CN101921010A - Water treatment facility for fuel cell - Google Patents

Water treatment facility for fuel cell Download PDF

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Publication number
CN101921010A
CN101921010A CN2010101876043A CN201010187604A CN101921010A CN 101921010 A CN101921010 A CN 101921010A CN 2010101876043 A CN2010101876043 A CN 2010101876043A CN 201010187604 A CN201010187604 A CN 201010187604A CN 101921010 A CN101921010 A CN 101921010A
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China
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exchange resin
anionite
fuel cell
water
ion
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CN101921010B (en
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伊藤美和
大江太郎
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PRGANO CORP
Organo Corp
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PRGANO CORP
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Priority claimed from JP2009132341A external-priority patent/JP5364450B2/en
Priority claimed from JP2009147490A external-priority patent/JP5478953B2/en
Priority claimed from JP2009190131A external-priority patent/JP2011041874A/en
Priority claimed from JP2010032755A external-priority patent/JP5551944B2/en
Application filed by PRGANO CORP filed Critical PRGANO CORP
Publication of CN101921010A publication Critical patent/CN101921010A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a water treatment facility for fuel cell capable of effectively reducing the concentration of chloride ions in water supplied to the fuel cell. The water treatment facility adopts ion exchange resin which contains anion exchange resin. The proportion of chloride ions in the whole exchange capacity of the anion exchange resin in a primary state is less than 10%.

Description

The water treatment device of fuel cell
Technical field
The present invention relates to make the water treatment device of the fuel cell of spent ion exchange resin.
Background technology
Fuel cell needs hydrogen, and in order to make hydrogen from gas or Sweet natural gas etc., need make water again in modified process, and water wherein uses pure water.In addition, when cooled fuel cell or when the polymeric membrane to polymer electrolyte fuel cell carries out humidification etc., also need to use pure water.
Pure water is normally made by the water treatment device removal foreign ion that possesses ion exchange resin.Except making from tap water the technology of pure water, had at present and multiplely handled by water of condensation that the electric power generation reaction from fuel cell is generated etc., this treating water (pure water) is recycled technology in fuel cell.
For example, a kind of like this technology is disclosed in the patent documentation 1: in the water treatment device that carbanion in the water coolant of supplying with for the corrosion subtend fuel cell that prevents fuel cell and bicarbonate ion (hereinafter referred to as carbanion etc. or only be called carbonic acid) are handled, by the usage rate of anionite-exchange resin and Zeo-karb is adjusted to suitable degree, reduce the amount of Zeo-karb, the miniaturization of implement device.In patent documentation 2, put down in writing by amount optimizing,, but anionite-exchange resin has not been inquired into the content of the miniaturization of implement device with Zeo-karb.
For example, disclose in the patent documentation 2 by using the high ion exchange resin of thermotolerance to improve the water treatment device of heat extraction yield.
In addition, owing to fuel cell is that target is developed with the life-time service, need the energy life-time service too so be used for the water treatment device of such fuel cell.But the water that uses in fuel cell is owing to contact with the air of being introduced by extraneous gas, and therefore according to the difference that environment is set of installing, bacterium may be by in this inclusion of air water treatment device and breed sometimes.If bacterial reproduction is arranged in the water treatment device, then not only can not get the water quality expected, also might cause and stop up and can't stably supply with treating water.
Vegetative method (for example, with reference to non-patent literature 1 and patent documentation 3) in the conventional art in existing several inhibition water treatment device.
Pointed out in the non-patent literature 1 by using the anionite-exchange resin of OH type, can play and suppress vegetative effect.And about the reason of having that effect, having mentioned is that anionite-exchange resin by the OH type has strong basicity and brings.In addition, the mixed bed resin that discloses OH type and H type in the non-patent literature 1 has the content of the sterilizing ability stronger than the anionite-exchange resin of OH type.About its reason, having mentioned is to be subjected to the cause that bigger pH changes because bacterium by in the resin time, contacts OH type and H type disorderly.
The antiseptic-germicides such as gac that disclose by carrying on a shoulder pole Ag-bearing in the patent documentation 3 mix the vegetative technology that suppresses with ion exchange resin.
Patent documentation 1: the spy opens flat 8-17457 communique
Patent documentation 2: the spy opens flat 11-204123 communique
Patent documentation 3: the spy opens flat 10-314727 communique
Non-patent literature 1: the sharp husband of left rattan etc., electrochemistry and industrial physicochemistry, 54 (3), 1986 years, 269 pages～273 pages
For the running of the long-term stability that realizes fuel cell, importantly remove the chloride ion in the water that fuel cell is supplied with.In other words, be fed in the fuel cell if contain the water of chloride ion, the danger that the parts of fuel cell are corroded will be very high.Therefore, be badly in need of a kind of water treatment device that is used for fuel cell that can effectively reduce the concentration of the chloride ion in the water that fuel cell is supplied with.
Simultaneously, also the water treatment device that is used for fuel cell of a kind of thermotolerance height, cheap and miniaturization appears in expectation.
In addition, in the water treatment device of the mixed bed resin that uses anionite-exchange resin and Zeo-karb, because the proportion of anionite-exchange resin and Zeo-karb is different, therefore this water treatment device carried, installed, running etc. and when causing vibration, heavy Zeo-karb can move to the bottom, and the little anionite-exchange resin of proportion can move to top, causes two kinds of ion exchange resin to separate.If isolating like this mixed bed resin is used for the water treatment device of the fuel cell of use under the high temperature of being everlasting, low flow state, main stripping Trimethylamine 99 from anionite-exchange resin sometimes then, and from Zeo-karb main stripping polystyrolsulfon acid.For example, if with processed water downward direction circulation, the stripping composition that then is derived from the Zeo-karb of bottom can not be captured, and if with processed water upward to circulation, the stripping composition that then is derived from the anionite-exchange resin on top can not be captured.Thereby cause the TOC in the treating water to increase.And, if these stripping compositions are sneaked in the treating water, then the TOC in the treating water increases, cause to reach the electric conductivity of desired water, perhaps these stripping compositions or as the ammonium ion that generates the source, nitrate ion, nitrite ion, sulfate ion etc. the power generation performance and life-span of fuel cell brought bad influence with these stripping compositions.
In addition, also the bacterial reproduction that a kind of life-time service that can suppress by fuel cell causes appears in expectation, guarantees the water treatment device of the long-term normal fuel cell that uses.
Summary of the invention
Given this, the object of the present invention is to provide a kind of water treatment device that can realize the fuel cell of following any one purpose at least: the concentration that reduces the chloride ion in the water that fuel cell is supplied with; Possesses thermotolerance, cheap and can miniaturization; Effectively reduce the TOC in the water that fuel cell is supplied with; The breeding of the bacterium that inhibition is generated by the life-time service of fuel cell is to realize life-time service.
(1) the invention provides a kind of water treatment device of fuel cell, it is characterized in that, the water treatment device of this fuel cell makes spent ion exchange resin, described ion exchange resin contains anionite-exchange resin, and the shared ratio of chloride ion is below 10% in the total exchange capacity of the described anionite-exchange resin of original state.
(2) the invention provides a kind of water treatment device of fuel cell, it is characterized in that, the water treatment device of this fuel cell makes spent ion exchange resin, described ion exchange resin contains anionite-exchange resin, the shared ratio of chloride ion is configured in the total exchange capacity of the described anionite-exchange resin of original state, the dissolved carbonate concentration is high more then more little in the processed water, and the target cl concn in the treating water is low more then more little.
(3) in the water treatment device of fuel cell of above-mentioned (1) or (2) record, preferred described anionite-exchange resin comprises the trimethylammonium ammonium strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is smaller or equal to by R in the total exchange capacity of the described anionite-exchange resin of original state Cl=4 * C Cl/ CO 2 0.53The value obtained of formula.Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be that dissolved carbonic acid in the processed water is converted into CO 2CO 2Concentration (ppm).
(4) in the water treatment device of fuel cell of above-mentioned (1) or (2) record, preferred described anionite-exchange resin comprises the dimethyl ethanol ammonium strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is by with R in the total exchange capacity of the described anionite-exchange resin of original state Cl=1.3 * C Cl/ CO 2 0.45The value obtained of formula below.
Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be that dissolved carbonic acid in the processed water is converted into CO 2CO 2Concentration (ppm).
(5) in the water treatment device of the fuel cell of any 1 record of above-mentioned (1)～(4), the anionite-exchange resin of preferred described original state is the anionite-exchange resin that is transformed to calcareous type through circulation carbonate.
(6) in the water treatment device of the fuel cell of any 1 record of above-mentioned (1)～(5), preferably, undertaken by direction circulation style under the processed water employing of described anionite-exchange resin.
(7) in the water treatment device of the fuel cell of any 1 record of above-mentioned (1)～(6), preferably, contain water of condensation in the processed water by described anionite-exchange resin by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
(8) the invention provides a kind of water treatment device of fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, described ion exchange resin comprises anionite-exchange resin, and the described anionite-exchange resin of original state is the anionite-exchange resin that is transformed to calcareous type through circulation carbonate.
(9) in the water treatment device of fuel cell of above-mentioned (8) record, in the total exchange capacity of the anionite-exchange resin of preferred described original state 70～100%, calcareous type.
(10) in the water treatment device of the fuel cell of above-mentioned (8) or (9) record, preferred described anionite-exchange resin is strongly basic anion exchange resin.
(11) in the water treatment device of the fuel cell of any 1 record of above-mentioned (8)～(10), preferably, contain water of condensation in the processed water by described anionite-exchange resin by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
(12) the invention provides a kind of water treatment device that makes the fuel cell of spent ion exchange resin, described ion exchange resin is the mixed bed resin that contains Zeo-karb and anionite-exchange resin, the median size of described Zeo-karb is more than the 0.2mm, and is below 80% of median size of described anionite-exchange resin.
(13) in the water treatment device of fuel cell of above-mentioned (12) record, the volume of preferred described anionite-exchange resin is 1.5～5 times of volume of described Zeo-karb.
(14) in the water treatment device of the fuel cell of above-mentioned (12) or (13) record, the shared ratio of chloride ion is below 10% in the total exchange capacity of the described anionite-exchange resin of preferred original state.
(15) in the water treatment device of the fuel cell of above-mentioned (12) or (13) record, the shared ratio of chloride ion is configured in the total exchange capacity of the described anionite-exchange resin of preferred original state, and the target cl concn in the processed water in the high more then more little and treating water of dissolved carbonate concentration is low more then more little.
(16) in the water treatment device of the fuel cell of above-mentioned (14) or (15) record, preferred described anionite-exchange resin comprises the strongly basic anion exchange resin that the trimethylammonium ammonium is in return basic, and the shared ratio of chloride ion is by R in the total exchange capacity of the described anionite-exchange resin of original state Cl=4 * C Cl/ CO 2 0.53The value obtained of formula below.Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be that dissolved carbonic acid in the processed water is converted into CO 2After CO 2Concentration (ppm).
(17) in the water treatment device of the fuel cell of above-mentioned (14) or (15) record, preferred described anionite-exchange resin comprises the dimethyl ethanol ammonium strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is by with R in the total exchange capacity of the described anionite-exchange resin of original state Cl=1.3 * C Cl/ CO 2 0.45The value obtained of formula below.Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be that dissolved carbonic acid in the processed water is converted into CO 2After CO 2Concentration (ppm).
(18) in above-mentioned (12)～(17) in the water treatment device of the fuel cell of any record, the described anionite-exchange resin of preferred original state is the anionite-exchange resin that is transformed to calcareous type by circulation carbonate.
(19) in the water treatment device of fuel cell of above-mentioned (18) record, in the total exchange capacity of the anionite-exchange resin of preferred described original state 70～100%, calcareous type.
(20) in the water treatment device of the fuel cell of any 1 record of above-mentioned (12)～(19), preferably, undertaken by direction circulation style under the processed water employing of described anionite-exchange resin.
(21) in the water treatment device of the fuel cell of any 1 record of above-mentioned (12)～(20), preferably in the processed water of described anionite-exchange resin circulation, contain water of condensation by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
(22) the invention provides a kind of water treatment device that makes the fuel cell of spent ion exchange resin, above-mentioned ion exchange resin, be to contain at least a solution in the middle of silver, copper and the zinc, the ion of ion exchange resin is obtained with any one displacement at least in the middle of silver ions, cupric ion and the zine ion by circulation.
(23) in the water treatment device of fuel cell of above-mentioned (22) record, preferred described ion exchange resin contains Zeo-karb, described solution be selected from the middle of nitrate solution, sulfate liquor, chloride soln, the complex salt solution at least any one.
(24) in the water treatment device of the fuel cell of above-mentioned (22) record, preferred described ion exchange resin contains storng-acid cation exchange resin, described solution be selected from the middle of the nitrate solution, sulfate liquor, chloride soln, complex salt solution at least any one.
(25) in the water treatment device of fuel cell of above-mentioned (22) record, preferred described ion exchange resin comprises anionite-exchange resin, and described solution is complex salt solution.
(26) in the water treatment device of the described fuel cell of above-mentioned (25) record, preferred described anionite-exchange resin is the strongly basic anion exchange resin that the trimethylammonium ammonium is in return basic.
(27) in the water treatment device of the fuel cell of above-mentioned (23), (25) or (26) record, preferably by the described complex salt solution of circulation in described ion exchange resin, with the ion exchange of ion exchange resin be in silver ions, cupric ion and the zine ion at least after any one, handle by reduction, silver, copper or zinc are precipitate into the surperficial and inner of described ion exchange resin.
It is (28) above-mentioned that (in the water treatment device of the fuel cell of 24 records, the degree of crosslinking of preferred described storng-acid cation exchange resin is more than 12%.
(29) in the water treatment device of the fuel cell of above-mentioned (22) record, preferred described ion exchange resin comprises the mixed bed resin of storng-acid cation exchange resin and strong basic ion exchange resin, and the median size of described storng-acid cation exchange resin is below 80% of median size of described strong basic ion exchange resin.
(30) in the water treatment device of the fuel cell of above-mentioned (22) record, preferred described ion exchange resin contains storng-acid cation exchange resin, and silver ions or the shared ratio of argentiferous coordination ion are the value (R that is obtained by following formula (3) in the complete exchange capacity of the described storng-acid cation exchange resin of original state Ag) below,
C Ag＝37exp(-2.4pH)R Ag 3+82exp(-2.0pH)R Ag 2+110000exp(-2.3pH)R Ag (3)
Wherein, C AgBe the target silver concentration of the water treatment device outlet side treating water of fuel cell, (C wherein AgThe scope of=0.001～10ppb), pH is the hydrogen ionexponent of the water treatment device inlet side processed water of fuel cell, (the wherein scope of pH=4～6), R AgBe the middle silver ions of total exchange capacity (eq/L-R) or the shared ratio (%) of argentiferous coordination ion (eq/L-R) of storng-acid cation exchange resin.
According to the present invention, the water treatment device that can provide the fuel cell that can effectively reduce the chloride ion in the water that fuel cell is supplied with to use.
Description of drawings
Fig. 1 is the synoptic diagram of an example of structure of water treatment device of the fuel cell of expression present embodiment 1～4.
Fig. 2 is the various CO that are illustrated in the processed water 2R under the concentration ClAnd C ClThe figure of relation.
Fig. 3 is the various CO that are illustrated in the processed water 2R under the concentration ClAnd C ClThe figure of relation.
Fig. 4 is the R under the various hydrogen ionexponents (pH) AgAnd C AgThe figure of relation.
Among the figure, 10 water treatment device, 12 fuel cells, 14 processed water pipelines, 16 condensation water tanks, 18 pumps, 20 condensing water conduits, 22 treating water pipelines, 24 fuel feed pipelines, 26 air supply pipes, 28 heat exchangers.
Embodiment
Below, embodiments of the present invention are described.Present embodiment only is to implement an example of the present invention, and the present invention is not limited by present embodiment.
(embodiment 1)
The water treatment device 10 of fuel cell shown in Figure 1 possesses the cylindrical shell (cartidge) that is filled with ion exchange resin.Cylindrical shell can have one or more.The ion exchange resin of filling in the cylindrical shell is the mixed bed resin of anionite-exchange resin or anionite-exchange resin and Zeo-karb.Wherein, the water treatment device 10 of fuel cell can be filled with outside the cylindrical shell of ion exchange resin, the additional again cylindrical shell that is filled with gac etc. that is provided with.
The water treatment device 10 of the fuel cell of present embodiment mainly is with the foreign ion that removes in the water that fuel cell 12 is supplied with.As the water of handling by the water treatment device 10 of fuel cell can be tap water (municipal water supply), pure water, the water of condensation that generates by the electric power generation reaction of fuel cell 12 etc.
Municipal water supplies such as tap water are delivered to the water treatment device 10 of fuel cell through processed water pipeline 14.In addition, the water of condensation of discharging from fuel cell 12 for example temporarily is stored in the condensation water tank 16, and is supplied to the water treatment device 10 of fuel cell from condensing water conduit 20 by pump 18.Then, the foreign ion of removing in the water by the water treatment device 10 of fuel cell.
The foreign ion that contains in the water comprises, for example carbanion, bicarbonate ion, chloride ion, sulfate ion etc.Contain a lot of carbonic acid in the water of condensation of fuel cell, and remove the negatively charged ion (chloride ion, sulfate ion etc.) of trace from the water of condensation that contains a large amount of carbonic acid, utilizing common anionite-exchange resin is the comparison difficulty.Especially because chloride ion is 1 valency negatively charged ion, poor by the adsorption efficiency of anionite-exchange resin absorption therefore compared with multivalent anions such as sulfate ions, thus the very difficult chloride ion that reduces in the water.
Use in the present embodiment in the total exchange capacity of anionite-exchange resin of original state that the shared ratio of chloride ion is below 10%, preferred anionite-exchange resin below 1%.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If the shared ratio of chloride ion surpasses 10% in the total exchange capacity of the anionite-exchange resin of original state, then anionite-exchange resin is easy to be sidelong out chloride ion to treating water, rather than, promptly be difficult to effectively reduce the chloride ion in the treating water with foreign ions such as carbanion absorption contained in the water.
In addition, when anionite-exchange resin comprises the trimethylammonium ammonium in return during the strongly basic anion exchange resin of base, the shared ratio of chloride ion is preferably below by the value of obtaining with following formula (1) in the total exchange capacity of the anionite-exchange resin of original state.Thus, when treating water contains a large amount of carbonic acid, also can reduce the emit ratio of chloride ion, can effectively reduce the chloride ion in the treating water to the treating water side.
R Cl＝4×C Cl/CO 2 0.53 …(1)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbanion, bicarbonate ion in the processed water are scaled CO 2After CO 2Concentration (ppm)
In addition, comprise the dimethyl ethanol ammonium in return during the strongly basic anion exchange resin of base at anionite-exchange resin, the shared ratio of chloride ion is preferably below by the value of obtaining with following formula (2) in the total exchange capacity of the described anionite-exchange resin of original state.Thus, the emit ratio of chloride ion can be reduced, the chloride ion in the treating water can be effectively reduced to the treating water side.
R Cl＝1.3×C Cl/CO 2 0.45 …(2)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbonic acid in the processed water is scaled CO 2After CO 2Concentration (ppm)
Following formula (1) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 2 of relation calculate.Following formula (2) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 3 of relation calculate.From following formula as can be known, dissolved CO in the little or processed water of the target chloride ion concentration in treating water 2Under the big situation of concentration, need be provided with the shared ratio of chloride ion in the total exchange capacity of the described anionite-exchange resin of original state very little.
In addition, the anionite-exchange resin that the water treatment device of fuel cell uses be except reducing the chloride ion, also needs to possess thermotolerance and can miniaturization etc.For example, the spy opens in the flat 11-204123 communique and discloses the example that uses the anionite-exchange resin with a plurality of alkyl in order to improve thermotolerance.In addition, for example open in the flat 8-17457 communique and disclose, make the optimized example of amount of the Zeo-karb of in the mixed bed resin post, filling in order to make equipment miniaturization the spy.And in the present embodiment, the preferred carbonate of circulation Ammonium Bicarbonate, Food Grade etc. and after being transformed to calcareous type in anionite-exchange resin uses as the anionite-exchange resin of original state.But,, when needs are removed carbonic acid, be preferably in latter stage and carry out decarbonate processing (utilize degassing film or utilize the decarburization acid tower that adopts the air contact) because the anionite-exchange resin of calcareous type can't be removed carbonic acid.The anionite-exchange resin of the anionite-exchange resin of calcareous type and OH type etc. compares, and under identical exchange capacity, its resin volume is relatively little.That is, the anionite-exchange resin of OH type is replaced into calcareous type, then the resin smaller volume.In addition, the anionite-exchange resin of calcareous type is compared the thermotolerance height with the anionresin ion of OH type etc.Therefore,, also can suppress the decomposition of the ion exchange resin that causes by heat, suppress the stripping of TOC in treating water even the such temperature of the water of condensation of object fuel cell is handled than higher processed water (for example 40～80 ℃).
In the calcareous type anionite-exchange resin of present embodiment, the shared ratio of chloride ion is below 10% in the total exchange capacity of the anionite-exchange resin of original state, the shared ratio of carbanion preferably more than 70%, is more preferably more than 90% in the total exchange capacity of the anionite-exchange resin of original state.In addition, becoming under the situation of calcareous type the most handy heavy carbonic radical ion (bicarbonate ion) displacement, rather than carbanion.This is because under the condition of fuel cell, bicarbonate ion is in more stable status than carbanion.
In the water treatment device 10 of the fuel cell of present embodiment, the processed water of supplying with to above-mentioned anionite-exchange resin (for example tap water, water of condensation etc.) adopts preferably from the top down that direction flows.Following direction by processed water flows, can be with the anionite-exchange resin extruding De Gengmi that fills in the cylindrical shell.Its result, processed water can evenly flow in resin, has improved handling property.
As mentioned above, handle by the water treatment device 10 of the fuel cell of present embodiment and the treating water (pure water) that reduced the concentration of foreign ion, especially chloride ion supplies to fuel cell 12 from treating water pipeline 22.Wherein, this fuel cell 12 is Solid Oxide Fuel Cell, and in this example, the water that is supplied to is used for gas etc. is modified as carbon monoxide (CO) and hydrogen (H 2).
Even the such water that contains a large amount of carbonic acid of water of condensation for discharging from Solid Oxide Fuel Cell utilizes the water treatment device 10 of the fuel cell of present embodiment also can effectively remove a spot of chloride ion that exists in this water.Therefore, the water treatment device 10 of the fuel cell of the utilization of condensed water present embodiment that will be produced by the electric power generation reaction of Solid Oxide Fuel Cell is handled, and this treating water is supplied to Solid Oxide Fuel Cell utilizes again, also can realize the running of fuel cell steady in a long-term.In addition, recycling under the situation of water of condensation, can supply with tap water or pure water in the start of run stage of fuel cell.And, recycling under the situation of water of condensation, preferably in water of condensation contained gaseous emission in the atmosphere after, utilize water treatment device 10 to handle and supply to fuel cell.
In addition, as the SUS304 of one of common used material,, also can cause stress corrosion crack according to different conditions even when other chloride ion of ppm level exists ,This is the known fact, therefore, turns round under the condition of long-term stability in order to make fuel cell, the chloride ion in the treating water need be reduced to below the 100ppb, preferably is reduced to below the 50ppb, more preferably is reduced to below the 10ppb.
In Solid Oxide Fuel Cell, fuel gas (for example gas) and air (containing aerobic) are supplied in (solid oxide type) fuel cell 12 from fuel feed pipeline 24 and air supply pipe road 26 respectively, and generate electricity by the hydrogen that obtained by the modified-reaction of fuel or the reaction of carbon monoxide and oxygen.Such Solid Oxide Fuel Cell is generated electricity under 600～1000 ℃ of high temperature, so preference is as by heat exchanger 28, and will generate electricity heat extraction and water of condensation and tap water carry out heat exchange and supply with warm water.
(embodiment 2)
In the water treatment device 10 of fuel cell shown in Figure 1, has the cylindrical shell that has been filled ion exchange resin.It also can be a plurality of that cylindrical shell can be 1.The ion exchange resin that is filled in the cylindrical shell is anionite-exchange resin, or the mixed bed resin of anionite-exchange resin and Zeo-karb.In addition, the water treatment device 10 of fuel cell can also add that the cylindrical shell be filled with gac etc. being set on the basis of the cylindrical shell that is filled with ion exchange resin.The water treatment device of fuel cell need possess thermotolerance and can miniaturization.For example, the spy opens in the flat 11-204123 communique and discloses the example that uses the anionite-exchange resin with a plurality of alkyl in order to improve thermotolerance.In addition, for example open in the flat 8-17457 communique and disclose, make the optimized example of amount of the Zeo-karb of in the mixed bed resin post, filling in order to make equipment miniaturization the spy.
And in the present embodiment, first carbonate such as circulation Ammonium Bicarbonate, Food Grade and after being transformed to calcareous type, the anionite-exchange resin that is re-used as original state uses in anionite-exchange resin, thus thermotolerance improved, realize miniaturization.The anionite-exchange resin of the anionite-exchange resin of calcareous type and OH type etc. compares, and under identical exchange capacity, its resin volume is relatively little.That is, the anionite-exchange resin of OH type is replaced into calcareous type, then the resin smaller volume.Thereby, but the miniaturization of implement device.In addition, the anionite-exchange resin of calcareous type is compared the thermotolerance height with the anionite-exchange resin of OH type etc.Therefore, even the water of condensation equitemperature that resembles fuel cell, also can suppress the decomposition of the ion exchange resin that caused by heat than higher processed water (for example 40～80 ℃), suppress TOC stripping in treating water.
In the calcareous type anionite-exchange resin of present embodiment, the shared ratio of carbanion preferably more than 70%, is more preferably more than 90% in the total exchange capacity of the anionite-exchange resin of original state, and especially preferably 100%.The calcareous type here is meant calcareous type and heavy carbonic type.Becoming under the situation of calcareous type, preferably with heavy carbonic radical ion (bicarbonate ion) displacement, rather than carbanion.This is because under the condition of fuel cell, bicarbonate ion is in more stable status than carbanion.In addition, consider the performance of removing foreign ion, compare that the anionite-exchange resin of calcareous type is strongly basic anion exchange resin more preferably with weak base anion-exchange resin.
In addition, owing to only can't remove carbonic acid, therefore when needs are removed carbonic acid, be preferably in latter stage and carry out decarbonate and handle (the decarburization acid tower that utilizes degassing film or utilization employing air to contact) with the anionite-exchange resin of the calcareous type of present embodiment.
In the present embodiment, under the situation of the mixed bed resin that uses anionite-exchange resin and Zeo-karb, the median size of Zeo-karb is preferably more than the 0.2mm, and is below 80% of median size of anionite-exchange resin.As mentioned above, the proportion of Zeo-karb and anionite-exchange resin is different, therefore (generalized case, Zeo-karb is more great than the ratio of anionite-exchange resin), if use the Zeo-karb of above-mentioned extraneous particle diameter, then two kinds of ion exchange resin can separate owing to the vibration that causes in processes such as the conveyance of water treatment device, installation, running, the stripping material that causes being derived from two kinds of ion exchange resin can't be captured, and can't fully remove the TOC in the water that fuel cell is supplied with.In addition, if the median size of Zeo-karb is less than 0.2mm, then the pressure-losses of cylindrical shell increases, cause processing cost to improve, if and surpass anionite-exchange resin median size 80%, then the difference of the final speed during water flowing becomes big, causes Zeo-karb and anionite-exchange resin separate easily.
The mixed bed resin of Zeo-karb particle diameter that used the such control of present embodiment just has been achieved the separation that suppresses two kinds of ion exchange resin being caused by vibration, makes the stable foreign ion of removal become possibility.
In addition, the particle diameter of anionite-exchange resin is not particularly limited, but the volume of the anionite-exchange resin in the mixed bed resin of present embodiment 1.5～5 times of volume of Zeo-karb preferably.In addition, if above-mentioned volume ratio is converted into exchange capacity, then the total exchange capacity of anionite-exchange resin is 0.85～3 times of total exchange capacity of Zeo-karb.Wherein, if the volume of anionite-exchange resin is less than 1.5 times of the volume of Zeo-karb, the ratio of then unnecessary Zeo-karb increases, sometimes can't fully remove the negatively charged ion in the water, if and the volume of anionite-exchange resin is greater than 5 times of the volume of Zeo-karb, then be derived from the TOC composition stripping of anionite-exchange resin, cause the TOC in the treating water to increase sometimes.
The foreign ion that contains in the water is carbanion, bicarbonate ion, chloride ion, sulfate ion etc. for example.Contain a lot of carbonic acid in the water of condensation of fuel cell, remove the negatively charged ion (chloride ion, sulfate ion etc.) of trace from the water of condensation that contains a large amount of carbonic acid, utilizing common anionite-exchange resin is the comparison difficulty.Especially when chloride ion be the negatively charged ion of 1 valency, therefore compare with multivalent anions such as sulfate ion, poor by the adsorption efficiency of anionite-exchange resin absorption, be difficult to reduce the chloride ion in the water.
Use in the present embodiment that the shared ratio of chloride ion is below 10%, preferably at the anionite-exchange resin below 1% in the total exchange capacity of anionite-exchange resin of original state.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If the shared ratio of chloride ion surpasses 10% in the total exchange capacity of the anionite-exchange resin of original state, then anionite-exchange resin is easy to be sidelong out chloride ion to treating water, rather than, promptly be difficult to effectively reduce the chloride ion in the treating water with foreign ions such as carbanion absorption contained in the water.
In addition, comprise the trimethylammonium ammonium in return during the strongly basic anion exchange resin of base at anionite-exchange resin, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (1) in the total exchange capacity of the anionite-exchange resin of original state.Thus, when treating water contains a large amount of carbonic acid, also can reduce the emit ratio of chloride ion, can effectively reduce the chloride ion in the treating water to the treating water side.
R Cl＝4×C Cl/CO 2 0.53 …(1)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbanion, bicarbonate ion in the processed water are scaled CO 2The time CO 2Concentration (ppm)
In addition, comprise the dimethyl ethanol ammonium in return during the strongly basic anion exchange resin of base at anionite-exchange resin, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (2) in the total exchange capacity of the described anionite-exchange resin of original state.Thus, the emit ratio of chloride ion can be reduced, the chloride ion in the treating water can be effectively reduced to the treating water side.
R Cl＝1.3×C Cl/CO 2 0.45 …(2)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbonic acid in the processed water is scaled CO 2The time CO 2Concentration (ppm)
Following formula (1) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 2 of relation calculate.Following formula (2) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 3 of relation calculate.From following formula as can be known, dissolved CO in the little or processed water of the target chloride ion concentration in treating water 2Under the big situation of concentration, need be provided with the shared ratio of chloride ion in the total exchange capacity of the described anionite-exchange resin of original state very little.
In the water treatment device 10 of the fuel cell of present embodiment, the circulation of the processed water of supplying with to above-mentioned anionite-exchange resin (for example tap water, water of condensation etc.) preferably uses down direction mobile.Following direction by processed water flows, can be with the anionite-exchange resin extruding De Gengmi that fills in the cylindrical shell.Its result, processed water can evenly flow in resin, has improved handling property.
As mentioned above, handle by the water treatment device 10 of the fuel cell of present embodiment and the treating water (pure water) that reduced foreign ion, especially chloride ion concentration supplies to fuel cell 12 from treating water pipeline 22.Wherein, this fuel cell 12 is Solid Oxide Fuel Cell, in this example, utilizes the water be supplied to that gas etc. is modified as carbon monoxide (CO) and hydrogen (H 2).
Even the such water that contains a large amount of carbonic acid of water of condensation from Solid Oxide Fuel Cell is discharged utilizes the water treatment device 10 of the fuel cell of present embodiment also can effectively remove a spot of chloride ion that exists in this water.Therefore, the water treatment device 10 of the fuel cell of the utilization of condensed water present embodiment that will be produced by the electric power generation reaction of Solid Oxide Fuel Cell is handled, and this treating water is supplied to Solid Oxide Fuel Cell utilizes again, also can realize the running of fuel cell steady in a long-term.Simultaneously, when the recycle condensed water, can supply with tap water or pure water in the start of run stage of fuel cell.In addition, if the recycle condensed water then is preferably in the gas that will comprise in the condensed water and arranges after atmosphere, handle by water treatment device 10, then the fueling battery.
In addition, as the SUS304 of one of general purpose material when other chloride ion of ppm level exists, according to different conditions, also can cause stress corrosion crack, this is the known fact, therefore, for fuel cell is turned round under the condition of long-term stability, chloride ion in the treating water need be reduced to below the 100ppb, preferably be reduced to below the 50ppb, more preferably be reduced to below the 10ppb.
In Solid Oxide Fuel Cell, fuel gas (for example gas) and air (containing aerobic) are supplied to (solid oxide type) fuel cell 12 from fuel feed pipeline 24 and air supply pipe road 26 respectively, and the hydrogen that is obtained by the modified-reaction of fuel or carbon monoxide and oxygen react and generates electricity.Such Solid Oxide Fuel Cell is generated electricity under 600～1000 ℃ of high temperature, and is therefore preferred by heat exchanger 28, and heat extraction and tap water are carried out supplying with warm water after the heat exchange.
(embodiment 3)
In the water treatment device 10 of fuel cell shown in Figure 1, can be equipped with the cylindrical shell that has been filled ion exchange resin.Cylindrical shell can be 1 or a plurality of.The ion exchange resin that is filled in the cylindrical shell, though mainly be the mixed bed resin of anionite-exchange resin and Zeo-karb, but, if one side also is provided with cylindrical shell at the upper reaches, also can be other anionite-exchange resin, or single of Zeo-karb etc.In addition, the water treatment device 10 of fuel cell can be on the basis of the cylindrical shell that is filled with ion exchange resin, the additional cylindrical shell of filling gac etc. that is provided with.In the mixed bed resin of the Zeo-karb of present embodiment and anionite-exchange resin, the median size of Zeo-karb is preferably more than the 0.2mm, and below 80% of median size of anionite-exchange resin preferably.As explained above, because the proportion of Zeo-karb and anionite-exchange resin different (proportion of general Zeo-karb is greater than the proportions of anionite-exchange resin), if therefore use the Zeo-karb of the particle diameter outside the above-mentioned scope, then two kinds of ion exchange resin can be because the vibration that causes in processes such as the conveyance of water treatment device, installation, running, heavy Zeo-karb moves to the bottom, the anionite-exchange resin that proportion is little moves to top, and two kinds of ion exchange resin separate.If separated like this mixed bed resin uses under high temperature, low flow, then might stripping from cation constituent such as the Trimethylamine 99 of anionite-exchange resin and from the anionic components such as polystyrolsulfon acid of Zeo-karb.Its result, the TOC in the treating water increases.In addition, if the median size of Zeo-karb is less than 0.2mm, then the pressure-losses of cylindrical shell increases, cause processing cost to improve, if and surpass anionite-exchange resin median size 80%, then the difference of the final speed during water flowing becomes big, causes Zeo-karb and anionite-exchange resin separate easily.
Present embodiment has been used the mixed bed resin of controlling the particle diameter of Zeo-karb, just suppressed the separation of two kinds of ion exchange resin causing by vibration, therefore realized being derived from stripping composition cation constituents such as () Trimethylamine 99s of anionite-exchange resin and caught, and stripping composition anionic components such as () polystyrolsulfon acids that is derived from Zeo-karb is caught by anionite-exchange resin by Zeo-karb.Its result, the TOC that can to reduce with above-mentioned stripping composition be principal constituent has realized the steady removal of foreign ion.
In addition, the particle diameter of anionite-exchange resin is not particularly limited, but the volume of the anionite-exchange resin in the mixed bed resin of present embodiment 1.5～5 times of volume of Zeo-karb preferably.In addition, if above-mentioned volume ratio is converted into exchange capacity, then the total exchange capacity of anionite-exchange resin is 0.85～3 times of total exchange capacity of Zeo-karb.If the volume of anionite-exchange resin is less than 1.5 times of the volume of Zeo-karb, the ratio of then unnecessary Zeo-karb increases, sometimes can't fully remove the negatively charged ion in the water, if and the volume of anionite-exchange resin is greater than 5 times of the volume of Zeo-karb, then be derived from the TOC composition stripping of anionite-exchange resin, cause the TOC in the treating water to increase sometimes.
The foreign ion that contains in the water is carbanion, bicarbonate ion, chloride ion, sulfate ion etc. for example.Contain a lot of carbonic acid in the water of condensation of fuel cell, remove the negatively charged ion (chloride ion, sulfate ion etc.) of trace from the water of condensation that contains a large amount of carbonic acid, utilizing common anionite-exchange resin is the comparison difficulty.Especially when chloride ion be the negatively charged ion of 1 valency, therefore compare with multivalent anions such as sulfate ion, poor by the adsorption efficiency of anionite-exchange resin absorption, be difficult to reduce the chloride ion in the water.
Use in the present embodiment that the shared ratio of chloride ion is below 10%, preferably at the anionite-exchange resin below 1% in the total exchange capacity of anionite-exchange resin of original state.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If the shared ratio of chloride ion surpasses 10% in the total exchange capacity of the anionite-exchange resin of original state, then anionite-exchange resin is easy to be sidelong out chloride ion to treating water, rather than, promptly be difficult to effectively reduce the chloride ion in the treating water with foreign ions such as carbanion absorption contained in the water.
In addition, comprise the trimethylammonium ammonium in return during the strongly basic anion exchange resin of base at anionite-exchange resin, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (1) in the total exchange capacity of the anionite-exchange resin of original state.Thus, when treating water contains a large amount of carbonic acid, also can reduce the emit ratio of chloride ion, can effectively reduce the chloride ion in the treating water to the treating water side.
R Cl＝4×C Cl/CO 2 0.53 …(1)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbanion, bicarbonate ion in the processed water are scaled CO 2CO 2Concentration (ppm)
In addition, comprise the dimethyl ethanol ammonium in return during the strongly basic anion exchange resin of base at anionite-exchange resin, the shared ratio of chloride ion is preferably below by the value of obtaining with following formula (2) in the total exchange capacity of the described anionite-exchange resin of original state.Thus, the emit ratio of chloride ion can be reduced, the chloride ion in the treating water can be effectively reduced to the treating water side.
R Cl＝1.3×C Cl/CO 2 0.45 …(2)
R Cl: the shared ratio (%) of chloride ion (eq/L-R) in the total exchange capacity of anionite-exchange resin (eq/L-R)
C Cl: the target chloride ion concentration (ppb) in the treating water
CO 2: dissolved carbonic acid in the processed water is scaled CO 2CO 2Concentration (ppm)
Following formula (1) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 2 of relation calculate.Following formula (2) is the various CO according to the expression processed water 2R under the concentration ClAnd C ClBetween Fig. 3 of relation calculate.By following formula as can be known, dissolved CO in the little or processed water of the target chloride ion concentration in treating water 2Under the big situation of concentration, need be provided with the shared ratio of chloride ion in the total exchange capacity of the described anionite-exchange resin of original state very little.
In addition, the anionite-exchange resin that the water treatment device of fuel cell uses be except reducing the chloride ion, also needs to possess thermotolerance and can miniaturization etc.For example, the spy opens in the flat 11-204123 communique and discloses the example that uses the anionite-exchange resin with a plurality of alkyl in order to improve thermotolerance.In addition, for example open in the flat 8-17457 communique and disclose, make the optimized example of amount of the Zeo-karb of in the mixed bed resin post, filling in order to make equipment miniaturization the spy.And in the present embodiment, preferred circulation carbonate such as Ammonium Bicarbonate, Food Grade and after being transformed to calcareous type in anionite-exchange resin uses as the anionite-exchange resin of original state.But,, therefore, when needs are removed carbonic acid, be preferably in latter stage and carry out decarbonate processing (utilizing the decarburization acid tower of degassing film or the contact of utilization employing air etc.) because the anionite-exchange resin of calcareous type can't be removed carbonic acid.The anionite-exchange resin of the anionite-exchange resin of calcareous type and OH type etc. compares, and under identical exchange capacity, its resin volume is less relatively.That is, the anionite-exchange resin of OH type is replaced into calcareous type, then the resin smaller volume.Therefore, miniaturization that can implement device.In addition, the anionite-exchange resin of calcareous type is compared the thermotolerance height with the anionresin ion of OH type etc.Therefore, though as the treatment temp of the condensed water of the fuel cell of processed water etc. than higher (for example, 40～80 ℃), also can suppress the decomposition of heat, and be suppressed TOC liquate in the treating water to ion exchange resin.
In the calcareous type anionite-exchange resin of present embodiment, the shared ratio of chloride ion is below 10% in the total exchange capacity of the anionite-exchange resin of original state, the shared ratio of carbanion is preferably more than 70% in the total exchange capacity of the anionite-exchange resin of original state, being more preferably more than 90%, most preferably is 100%.Here said calcareous type comprises calcareous type and heavy carbonic type.If when being calcareous type, not by carbonate, and comparatively suitable by hydrocarbonate (supercarbonate) displacement.This is owing under the condition of fuel cell, the reason that bicarbonate ion is more in stable condition than carbanion.
In the water treatment device 10 of the fuel cell of present embodiment, to passing through above-mentioned anionite-exchange resin processed water (for example tap water, water of condensation etc.), direction flows under preferred the employing.Following direction by processed water flows, and the anionite-exchange resin of filling in the cylindrical shell is squeezed and becomes closeer.Its result, processed water can evenly flow in resin, has improved handling property.
As mentioned above, handle by the water treatment device 10 of the fuel cell of present embodiment and the treating water (pure water) that reduced the concentration of foreign ion, especially chloride ion supplies to fuel cell 12 from treating water pipeline 22.Wherein, this fuel cell 12 is Solid Oxide Fuel Cell, and in this example, the water conservancy that is supplied to is used for gas etc. is modified as carbon monoxide (CO) and hydrogen (H 2).
Even the such water that contains a large amount of carbonic acid of water of condensation from Solid Oxide Fuel Cell is discharged utilizes the water treatment device 10 of the fuel cell of present embodiment also can effectively remove a spot of chloride ion that exists in this water.Therefore, the water treatment device 10 of the fuel cell of the utilization of condensed water present embodiment that will be produced by the electric power generation reaction of Solid Oxide Fuel Cell is handled, and this treating water is supplied to Solid Oxide Fuel Cell utilize again, also can realize the running of fuel cell steady in a long-term.In addition, recycling under the situation of water of condensation, tap water or pure water are as long as supply with in the start of run stage of fuel cell.And, recycling under the situation of water of condensation, after the gas that preferably contains in water of condensation is released in the atmosphere, utilize water treatment device 10 to handle and supply to fuel cell.In addition, if the recycle condensed water then is preferably in after airborne release goes out the gas that comprises in the condensed water, handle by water treatment device 10, then the fueling battery.
In addition, as the SUS304 of one of general purpose material when other chloride ion of ppm level exists, difference according to condition, also can cause stress corrosion crack, this is the known fact, therefore, for fuel cell is turned round under the condition of long-term stability, chloride ion in the treating water need be reduced to below the 100ppb, preferably be reduced to below the 50ppb, more preferably be reduced to below the 10ppb.
In Solid Oxide Fuel Cell, fuel gas (for example gas) and air (containing aerobic) supply to (solid oxide type) fuel cell 12 from fuel feed pipeline 24 and air supply pipe road 26 respectively, and then the hydrogen that is obtained by the modified-reaction of fuel or carbon monoxide and oxygen react and generates electricity.At such soild oxide shape fuel cell at 600～1000 ℃ of high temperature DownGenerate electricity, so, preferably the heat extraction of heat exchanger 28 and tap water are carried out heat exchange after, supply with warm water.
(embodiment 4)
The water treatment device 10 of fuel cell shown in Figure 1 has the cylindrical shell that has been filled ion exchange resin.Cylindrical shell can be one or more.Being filled into the ion exchange resin in the cylindrical shell, is anionite-exchange resin, Zeo-karb, or the mixed bed resin of anionite-exchange resin and Zeo-karb.The ion exchange resin that uses in the present embodiment contains at least a solution in silver, copper and the zinc by circulation and the ion exchange of ion exchange resin is at least a ion exchange resin in the middle of silver ions, cupric ion and the zine ion (hereinafter referred to as the ion exchange resin of silver-colored type, the ion exchange resin of copper type, the ion exchange resin of zinc type).And, by the ion exchange resin that uses so silver-colored type, the ion exchange resin of copper type, the ion exchange resin of zinc type,, also can suppress its breeding even in the water treatment device of fuel cell, sneak into bacterium, realize life-time service.
Circulation contains the time, temperature of any one the solution (making contact) at least in silver, copper and the zinc etc. in ion exchange resin, and the shared ratio of silver ions (cupric ion, zine ion) reaches the top condition of desired proportion in the total exchange capacity of ion exchange resin (ion exchange resin of the ion exchange resin of copper type, zinc type) of silver-colored type as long as selection makes.
The shared ratio of silver ions (cupric ion, zine ion) is preferably in 0.01%～90% scope, more preferably in 0.1%～70% scope in the total exchange capacity of ion exchange resin (ion exchange resin of the ion exchange resin of copper type, zinc type) of silver type.If the ratio of silver ions is less than 0.01% in the total exchange capacity of the ion exchange resin of silver-colored type (copper type, Ami type is also identical), then can not fully suppress to be blended into the breeding of the bacterium in the water treatment device of fuel cell, and if more than 90%, then the stripping quantity of silver ions (cupric ion, zine ion) to the treating water of discharging from the water treatment device of fuel cell will increase sometimes.This is likely because contain a lot of carbonic acid sometimes in the water of condensation of fuel cell and shows acidity, if and, cause with reacting attached to the silver ions on the ion-exchange group, cupric ion or zine ion with such tart water, when promptly containing the ion exchange resin of a lot of hydrionic current logical silver-colored type, copper type or zinc type.And, if having the treating water of silver ions etc. to supply with stripping, then may influence its life-time service to fuel cell.
At ion exchange resin is under the situation of Zeo-karb, as any one solution at least that contains in the middle of silver, copper and the zinc, preferably select in the middle of nitrate solution (silver nitrate solution, copper nitrate solution, zinc nitrate solution etc.), sulfate liquor (silver sulfate solution, copper-bath, solution of zinc sulfate etc.), hydrochloride solution (silver chloride solution, Cupric Chloride Solution, liquor zinci chloridi etc.), the complex salt solution (silver-colored complex salt solution, copper complex salt solution, zinc complex salt solution etc.) at least any one.
In addition, at ion exchange resin is under the situation of storng-acid cation exchange resin, as any one solution at least that contains in the middle of silver, copper and the zinc, preferably select in the middle of nitrate solution, sulfate liquor, hydrochloride solution, the complex salt solution at least any one.
Further, be under the situation of storng-acid cation exchange resin at ion exchange resin, its degree of crosslinking is preferably more than 12%.If the degree of crosslinking of storng-acid cation exchange resin is less than 12%, then the stripping of silver ions (cupric ion, zine ion) meeting sometimes is to the treating water of discharging from the water treatment device of fuel cell.
Simultaneously, as containing solution at least a in silver, copper and the zinc, when ion exchange resin is anionite-exchange resin, complex salt solution preferably.In addition, consider the removal performance of foreign ion, the strongly basic anion exchange resin that anionite-exchange resin is preferably in return basic with the trimethylammonium ammonium.
In the present embodiment, use Zeo-karb at ion exchange resin, under the situation of anionite-exchange resin (especially use) with the in return basic strong basic ion exchange resin of trimethylammonium amido, in ion exchange resin, can circulate (making contact) contain silver, any one complex salt solution at least in copper and the zinc, thereby with the ion exchange of ion exchange resin is silver ions, at least a in the middle of cupric ion and the zine ion, then to silver ions, cupric ion, zine ion reduces processing, thereby separates out silver in the surface and the inside of ion exchange resin, at least a in the middle of copper and the zinc.Like this, by after carrying out ion-exchange, reducing processing,, also can suppress to sneak into the breeding of the bacterium in the water treatment device of fuel cell even adopt the ion exchange resin that silver, copper, zinc are separated out.Its result can life-time service be used for the water treatment device of fuel cell.
Though handling, reduction can pass through H 2Reducing gas such as gas contact with ion exchange resin and carry out, but are to use the reduction of reducing gas to handle and need carry out for a long time under than higher temperature.Therefore, preferred employing can be handled in the wet type reduction that the following short period of time of comparatively gentle condition handles.The wet type reduction is handled, and for example can circulate in ion exchange resin by the solution that will be dissolved with reductive agent (contact) carried out.
Reductive agent can use hydrazine, hydrogen peroxide, xitix, sodium ascorbate, formaldehyde, formic acid, sodium formiate, sodium borohydride etc.
When separating out silver, copper, zinc and the duration of contact solution that contains reductive agent, temperature, pH etc. can suitably set according to the ionic kind of separating out, the kind of reductive agent etc.In addition, handle to obtain the amount of separating out of enough silver, copper, zinc the time, preferably carry out ion-exchange repeatedly and reduction is handled, up to the amount of separating out that obtains expectation when the ion-exchange of only carrying out silver ions, cupric ion, zine ion and reduction.
In the present embodiment, under the situation of the mixed bed resin that uses storng-acid cation exchange resin and strongly basic anion exchange resin, the median size of storng-acid cation exchange resin is below 80% of median size of strongly basic anion exchange resin preferably.This is because Zeo-karb is different with anionite-exchange resin proportion (usually, Zeo-karb compared with anionite-exchange resin than great), if use the storng-acid cation exchange resin of above-mentioned extraneous particle diameter, then two kinds of ion exchange resin can separate owing to the vibration that causes in processes such as the conveyance of water treatment device, installation, running, the stripping material that causes being derived from two kinds of ion exchange resin can't be captured, and can't fully remove the TOC in the water that fuel cell is supplied with.
In the present embodiment, under the situation of using storng-acid cation exchange resin, the value (R that the shared ratio of silver ions or argentiferous coordination ion is preferably obtained by following formula (1) in the total exchange capacity of the storng-acid cation exchange resin of original state Ag) below.In addition, formula (1) is according to the R that is illustrated under the various hydrogen ionexponents (pH) AgAnd C AgBetween Fig. 4 of relation obtain.C Ag＝37exp(-2.4pH)R Ag 3+82exp(-2.0pH)R Ag 2+110000exp(-2.3pH)R Ag (1)
(wherein, C AgBe the target silver concentration of the water treatment device outlet side treating water of fuel cell, (C wherein AgThe scope of=0.001～10ppb), pH is the hydrogen ionexponent (the wherein scope of pH=4～6) of the water treatment device inlet side treating water of fuel cell, R AgBe the middle silver ions of total exchange capacity (eq/L-R) or the shared ratio (%) of argentiferous coordination ion (eq/L-R) of storng-acid cation exchange resin.)
If the ion exchange resin that water treatment device uses has surpassed the value (R that is obtained by formula (1) Ag), the silver ions more than the stripping aimed concn easily from the treating water that the water treatment device of fuel cell is discharged then.
As mentioned above, in the water treatment device of the fuel cell of present embodiment, even in the water treatment device of fuel cell, sneak into bacterium, the germicidal action of silver ions that also can be by being adsorbed by ion exchange resin, cupric ion, zine ion suppresses the breeding of bacterium, guarantees the life-time service of water treatment device.That is, the condensed water that produces because of the electric power generation reaction of fuel cell can be handled by the fuel cell water treatment device of present embodiment,, utilized again, can make that fuel cell is long-term, runs steadily this treating water fueling battery.In addition,, preferably after atmosphere is emitted the gas that comprises in the condensed water, handle, resupply fuel cell 12 by water treatment device 10 if during the recycle condensed water.
(embodiment)
Below, by embodiment and comparative example, the present invention is carried out more specifically and explains, but the present invention is not limited by following embodiment.
(embodiment 1,2)
Use device shown in Figure 1 that the water of condensation of discharging from Solid Oxide Fuel Cell has been carried out water treatment.Dissolved CO in the water of condensation 2Concentration is 250ppm approximately, and chloride ion concentration is 150ppb approximately.The ion exchange resin of filling in the cylindrical shell used with the trimethylammonium amido in return the base strongly basic anion exchange resin 30mL and the mixed bed resin of storng-acid cation exchange resin 10mL.The anionite-exchange resin of embodiment 1 is, (Rohmand Hass company makes at chlorine-based strong alkali anionite-exchange resin, AMBERJET 4002C1) the NaOH aqueous solution 1500mL of circulation 7% in, be transformed to the OH type, make the shared ratio of chloride ion in the total exchange capacity of anionite-exchange resin (below, only be called R sometimes Cl) at the anionite-exchange resin below 1%.The anionite-exchange resin of embodiment 2 is, the anionite-exchange resin of embodiment 1 and the anionite-exchange resin that is not transformed to the OH type are mixed, and makes R ClBe 10% anionite-exchange resin.The Zeo-karb of embodiment 1,2 is AMBERJET 1024H (manufacturing of the Rohm and Hass company) Zeo-karb of Hydrogen.
Among the embodiment 1,2, downward circulation style has all been adopted in the circulation of the processed water in the ion exchange resin.Under this condition, after turning round 24 hours, to taking a sample by the treating water of anion exchange process and having measured chloride ion concentration.Table 1 has gathered its result.
(comparative example 1)
R except the anionite-exchange resin that uses ClBe beyond 20%, comparative example 1 is identical with embodiment 1.
Table 1
Water quality before the water treatment Embodiment 1 Embodiment 2 Comparative example 1
pH 4.3 4.3 4.3 4.3
CO 2Concentration of ordinary dissolution 250ppm 250ppm 250ppm 250ppm
Chloride ion concentration 150ppb ＜10ppb 49ppb 110ppb
As known from Table 1, use R ClBe that chloride ion concentration is lowered to below the 50ppb among the embodiment 2 of 10% anionite-exchange resin.In addition, use R ClBe that chloride ion concentration is lowered to less than 10ppb among the embodiment 1 of the anionite-exchange resin below 1%, shown than embodiment 2 higher chloride ions and removed performance.On the contrary, use R ClBe that chloride ion concentration is 110ppb, the chloride ion of failing fully to remove in the comparative example 1 of 20% anionite-exchange resin.
At R Cl=4 * C Cl/ CO 2 0.53Formula in the CO of substitution processed water 2Chloride ion concentration 50ppb in concentration 250ppm, the treating water then draws R ClBe 10.7%.That is, if with CO 2The processed water of concentration 250ppm is handled, and the chloride ion concentration in the treating water is reached below the 50ppb, then needs to make the shared ratio of chloride ion in the total exchange capacity of anionite-exchange resin below 10.7%.And the value of the foregoing description 1,2 is below the value that above-mentioned formula is calculated.If can make chloride ion concentration in the treating water below 50ppb, fuel cell is turned round long-term and stably.
(embodiment 3,4)
Use device shown in Figure 1 that the water of condensation of discharging from Solid Oxide Fuel Cell has been carried out water treatment.Dissolved CO in the water of condensation 2Concentration is 250ppm approximately, and chloride ion concentration is 150ppb approximately.The ion exchange resin of filling in the cylindrical shell used with the dimethyl ethanol amido in return the base strong basicity Ag ion exchange resin 30mL and the mixed bed resin of storng-acid cation exchange resin 10mL.The anionite-exchange resin of embodiment 3 is that the NaOH aqueous solution 1500mL of circulation 7% is transformed to the OH type in chlorine-based strong alkali anionite-exchange resin (Rohm and Hass company makes, AMBERLITE IRA410C1), makes R ClAt the ion exchange resin below 1%.The anionite-exchange resin of embodiment 4 is, the anionite-exchange resin of embodiment 3 and the anionite-exchange resin that is not transformed to the OH type mixed, and make R ClBe 5% ion exchange resin.The Zeo-karb of embodiment 3,4 is the AMBERJET 1024H (manufacturing of Rohm and Hass company) of Hydrogen.
Among the embodiment 3,4, downward circulation style has all been adopted in the circulation of the processed water in the ion exchange resin.Under such condition, turn round after 24 hours, to taking a sample by the treating water of anion exchange process and having measured chloride ion concentration.Table 2 has gathered its result.
(comparative example 2)
R except the anionite-exchange resin that uses ClBe set at beyond 20%, comparative example 2 is identical with embodiment 3.
Table 2
Water quality before the water treatment Embodiment 3 Embodiment 4 Comparative example 2
pH 4.3 4.3 4.3 4.3
CO 2Concentration of ordinary dissolution 250ppm 250ppm 250ppm 250ppm
Chloride ion concentration 150ppb ＜10ppb 50ppb 210ppb
As known from Table 2, use R ClBe that chloride ion concentration is lowered to below the 50ppb among the embodiment 4 of 5% anionite-exchange resin.In addition, use R ClBe that chloride ion concentration is lowered to below the 10ppb among the embodiment 3 of the anionite-exchange resin below 1%, shown than embodiment 4 higher chloride ions and removed performance.On the contrary, use R ClBe that chloride ion concentration is 210ppb, the chloride ion of failing fully to remove in the comparative example 2 of 20% anionite-exchange resin.
At R Cl=1.3 * C Cl/ CO 2 0.45Formula in the CO of substitution processed water 2Chloride ion concentration 50ppb in concentration 250ppm, the treating water then draws R ClBe 5.4%.That is, if with CO 2The processed water of concentration 250ppm is handled, and the chloride ion concentration in the treating water is reached below the 50ppb, then needs to make the shared ratio of chloride ion in the total exchange capacity of anionite-exchange resin below 5.4%.And the foregoing description 3,4 is lower than the value of being calculated by following formula.
(embodiment 5,6)
Use device shown in Figure 1 that the water of condensation of discharging from Solid Oxide Fuel Cell has been carried out water treatment.The ion exchange resin of filling in the cylindrical shell has used the in return basic strongly basic anion exchange resin of trimethylammonium amido that is equivalent to 0.13eq with exchange capacity.The anionite-exchange resin of embodiment 5,6 is circulation 4L Ammonium Bicarbonate, Food Grade (sodium bicarbonate NaHCO in OH type strongly basic anion exchange resin (Rohm and Hass company makes, AMBERJET 4002OH) 3) (1 regulation), make the shared ratio (RCl) of chloride ion in the total exchange capacity of anionite-exchange resin below 1%, the ratio of carbanion (below, abbreviate R-carbonic acid sometimes as) more than 90%, 70% anionite-exchange resin.
Supply with the water of condensation (about 60 ℃) that generates from Solid Oxide Fuel Cell in the water treatment device of embodiment 5,6, turned round 24 hours with 1kW generated energy.Downward circulation style has all been adopted in the circulation of the processed water in the ion exchange resin.Table 3 has gathered the result that the volume of the anionite-exchange resin of embodiment 5,6 and the TOC concentration in the treating water are measured.
(comparative example 3)
Except the R-carbonic acid of the anionite-exchange resin that uses less than 1%, comparative example 3 is identical with embodiment 5.
Table 3
Embodiment 5 Embodiment 6 Comparative example 3
R-carbonic acid ＞90％ 70％ ＜1％
Exchange capacity 0.13eq 0.13eq 0.13eq
The resin volume 80mL 86mL 100mL
TOC ＜0.1ppm ＜0.1ppm 0.5ppm
As known from Table 3, by making ion exchange resin become calcareous type, realized comparing among the embodiment 5,6, under the situation of not damaging loading capacity, reduced the resin volume with the OH type ion exchange resin of comparative example 3.Especially R-carbonic acid is compared with comparative example 3 at the embodiment more than 90% 5, and the resin volume has reduced by 20%.In addition, though in the calcareous type ion exchange resin of embodiment 5,6 water of condensation of 60 ℃ of circulations and handling, the TOC in the treating water also is below the 0.1ppm, therefore the decomposition of the resin that is caused by heat as can be known is suppressed.Relative with it, if in the OH of comparative example 3 type ion exchange resin the water of condensation of 60 ℃ of circulations and handling, then in treating water, can detect the TOC of 0.5ppm, and this be likely the resin that causes by heat decomposition caused.
As mentioned above, be transformed to calcareous type in advance, can reduce the space that is provided with of device, can suppress simultaneously the decomposition of the resin that causes by heat, reduce the stripping of TOC by anionite-exchange resin with original state.
(embodiment 7)
Except the circulating direction of the processed water in the ion exchange resin being changed into the circulation style that makes progress, embodiment 7 is identical with embodiment 1.Under this condition, to taking a sample, and measured the concentration of chloride ion by the treating water of ion exchange resin treatment.Table 4 has gathered its result (in addition, for ease of relatively, also having listed the result of embodiment 1 in the table 4).
Table 4
Water quality before the water treatment Embodiment 1 Embodiment 7
pH 4.3 4.3 4.3
CO 2Concentration of ordinary dissolution 250ppm 250ppm 250ppm
Chloride ion concentration 150ppb ＜10ppb 13ppb
Be made as among the embodiment 7 of upwards circulation at the circulating direction with processed water, resin is not extruded and becomes closely knit, has only observed a bit to flow.Therefore, short-circuit flow occurred among the embodiment 7, the chloride ion concentration in the treating water is compared than the embodiment 1 that circulates downwards and has been risen a bit.Hence one can see that, as embodiment 1, adopts downward circulation style to carry out water treatment.
(embodiment 8)
Made anionite-exchange resin (real density 1080kg/m with median size 0.7mm 3) and Zeo-karb (the real density 1140kg/m of median size 0.5mm 3) with 3: 1 (=anionite-exchange resin: the cylindrical shell (diameter 40mm * height 200mm) of the mixed bed resin that ratio Zeo-karb) is filled of volume ratio.It was shaken 24 hours.To the speed circulation pure water of the cylindrical shell after shaking, measured the TOC for the treatment of water again with 10mL/min.The isolating situation and the TOC concentration that whether occur ion exchange resin after table 5 has been represented to shake.
(comparative example 4)
In the comparative example 4, except using anionite-exchange resin (the real density 1080kg/m of median size 0.7mm 3) and Zeo-karb (the real density 1140kg/m of median size 0.7mm 3) outside, under the condition identical, test with embodiment 3.The isolating situation and the TOC concentration that have or not ion exchange resin after table 5 has been concluded and shaken.
Table 5
Figure GSA00000126236500271
Figure GSA00000126236500281
As known from Table 5, in embodiment 8, even shake 24 hours, do not observe separating of anionite-exchange resin and Zeo-karb, and the TOC of the treating water behind the circulation pure water is below the 0.1ppm afterwards by observing.By comparison, in comparative example 4, shake and to observe the bottom that about 80% Zeo-karb gathers cylindrical shell after 24 hours, promptly can confirm to separate.And the TOC in the treating water under this state behind the circulation pure water is 0.5ppm.
(embodiment 9)
Use device shown in Figure 1, the water of condensation of discharging from Solid Oxide Fuel Cell has been carried out water treatment.Dissolved CO in the water of condensation 2Concentration is about 250ppm.Water treatment device has used the cylindrical shell (diameter 40mm * height 200mm) with the mixed bed resin of anionite-exchange resin 30mL and Zeo-karb 10mL mixing filling.The TOC concentration that has gathered the treating water after turning round 24 hours in the table 6.
(comparative example 5,6)
Only fill the cylindrical shell of anionite-exchange resin 40mL in the comparative example 5 except use, and comparative example 6 is except the cylindrical shell (diameter 40mm * height 200mm) of the mixed bed resin of use to mix filling anionite-exchange resin 36mL and Zeo-karb 4mL, tests under the condition identical with embodiment 9.The TOC concentration that has gathered the treating water after turning round 24 hours in the table 6.
Table 6
Water quality before the water treatment Embodiment 9 Comparative example 5 Comparative example 6
pH 4.4 4.4 4.4 4.4
CO 2Concentration of ordinary dissolution 200ppm 200ppm 200ppm 200ppm
TOC 20ppb 20ppb 320ppb 50ppb
Trimethylamine 99 concentration ＜1ppb ＜1ppb 450ppb ＜1ppb
Polystyrolsulfon acid concentration ＜1ppb ＜1ppb ＜1ppb 38ppb
As known from Table 6, the ratio of anionite-exchange resin and Zeo-karb is controlled at the embodiment 9 of appropriate value, compares with the comparative example 6 of filling male ion-exchange resin only with the comparative example 5 of only filling anionite-exchange resin, and TOC is suppressed lowlyer.Only fill in the comparative example 5 of anionite-exchange resin, from treating water, detected the Trimethylamine that is derived from the functional group of anionite-exchange resin probably.In addition, only in the comparative example 6 of filling male ion-exchange resin, detected the polystyrolsulfon acid that is derived from the functional group of Zeo-karb probably from treating water.In addition, from described embodiment 8,9 result as can be known, the ratio of anionite-exchange resin and Zeo-karb is set in proper range and mixes, even then in the conveying of resin cylindrical shell, cause the vibration or after installation by the vibration etc., also can suppress separating of Zeo-karb and anionite-exchange resin.Its result can suppress to be derived from the stripping of the TOC composition of ion exchange resin, water that can supplying high purity.
(embodiment 10,11)
Adopt device shown in Figure 1, carried out the water treatment of the condensed water of being discharged by Solid Oxide Fuel Cell.The about 16ppm of dissolved CO2 concentration in the condensed water, the about 100ppb of chloride ion concentration, the pH of condensed water is 5.The ion exchange resin that is filled into cylindrical shell has used the strongly basic anion exchange resin 30mL that the trimethylammonium amido is in return basic to mix the ion exchange resin of filling with storng-acid cation exchange resin 10mL.The strongly basic anion exchange resin of embodiment 10,11 has used the strongly basic anion exchange resin (Amberjet4002 (OH)) of OH type.Simultaneously, the storng-acid cation exchange resin of embodiment 10, use the Zeo-karb (Amberjet1024 (H)) of degree of crosslinking 12%, the AgNO3 aqueous solution 1500mL that makes 0.15ppb is by this resin, make it convert the Ag type to, the ratio of the silver ions that occupies in the complete exchange capacity of Zeo-karb adjusts to 9%.The storng-acid cation exchange resin of embodiment 11, its degree of crosslinking Zeo-karb of 12% (Amberjet1024 (H)), this resin is done the AgNO3 aqueous solution 1500mL circulation of 10g/L, convert the Ag type to, the ratio of the silver ions that occupies in the complete exchange capacity of Zeo-karb is adjusted to more than 90%.
By the processed water of ion exchange resin, all circulations downwards in embodiment 10,11.And, turning round after 10 days, the treating water that sampling is crossed by ion exchange resin treatment is measured concentration of silver ions, chloride ion concentration, has investigated having or not of bacterium.Its result is summarized in the table 7.
(comparative example 7)
Comparative example 7 does not convert to the storng-acid cation exchange resin of Ag type except that having used, and is identical with examples of implementation 10.
Table 7
Embodiment 10 Embodiment 11 Comparative example 7
Bacterium has or not Do not have Do not have Have
Concentration of silver ions ＜10ppb About 1000ppb ?＜10ppb
Chloride ion concentration ＜10ppb ?＜10ppb ?＜10ppb
Can judge according to table 7, used among the embodiment 10,11 of the storng-acid cation exchange resin that converts the Ag type to, even also almost do not produce bacterium after turning round 10 days, still, use the comparative example 7 of the storng-acid cation exchange resin that does not convert the Ag type to, be observed and produced bacterium.Simultaneously, the shared ratio of silver ions is adjusted in the examples of implementation 11 more than 90% in the complete exchange capacity of Zeo-karb, the silver ions that comprises about 1000ppb in the treating water, but, the silver ions proportion is adjusted among 9% the embodiment 10 in the complete exchange capacity of Zeo-karb, is able to the silver ions in the treating water is suppressed at below the 10ppb.In addition, in embodiment 10,11 and the comparative example 7, the chloride ion concentration in the treating water is below 10ppb, can fully remove chloride ion.
At C Ag=37exp (2.4pH) R Ag 3+ 82exp (2.0pH) R Ag 2+ 110000exp (2.3pH) R Ag
Formula in, if substitution pH5, C Ag10ppb is R then AgBecome 9.4%.That is, handle pH and be 5 processed water, want the concentration of silver ions in the treating water is made as below the 10ppb, need establish the ratio that silver ions occupies in the complete exchange capacity of anionite-exchange resin is below 9.4%.And it is below the value that is calculated by above-mentioned numerical expression that the foregoing description 10 satisfies.Therefore, clear and definite embodiment 10 is more suitable for secular utilization than embodiment 11.
(embodiment 12)
Among the embodiment 12, use the storng-acid cation exchange resin (Amberjet1024 (H)) of degree of crosslinking 8%, with the AgNO3 aqueous solution of 1500mL0.27ppb this resin that circulates, convert the Ag type to, except that the ratio that silver ions accounts in the complete exchange capacity of Zeo-karb is adjusted to 9%, carried out the test same with embodiment 10.And, turning round after 10 days, the treating water that sampling is crossed by ion exchange resin treatment is measured concentration of silver ions, and has been investigated having or not of bacterium.Table 8 has been concluded its result.
[table 8]
Embodiment 10 Embodiment 12
Having or not of bacterium Do not have Do not have
Concentration of silver ions ＜10ppb 17ppb
Can judge from table 8, use the embodiment 12 of the storng-acid cation exchange resin of degree of crosslinking 8%, with embodiment 10 comparisons of the storng-acid cation exchange resin that has used degree of crosslinking 12%, the silver ions of liquate increases in treating water.Therefore, in order to suppress liquate silver ions in treating water, preferably adopt the exchange resin of degree of crosslinking at the highly acidic cation more than 12%.

Claims (30)

1. the water treatment device of a fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, it is characterized in that: described ion exchange resin comprises anionite-exchange resin, and the shared ratio of chloride ion is below 10% in the total exchange capacity of the described anionite-exchange resin of original state.
2. the water treatment device of a fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, it is characterized in that; Described ion exchange resin comprises anionite-exchange resin, the shared ratio of chloride ion is configured in the total exchange capacity of the described anionite-exchange resin of original state, the dissolved carbonate concentration is high more then more little in the processed water, and the target cl concn in the treating water is low more then more little.
3. the water treatment device of fuel cell as claimed in claim 1 or 2, it is characterized in that: described anionite-exchange resin comprises the strongly basic anion exchange resin that the trimethylammonium ammonium is in return basic, and the shared ratio of chloride ion is smaller or equal to the value (R that is obtained by following formula (1) in the total exchange capacity of the described anionite-exchange resin of original state Cl):
R Cl＝4×C Cl/CO 2 0.53…(1)
Wherein, R ClBe shared ratio (%), the C of chloride ion (eq/L-R) in the total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be the CO that is dissolved in the processed water 2Concentration (ppm).
4. the water treatment device of fuel cell as claimed in claim 1 or 2, the water treatment device of this fuel cell uses anionite-exchange resin, it is characterized in that: described anionite-exchange resin comprises the dimethyl ethanol ammonium strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is for smaller or equal to by the value (R that obtains with following formula (2) in the total exchange capacity of the described anionite-exchange resin of original state Cl):
R Cl＝1.3×C Cl/CO 2 0.45…(2)
Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be dissolved CO in the processed water 2Concentration (ppm).
5. the water treatment device of fuel cell as claimed in claim 1 or 2 is characterized in that The anionite-exchange resin of described original state is the anionite-exchange resin that is transformed to calcareous type by circulation carbonate.
6. the water treatment device of fuel cell as claimed in claim 1 or 2 is characterized in that: the processed water of the described anionite-exchange resin of flowing through adopts down the direction circulation style to carry out.
7. the water treatment device of fuel cell as claimed in claim 1 or 2, it is characterized in that: contain water of condensation in the processed water by described anionite-exchange resin by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
8. the water treatment device of a fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, it is characterized in that: described ion exchange resin comprises anionite-exchange resin, and the described anionite-exchange resin of original state is transformed to the anionite-exchange resin of calcareous type by circulation carbonate.
9. the water treatment device of fuel cell as claimed in claim 8 is characterized in that: in the total exchange capacity of the anionite-exchange resin of described original state 70～100%, and calcareous type.
10. the water treatment device of fuel cell as claimed in claim 8 or 9, it is characterized in that: described anionite-exchange resin is strongly basic anion exchange resin.
11. the water treatment device of fuel cell as claimed in claim 8 or 9, it is characterized in that: contain water of condensation in the processed water by described anionite-exchange resin by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
12. the water treatment device of a fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, it is characterized in that: described ion exchange resin contains the mixed bed resin of Zeo-karb and anionite-exchange resin, the median size of described Zeo-karb is more than the 0.2mm, and is below 80% of median size of described anionite-exchange resin.
13. the water treatment device of fuel cell as claimed in claim 12 is characterized in that: the volume of described anionite-exchange resin is 1.5～5 times of volume of described Zeo-karb.
14. the water treatment device of fuel cell as claimed in claim 12 is characterized in that: the shared ratio of chloride ion is below 10% in the total exchange capacity of the described anionite-exchange resin of original state.
15. the water treatment device of fuel cell as claimed in claim 12 is characterized in that: the shared ratio of chloride ion is configured in the total exchange capacity of the described anionite-exchange resin of original state, dissolved CO in the processed water 2Concentration is high more then more little, and the target cl concn in the treating water is low more then more little.
16. water treatment device as claim 14 or 15 described fuel cells, it is characterized in that: described anionite-exchange resin comprises the trimethylammonium amido strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is smaller or equal to the value (R that is obtained by following formula (1) in the total exchange capacity of the described anionite-exchange resin of original state Cl):
R Cl＝4×C Cl/CO 2 0.53…(1)
Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be dissolved CO in the processed water 2Concentration (ppm).
17. water treatment device as claim 14 or 15 described fuel cells, it is characterized in that,: the water treatment device of this fuel cell uses anionite-exchange resin, described anionite-exchange resin comprises the dimethyl ethanol ammonium strongly basic anion exchange resin of base in return, and the shared ratio of chloride ion is smaller or equal to by the value (R that obtains with following formula (2) in the total exchange capacity of the described anionite-exchange resin of original state Cl):
R Cl＝1.3×C Cl/CO 2 0.45…(2)
Wherein, R ClBe middle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anionite-exchange resin ClBe target chloride ion concentration (ppb), the CO in the treating water 2Be dissolved CO in the processed water 2Concentration (ppm).
18. the water treatment device of fuel cell as claimed in claim 12 is characterized in that: the described anionite-exchange resin of original state is the anionite-exchange resin that is transformed to calcareous type by circulation carbonate.
19. the water treatment device of fuel cell as claimed in claim 18 is characterized in that: in the total exchange capacity of the anionite-exchange resin of described original state 70～100%, calcareous type.
20. the water treatment device of fuel cell as claimed in claim 12 is characterized in that: undertaken by direction circulation style under the processed water employing of described anionite-exchange resin.
21. the water treatment device of fuel cell as claimed in claim 12, it is characterized in that: contain water of condensation in the processed water by described anionite-exchange resin by the electric power generation reaction generation of fuel cell, described processed water is reused in described fuel cell after by described anion exchange process.
22. the water treatment device of a fuel cell, the water treatment device of this fuel cell makes spent ion exchange resin, it is characterized in that: by making at least a solution that contains in silver, copper and the zinc, with any one displacement at least in the middle of ion usefulness silver ions, cupric ion and the zine ion of ion exchange resin by described ion exchange resin.
23. the water treatment device of fuel cell as claimed in claim 22, it is characterized in that: described ion exchange resin contains Zeo-karb, described solution be selected from the middle of the nitrate solution, sulfate liquor, chloride soln, complex salt solution at least any one.
24. the water treatment device of fuel cell as claimed in claim 22, it is characterized in that: described ion exchange resin comprises storng-acid cation exchange resin, described solution be selected from the middle of the nitrate solution, sulfate liquor, chloride soln, complex salt solution at least any one.
25. the water treatment device of fuel cell as claimed in claim 22 is characterized in that: described ion exchange resin comprises anionite-exchange resin, and described solution is complex salt solution.
26. the water treatment device of fuel cell as claimed in claim 25 is characterized in that
Figure FSA00000126236400051
Described anionite-exchange resin is the strongly basic anion exchange resin that the trimethylammonium ammonium is in return basic.
27. the water treatment device as claim 23,25 or 26 described fuel cells is characterized in that
Figure FSA00000126236400052
By the described complex salt solution of circulation in described ion exchange resin, with the ion exchange of ion exchange resin be in silver ions, cupric ion and the zine ion at least after any one, handle by reduction, silver, copper or zinc are precipitate into the surperficial and inner of described ion exchange resin.
28. the water treatment device of fuel cell as claimed in claim 24 is characterized in that
Figure FSA00000126236400053
The degree of crosslinking of described storng-acid cation exchange resin is more than 12%.
29. the water treatment device of fuel cell as claimed in claim 22 is characterized in that
Figure FSA00000126236400054
Described ion exchange resin comprises the mixed bed resin of storng-acid cation exchange resin and strong basic ion exchange resin, and the median size of described storng-acid cation exchange resin is smaller or equal to 80% of the median size of described strong basic ion exchange resin.
30. the water treatment device of fuel cell as claimed in claim 22 is characterized in that Described ion exchange resin comprises storng-acid cation exchange resin, and the shared ratio of silver ions or argentiferous coordination ion is smaller or equal to the value (R that is obtained by following formula (3) in the total exchange capacity of the described storng-acid cation exchange resin of original state Ag):
C Ag＝37exp(-2.4pH)R Ag 3+82exp(-2.0pH)R Ag 2+110000exp(-2.3pH)R Ag (3)
Wherein, C AgBe the target silver concentration of the water treatment device outlet side treating water of fuel cell, and C AgThe scope of=0.001～10ppb, pH is the hydrogen ionexponent of the water treatment device inlet side processed water of fuel cell, and the scope of pH=4～6, R AgBe the middle silver ions of total exchange capacity (eq/L-R) or the shared ratio (%) of argentiferous coordination ion (eq/L-R) of storng-acid cation exchange resin.
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