambers including the anode chamber and the cathode ‘chamber from a eirulation tank containing the electrolyte: fn anode-side gas-liquid separator ad an anode-side water seal device are connected to the anode chamber, and & ‘cathode-side ga-liguid sepanior und a eathode-side water- seal device are connected to the cathode chamber, and ‘electrolysis is continued while the alkali concentration in the ‘electrolyte supplied to both electrolysis chambers is main= tained at a constant concentration by circularly supplying, to the cirelato tenerated from each of the anode-side gas-liquid separator and the cathode-side gas-liquid. separator is. separated, thereby enriching heavy water in the electrolyte, At the same time, the hydrogen gas is reeovered or discharged from the ceathode-side gas-liquid separator, and the oxygen gas is recovered or discharged from the anode-side gas-liquid separator. Tn oder to achieve the object, second resolving means of the present invention sto provide an electrolytic enrichment method for heavy water wherein electolysis is continued while the alkali concentration of the electrolyte is main- tained at the initial eoneentration by supplying the raw material water in. an amount comesponding to the water disappearing by electrolysis to the circulation tank. In order to achieve the object, third resolving means ofthe present invention is to provide an electrolytic enrichment method for heavy water wherein the alkali concentration of the electolyte is 1.5% to 40% by mas. In onder fo achieve the object fourth resolving means of the present invention sto provide an elecirolytic enrichment method for heavy’ water wherein the slkali concenteation of the electrolyte is 20% to 30% By mass TInorder to achieve the object, fifth resolving means ofthe present invention is to provide an electrolytic enrichment method for heavy water wherein electrolysis is continued while the alkali concentration of the electrolyte is maine tained at a constant concentration by supplying the raw material water to the cirelation tank so that the alkali ‘concentration of the eleetrolyte does not exceed 40% by Tnorder to achieve the object, sixth resolving means of the present invention isto provide an electrolytic enrichment method for heavy water wherein electrolysis is continued while the alkali concentration of the electrolyte is main- tained at a constant concentration by supplying the raw material water to the cienfation tank so that the alkali ‘concentration of the eleetrolyte does not exceed 30% by Tn order to achieve the object, seventh resolving means of the present invention isto provide an electrolytic enrichment mthod for heavy water wherein the pressure in the cathode ‘chamber and the pressure in the anode chamber are adjusted tank, the electolyte from which the gas 2 4 by adjusting the height ofa water surface in the eathode-side waterseal device and the height of a water surface in the anode-side water-seal device, respectively, inorder 10 eon- trol a ratio ofthe oxygen gas generated in the anode chamber and mixed in the hydrogen gas generated in the cathode chamer andlor a rtio of the hydrogen gas generated in the eathode chamber and mixed inthe oxygen gas generate in the anode chamber ‘In order to achieve the object, eighth resolving means of the present invention is to provide an electrolytic enrichment method for heavy watee Wherein the diphragm isa neutal Gaphragm, In onder to achieve the object, ninth resolving means of the present invention is to provide an electrolytic enrichment ‘method for heavy water wherein the diaphragm i a eation- ‘exchange membrane. “According to the present invention, a radioactive waste containing & large amount of tritium can be effectively enriched and fractionated by alkaline water elecirolysis, and hhigh-conceatration and high-purity hydrogen gas andlor ‘oxygen gas can be effectively recovered. Punber, agcording to the preseat invention, the anode chamber and the cathode chamber are provided om bath Sides ofthe diaphragm, and the common alkaline elecralyte is circularly supplied tothe anode chamber andthe cathode chamber from one eireulation tak, so that i the operation system, the alkali concentrations inthe anole chamber and the cathode chamber can be always controlled to the same ‘concentration by returning and maintaining, to and in the same circulation tank, the electoyte diseharged from each fof the anode chamber and the cathode chamber by electeo- Iyte electrolysis whieh decreases the alkali concentration in the anode chamber and increnses the alkali concentration in the cathode chamber. Also, the alkali concentration in the system can be always kept at a predetermined inital eon- dition by supplying the raw ataterial water in an amount ‘orresponding to the water diseppearing by electrolysis. in any case, a method! for operating an alkaline water elec- trolysis ciculation process isan ellctve operation method because multi-purpose operation management of ated ‘opertion and continous operation ofa plant can be realized according to purposes of plant operation only by adjusting a Predetermined alkali concentration in the carly stage of ‘operation. Also, operation management is not complicated, ‘and thus safe operation eaa be performed in a plaat level. On the other hand, when the alkali concentration cannot be controlled under predetermined conditions, a cell voltage changes with changes in the alkali concentration, thereby changing the quantity of heat generated with Joule heat. ‘When the cell temperatuee is increased, the amount of water evaporated is increased, and thus cooling conditions are also changed. Therefore, variation in the alkali concentration is ‘undesired because of variation ia operation conditions With variation in the alkali concentration. However, this problem can he resolved by alkaline water electrolysis aeconding to the present invention, Punber, according to the present invention, heavy water can he effectively enriched by alkaline water electrolysis ‘ith the electrolyte at the alkali concentration of 1.5% to 4% bby mass. Continuous water electrolysis permits theoretical desired Volume reduction, thereby permitting enrichment 10 1 desired value, Funtber, according to the present invention, in the ele trolysis process, when each ofthe anade gas and the eathode ans is separated by the gavliquid separator, then water Scaled, and discharged, a ratio ofthe oxygen gas generated the anode chamber and transferred o the eathode eatherUS 9,890,062 B2 5 ‘can be contd by controlling the gas pressure on the ‘cathode side to be higher or lower than the gas pressure oa the anode side. Therefore, according to the present inven- tion, dhe electrolysis process can be controlled within explo- sion limits by controlling a mixing rato between the oxygen as and the hydrogen gas, thereby decreasing a danger of ‘explosion and producing high-purity hydmgen gas andor high-purity oxygen gas. BRIBE DESCRIPTION OF THE DRAWING FIGURE is a flow diagram illustrating an electrolytic ‘earichment method for heavy water according to an embod iment of the present invention. DESCRIPTION OF THE PREI EMBODIMENTS, "ERRED An emboxiiment of the present invention is deseribed below with reference tothe drawing. FIGURE is a flow diagram illustrating an electrolytic ‘enrichment method for heavy water aeconding t an embodi- tment of the present invention. In FIGURE, reference ‘numeral 1 denotes an alkaline water electrolysis cell and the alkaline water electrolysis cell 1 inclndes an anode chamber 2 that holds an anode, a cathode chamber 3 that holds a cathode, and a diaparagm 4 that divides betwoen the anode ‘chamber 2 and the cathode chamber 3, Reference numeral § ‘denotes « circulation tank; reference numeral 6, an allline ‘water tank that stores high concentration of alkaline water 7 generally required only for adjusting the initial alkaline ‘leciolyte: reference numeral 8, a feed pump that supplies the alkaline water 7 in the alkaline water tank 6 to the culation tank 5; reference numeral 9, a raw material tank that stores raw material water 10; and reference numeral ‘feed pump that supplies the aw’ material Water 10 in the raw material tank 9 to the eiculation tank §. The alkaline ‘water T and the raw material Water 10 are mixed in the circulation tank S to produce an electrolyte 16 adjusted t0 alkaline water a a predetermined concentration. “The electrolyte cantrolled to a predetermined concentra tion by mixing in the circulation tank 5 is supplied to the anode chamber 2 of the alkaline water electrolysis cell 1 through a circulation pump 12a and a heat exchanger 130 ‘and is supplied to the cathode chamber 3 of the alkaline ‘water electrolysis cell f through a eireulation pump 12 and ‘a heat exchanger 134, ‘The electrolyte controlled to a predetermined concentra tion of alkaline water is electolyzed in the anode chamber 2 and enriched by electrolysis to produce an enriched ‘electrolyte, and oxygen gas is generated inthe anode cham- ber 2. The generated oxygen gas and electrolyte are sepa rated into gas und liquid by a gas-liquid separator 14a, and the separated electrolyte is cicula 5. The oxygen gas separated by the anode-side gas-liquid separator 14a is exhausted through an anode-sce water seal device 18a ‘At the same time, hydrogen gas is generated in the ‘cathode chamber 3. The penerated hydrogen yas and elec trolyte are separated into gas and liquid by a eathode-side as-iguid separator 14b, and the separated electrolyte is reulated to the circulation tank §. The hydrogen ens separated by the anode-side gas-liquid separator 146 is ‘exhausted through a cathode-side water seal device 18. In ‘addition, water is supplied as raw material water to be supplied fom the rave material tank 9 by supplying the raw material water in an amount comesponding to the water 0 o 6 isappearing by electrolysis ia onder to continue electrolysis ‘while maintaining the electrolysis conditions constant and to ‘control the alkali concentrations ia both electrolysis eham- bets ‘The clectolyte at the alkali concentration initially adjusted can he maintained by continuously supplying the ‘aw material water in an amount corresponding to the water disappearing by electrolysis, On the other hind, an inter mittent operation of volume reduction ofthe electrolyte (rae material water to be treated) can also be curried out by continuing intermittent alkaline water electolysis circu tion without continuous supply of the raw material Wate, (Condition for Alkaline Water Electrolysis) In alkaline water electrolysis according t the present invention, an electrolyte prepared by adding high-concen- tration alKaline water fo the raw material water composed of heavy water containing titi so that predetermined alkali concentration ie obtained is used as the electrolyte, The electrolyte is preferably a caustic alkali such 36 caustic potassium, caustic sodium, or the like, and the onceatration {thoreo is preferably 1-5% to 40% by mass. In particular, in view of suppressing the power consumption, a concentration fof 15% to 40% by mass within a region with high electric conductivity is preferred. However, in view of electrolysis cost, corrosion resistance, viscosity, and operational, the concentration is more preferably 20% to 30% by mas. The concentration of the high-concentrstion alkaline ater added tothe raw material water is preferably 10% 10 30% by mass. A method for operation ata constant alkali concentration includes, for example, continuously supplying the rw mate- fal water in an amount comesponding to the amount of ‘water consumed afer controlling the initial alkali enncen- ‘cation, When an intermittent operation is desired for redve- ing the volume of the raw material water to be treated. @ method of checking a reduetion in amount ofthe elestrolyte initially adjusted may be used. In this ease, the intially adjusted alkali concentration is increased in proportion 10 the amount of water reduced, "As the region of the alkali concentration, a region in which liquid resistance is increased is undesired. Por ‘example, When the alkali concentration exceeds 40% by ‘mass, generated gases tend to become difficult to remove {rom the eleetolyte (due to increase in liquid viscosity), and thus the cll Vollage is increased, resulting in an increase in cel temperature de fo the generation of Joule heat and the need for an exeessive operation management such as the reed for evoling the electrolyte or the like, “Therefore, since the alkali concentration is increased by enrichment ofthe rw material wate, its preferred thatthe alkali concentration is kept constant by adding the raw ‘material water so that the alkali concentration does not exceed 40% by mass or 30% by mass, TInthe present invention in view of economy, heavy water is enriched about 10 times by electrolytic volume reduction, And when the initial concentration of heavy water in the a? material water is 2.5% by mass, the final concentration is 25% by mass because water is released hy electrolysis. (Water Seal System) unter, in the present invention, the electrolyte from Whiel the generated was is separated by each of the gas- Jiquid separators 14a and 140 is cireuary supplied o each of the eloctrolysis chambers including the anode chamber 2 ‘and the eathode chamber 3, thereby controling the alkali concentrations in both electrolysis chambers. At the same time, the raw material water in an amount comrespondling to the amount of water disappearing by electrolysis is suppliedUS 9,890,062 B2 1 to both electrolysis chambers including the anode chamber 2 and the cathode chamber 3 from the raw material tank 9 ‘hough the circulation tank 8, Therefore heavy water in the raw material water is enriched by continuing electrolysis ‘while maintaining tho electrolysis conditions constant. Tn order to contol the eoncentrtion constant, the raw material water 10 in an amount coresponing to the water ‘consumed is continuously supplied to the circulation tak 5 ‘On the other hand, even when the alkali concentration is allowed to gradually increase to a high concentration up to ‘8 concentration limit of the alkaline water electrolysis of 40% by mass, volume reduction of the electrolyte can be ‘confirmed. Also, under these conditions, the final concen= tration of 40% by mass can be then maintained by starting the supply of the raw material water Therefore the ereulaton system proposed in the present invention can be operated by any of the methods and thus has lenibiity Funher, in the present invention, the pressure in the ‘eathode chamber 3nd the pressure in the anode chamber 2 ‘controlled by controlling the height of the water surface ‘nthe eathode-side waterseal devie 18b and the anode-side ‘water-seal device 18a, respectively, in onder to control a ratio ofthe oxygen gas penerated in the anode chamber 2 and mixed withthe hydrogen gas generated in the cathode chamber 3 ‘The anode gas (oxygen gas) and th cathode gas (hydro= ten gas) are separated by the aode-sde gas-liquid separator 1a and the eathode-side gas-liquid separator 145, water- sealed in the anode-side waterscal device 18a and the cothode-side water-scal device 15h, respectively. and then ‘exhausted. In this ese, the height of the water surface in the ‘ethode-side water-eal device 15h is controlled tobe higher than that inthe anode-side water-seal device 1Sa so that the aus pressure on the cathode side is higher than the gas pressure on the anode sie, This can decrease the transfer of the oxygen gas generated in the anode chamber 2 40 the ‘eathode chamber 3, thereby improving the purity of hydeo= igen gas. Conversely, when the purty of oxygen gos is ‘desired to be improved, the height ofthe water surface inthe lnode-side water-seal device 18a is controlled to be bigher than that in the cathode-side waterseal device 15H so that the gas pressure on the anode side is higher than the gas pressure on the eaode side, This ean decrease the transfer ‘of the hydrogen pas generated in the cathode chamber 310 the anode chamber 2, thereby improving the purity of ‘oxygen gas (Alkaline Water Eleewolysis Cell) ‘A two-chamber electrolysis cell including an anode and a cathode provided on both sides of the diaphragm 4 is used as the alkaline water electrolysis cell 1 Also, a zero-gap ‘elecirolysis cell including an anode and a cathode whieh adhere tothe diaphragm 4a finite electrolysis cll including fn anode and a eathode which are provided slightly apart from the diaphragm 4, or a spaced-iype electrolysis cell jnchiding an anode and a eathode which are provided apart from the diaphragm 4 can be used. In order 10 prevent variation in position and oscillation ofthe membrane al t0 prevent damage to the membrane diaphram 4 during the ‘operation, an operating diferential pressure is preferably provided between the anode chamber and the eaubode ca- ber, depending on the operation electric current density. For ‘eximple, differential pressure of 50 to 500 mmii,0 can be provid, and ths differential pressure pemits further con- tol of the ratio of the oxygen gas generated in the anode ‘chamber 2 and mixed in the hydrogen ges generated in the ‘eathode chamber 3 0 o 8 In addition, when a neucal diaphragm is used a5 the iaphragm, the pore size of the diaphragm used is decreased or the diaphragm with a specially-teated surface is used so that trnsler of the oxygen gas generated in the anode chaunber wo the eathode chamber or ranser of the hydrogen gas generated in the cathode chamiber fo the anode chamber fan he decrease. (Diaphragm) Arcata diaphragm, a uorine-type or hydrocarbon-type cation exchange membrane for brine eleetolysi, and. a sation exchange membrane for fuel cells can be wed as the diaphragm 4. Whea a cation exchange membrane is used, a hydrogen concentration in oxygen is about 0.13% at an ‘oxygen concentration in hydrogen of 0.07%, ‘On the other hand, when a neural diaphragm specially treated is used as the diaphragm 4, a hydrogen concentration in oxygen is 0.05% to 108% at an oxygen concentration ia hydrogen of 0.06% to 0.05%. (Anode and Cathode) ‘The anode and the cathode are selected 19 be made of a ‘material which cun resist alkaline water electrolysis and to hhave low anode overvoltage and cathode overvolage, respectively. In general, the anode composed of iron oF [Nplate iron is used, and the cathode composed of a Ni base material or a Ni hase material coated sith an active cathode material is used. A nickel expanded mesh, a porous kel expanded mesh, a metal electrode including an ion ase having a surface coated with a noble metal or an oxide thereo, or the ike can be used as each of the anode ad the cathode. EXAMPLES ‘Next, examples of the present invention are described, but ‘he present invention isnot limited t these examples, Prample 1 A test was conducted with an electrolysis cell having an lectrolysis area of 10 din®, Both an anode chamber (vol- ‘ume 400 ml) and a cathode chamber (volume 400 ml) were ‘composed of Ni, and the anode included an expanded mesh (Whickness 0.8 mmxshort width (SW) 3.7 mmlong wits (LW) 80 mm) with an active anode coatiag, The cathode included a fine mesh (thickness 0.15 mm>SW 2.0 mmx. W 110 mm) with a noble metal-based active eathode coating, ‘A polypropylene-based film of 100 jum was used as & iaphragm, Reld herween both electrodes, and assembled ‘with a 2em0 gap, ‘A est process is a illustrated in FIGURE, in which an clecirolyss temperature is controlled with a heater provided at the bottom of an electrolysis cell. An electolyte is circulated by a method in which the electrolyte is supplied ‘with citeulation pumps 12a and 126 at a flow rate of 40 t0 60 ml/min tothe anode chamber 2 and the eathode chamber 3 through electrolyte supply nozzles from the circulation tank $ (electrolyte volume: 2.5 1) provided helow the alkaline Water electrolysis coll 1. The liquids in gas-liquid ‘Tuids discharyed from upper nozzles ofthe electolyss cell ‘ace returned tothe circulation tank 5 through the gas-liquid separators 14a and 144, and gases are discharged to the ‘outside. The operation conditions include 40.Alim’, 10% by ‘mass KOH, an electrolysis temperature of 75°C. 85°C, ‘nd pressure in the cell system which is determined by \water-sealing the oxygen gas and hydrogen pas discharged from the anode chamber and the esthode chamber. respec- tively In onder to prevent vibration ofthe digphragm duringUS 9,890,062 B2 9 the operation, @ diferential pressure between the anode ‘chamber aad the cathode chamber is Kept at 50 10 100 rimil,0. On the other hand, the liguid height in each of the waterseal systems ean be controlled depending on which of the prodaced hytlrogen gas and oxygen gas is expected 0 have desired purity. In this example, in onder to increase hhydroen purity, differential pressure was 50 mmHl,O with pressure applied to the cathode, nan aetval process large amount of raw material water js simply treated by continuously supplying the raw material Water in an amount corresponding to the amount of water hydrolyzed, However, in this example, ellectiveness was ‘examined by measuring the enrichment rate of sample water ‘containing tritium, cell voltage, and hydrogen purty without adding the raw material water in an amount corresponding ‘w the amount of water hydrolyzed to the inti prepared ‘electrolyte in the circulation system, ‘When the operation was eontinved until an integrated ‘curent value was 4800 Ah (continuous operation for S day’), the fotal amount of the electrolyte was decreased 10 1.7L from the initial prepared volume of 3.3L. la view of slight evaporation and the amount of wnrccovered water ia ‘electrolysis pipes in spite of recovery from the system, the amount of water rediced is a value substantially equivalent 1w a thooretical value As rst, the olecteolye in a Volume of 4.125 times the volume of the electrolysis ell as enriched 1.96 times. This represents that raw material water in a volume of 4 times oF ‘more the volume of the electrolysis eell can be treated with ro trouble, and continuous enrichment can be performed by ‘continsowsly supplying raw material water, Tati, fom the viewpoint of volume reduction of rw material water, the volume of rw material water can be reduced in proportion 1o the integrated current value applied to the system. ‘The 10 mass % KOH electrolyte initially prepared was finally 19.6 mass % KOH after current supply of 4800 Ah. “This represents that the concentration was increased by 3 value corresponding tothe water disappearing. That is, this indicates tha the initially prepared alkali (here, caustic alkali KOH) i stayed in the system without being consumed. The same apples to the case where eaustc soda NaOH is used asthe alkali and the alkali is not limited to caustic potassinm KOU. (On the other hand the intial adjusted alkali concentration, ‘can be kept at the initial value by continuously supplying the raw material water in. an amount corresponding to the ‘amount of water hydrolyzed, ‘When the integrated current was 4800 Ah, the voltage, hydrogen purity and tetium rooovery rate were as follows. "Test resis: 17 V, hydrogen purty 99.9%, tritium recov ery re 0.6 | ‘All ofthe gas purity, tritium recovery rate, and operation voltage were good. Example 2 Atest was conducted by the same method as in Example 1 except that a PTFE film having a thickness of 70 to 90 ym and an average pore size of | jim of less was used as @ diaphragm. The test results were as follows ‘Test results: 1.95 V, hydrogen purity 98.9%, tritium recovery rate 0.6 “All ofthe gas purity, tritium recovery rate, and operation voltage were good. 0 o 10 Example 3 A test was conducted by the same method as in Example 1 except that an jon exchange membrane for brine electroly- sis was used as. diaphragm, The test results were as follows, ‘Cation exchange membrane used Pleminn (trade name of Asthi Glass Co. L,) F8O20SP Test results: 21 0 24 V, hydrogen purity 9.93%, tritium recovery rate 0.6 The highest gas purity and good tritium recovery rate were obtained, but the operation voltage was high, resulting in the tendeney to increase power consumption. Example 4 Atest was conducted by the same method as in Example 1 except that an ion exchange membrane for fuel cells oseribod below was used 28.8 diaphragm, The test results were as follows. Cation exchange membrane used: Nafion (ade name of DuPont Company) NUIT "Test resus: 2.3 to 26 V, hydrogen purity 99.92 recovery rate 0.6 ‘The good gas purity and good witium recovery rate were ‘oblained, but the operation voltage Was very high, resulting in the tendeney to increase power consumption ‘According to the present invention, radioactive waste containing lage amount of tritium can be efficiently enriched and fractionated by electrolysis with high-concer tration alkaline water, and high-concentration, high-purity hydrogen gas ean be efliciently recovered. Also, the alkali concentration in the system can be always kept constant by providing an anode chamber and a cathode chamber on bats Sides of a diaphragm and circulaely supplying a common alkaline electrolyte to both the anode chamber and the cathode chamber from a eeculation tank. Therefore plant- level operation can be safely performed, thereby expecting ‘wide-ranging utilization, The invention claimed is 1. An electrolytic enrichment method for heavy water, the ‘method comprising ‘cariching heavy water by electrolysis using an alkaline ‘water electrolysis cell consisting of an anode chamber that holds an anode, ¢ cathode chamber that holds a cathode, and a diaphragm that divides between the ‘anode chamber and the cathode chamber, ‘wherein an electrolyte prepared by adding high-concen- ‘ration alkaline water to raw material water consisting ‘of heavy water containing tritium is circularly supplied to both electrolysis chambers including the anode chamber and the cathode chamber from a citcultion tank containing the electrolyte, fn anode-side gas-liquid separator and an anode-side Waterseal devi are eonneeted tothe anode chamber, ‘and a cathode-sde gas-liquid separator and a eathode- side waterseal device are connected to the cathode chamber; and ning electrolysis while the alkali concenteatio the electrolyte supplied to the both electolysis cham- bers is maintained at a constant concentration by eit- cclarly supplying, to the eirevlation tank, the electro Iyte from which the gas generated from each of the ‘anode-side gas-liquid separator and the eathode-sde ‘es-liquid separator is separated, so that heavy water in the electrolyte is enriched and, at the same time, the hydrogen gas is recovered o¢ discharged from theUS 9,890,062 B2 un ‘athode-sde gas-iquid separator and the oxygen gs is recovered or discharged from the anode-side gas-liquid separator 2. The electrolytic enrichment method for heavy water ‘seconling to elas 1, wherein electrolysis is continued while Is concentration of the electrolyte is maintained at ial concentration by supplying raw material water in the amount comesponding tothe water disappearing by the ‘eleciolysis 0 the eieulation tank 3. The electrolytic enrichment method for heavy water ‘seconting o claim 1, wherein the alkali coneentation ofthe ‘electrolyte is 1.5% to 40% by mass. 4. The electrolytic enrichment method for heavy water ‘scconling to claim 1, wherein the alkali concentration ofthe ‘electrolyte is 20% to 30% by mass. 5, The electrolytic enrichment method for heavy water socording to claim 1, wherein electolysis is continued while the alkali concenteation ofthe electrolyte is maintained a 2 ‘constant to the circulation tank so tha te alkali concentration of the ‘electrolyte does not exceed 40% by mass, 6. The electrolytic enrichment method for heavy water acconting 1 claim §, tration by supplying the raw material water 12 ‘wherein electrolysis is continued while the alkali concen tration of the electolyte is maintained at a constant ‘concentration by supplying the raw material water to the eirclation tank so thatthe alll concentration of the electrolyte does not excced 30% by mass 7. The electrolytic enrichment method for heavy water according to claim 1, ‘wherein the pressure in the cathode chamber and the presure in heanode chamber are adjusted by adjusting the height ofa water suclae inthe eathode-side water- seal device and the height of 2 water surface in the ‘anode side Waterseal device, respectively, in onder to ‘contol the ratio of the oxygen gas generated in the anode chamber mixed into the hydrogen gas generated inthe eathode chamber andor the ratio of the hydrogen ‘2s penerate in the eathose chamber mixed into the ‘oxygen gas generated in the anode chamber. 8, The electrolytic enrichment method for heavy water according t0 claim 1, wherein the digphragm is a neutral igphragm, 9. The electrolytic enrichment method for heavy water according to claim 1, wherein the diaphragm is a eation- exchange membrane.