CN101921010B - Water treatment facility for fuel cell - Google Patents

Water treatment facility for fuel cell Download PDF

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CN101921010B
CN101921010B CN2010101876043A CN201010187604A CN101921010B CN 101921010 B CN101921010 B CN 101921010B CN 2010101876043 A CN2010101876043 A CN 2010101876043A CN 201010187604 A CN201010187604 A CN 201010187604A CN 101921010 B CN101921010 B CN 101921010B
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exchange resin
water
ion
fuel cell
anion exchange
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CN101921010A (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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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
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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

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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 facilities of fuel cell
Technical field
The present invention relates to make the water treatment facilities of the fuel cell of spent ion exchange resin.
Background technology
Fuel cell needs hydrogen, and, in order from gas or natural gas etc., to manufacture hydrogen, need in modified process, make again water, and water is wherein used pure water.In addition, also need to use pure water when cooled fuel cell or when the polymeric membrane to polymer electrolyte fuel cell carries out humidification etc.
Pure water is normally made by the water treatment facilities removal foreign ion that possesses ion exchange resin.Except manufacturing from running water the technology of pure water, there is the multiple condensed water generated by the electric power generation reaction to from fuel cell etc. to be processed at present, this processing water (pure water) is recycled to the technology in fuel cell.
For example, a kind of like this technology is disclosed in patent documentation 1: in the water treatment facilities that the carbanion in the cooling water of supplying with at the corrosion subtend fuel cell for preventing fuel cell and bicarbonate ion (hereinafter referred to as carbanion etc. or only be called carbonic acid) are processed, adjust to suitable degree by the usage rate by anion exchange resin and cation exchange resin, reduce the amount of cation exchange resin, the miniaturization of implement device.Put down in writing in patent documentation 2 by by the amount optimization of cation exchange resin, with the content of the miniaturization of implement device, but anion exchange resin has not been inquired into.
For example, in patent documentation 2, disclose by using the high ion exchange resin of thermal endurance to improve the water treatment facilities of heat extraction yield.
In addition, because fuel cell be take to use for a long time as target and is developed, so need too to use for a long time for the water treatment facilities of such fuel cell.But the water used in fuel cell is because the air with being introduced by extraneous gas contacts, therefore, according to the difference that environment is set of device, bacterium may be sneaked in water treatment facilities and be bred by this air sometimes.If bacterial reproduction is arranged in water treatment facilities, not only can not get the water quality of expectation, also likely cause and stop up and can't stably supply with processing water.
Vegetative method (for example,, with reference to non-patent literature 1 and patent documentation 3) in conventional art in existing several inhibition water treatment facilities.
In non-patent literature 1, pointed out the anion exchange resin by using the OH type can play the effect that anti-bacteria is bred.And, about the reason of having that effect, having mentioned is that anion 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 non-patent literature 1 has the content of the sterilizing ability stronger than the anion exchange resin of OH type.About its reason, having mentioned is to be subject to because bacterium, by resin the time, contacts disorderly OH type and H type the cause that larger pH changes.
The technology that the antiseptics such as active carbon by carrying on a shoulder pole Ag-bearing mix to come the anti-bacteria breeding with ion exchange resin is disclosed in patent documentation 3.
Patent documentation 1: Unexamined Patent 8-17457 communique
Patent documentation 2: Unexamined Patent 11-204123 communique
Patent documentation 3: Unexamined Patent 10-314727 communique
Non-patent literature 1: left rattan profit husband 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 of supplying with to fuel cell.In other words, if the water that contains chloride ion is fed in fuel cell, 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 facilities for fuel cell that can effectively reduce the concentration of the chloride ion in the water of supplying with to fuel cell.
Simultaneously, the water treatment facilities for fuel cell that high, the cheap and miniaturization of a kind of thermal endurance also expect to occur.
In addition, in the water treatment facilities of the mixed bed resin that uses anion exchange resin and cation exchange resin, because the proportion of anion exchange resin and cation exchange resin is different, therefore this water treatment facilities is carried, install, running etc. and while causing vibration, heavy cation exchange resin can move to bottom, and the little anion exchange resin of proportion can move to top, cause two kinds of ion exchange resin to separate.If the mixed bed resin that will separate like this is for the water treatment facilities of the fuel cell that uses under the high temperature of being everlasting, low discharge state, main stripping trimethylamine from anion exchange resin sometimes, and from cation exchange resin main stripping polystyrolsulfon acid.For example, if by processed water downward direction circulation, the dissolved element that is derived from the cation exchange resin of bottom can not be captured, and if, by processed water upward direction circulation, the dissolved element that is derived from the anion exchange resin on top can not be captured.Thereby the TOC that causes processing in water increases.And, if sneaking into, process in water these dissolved elements, the TOC processed in water increases, cause reaching the conductance of desired water, or these dissolved elements or using these dissolved elements, as the ammonium ion that generates source, nitrate ion, nitrite ion, sulfate ion etc., power generation performance and life-span of fuel cell brought to bad impact.
In addition, the bacterial reproduction that a kind of long-term use that can suppress by fuel cell causes also expect to occur, guarantee the water treatment facilities of the long-term normal fuel cell used.
Summary of the invention
Given this, the object of the present invention is to provide a kind of water treatment facilities that can realize the fuel cell of following at least any one purpose: the concentration that reduces the chloride ion in the water of supplying with to fuel cell; Possesses thermal endurance, cheap and can miniaturization; Effectively reduce the TOC in the water of supplying with to fuel cell; The breeding of the bacterium that inhibition is generated by the long-term use of fuel cell is to realize long-term use.
For this reason, technical scheme of the present invention is as follows:
A kind of water treatment facilities of fuel cell, it makes spent ion exchange resin, described ion exchange resin contains anion exchange resin, in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is below 10%, described anion exchange resin comprises the trimethyl ammonium strong-base anion-exchange resin of base in return, and in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is less than or equal to by R cl=4 * C cl/ CO 2 0.53the value obtained of formula.Wherein, R clmiddle shared ratio (%), the C of chloride ion (eq/L-R) of total exchange capacity (eq/L-R) of anion exchange resin cltarget chloride ion concentration (ppb), the CO processed in water 2that the carbonic acid dissolved in processed water is converted into to CO 2cO 2concentration (ppm).
Preferably, the anion exchange resin of described initial condition is to be transformed to the anion exchange resin of calcareous type through circulation carbonate.
Preferably, the processed water by described anion exchange resin adopts lower direction circulation style to carry out.
Preferably, contain the condensed water produced by the electric power generation reaction of fuel cell in the processed water by described anion exchange resin, described processed water after by described anion exchange resin process, is reused in described fuel cell.
According to the present invention, the water treatment facilities that can provide the fuel cell that can effectively reduce the chloride ion in the water of supplying with to fuel cell to use.
The accompanying drawing explanation
Fig. 1 means the schematic diagram of an example of structure of water treatment facilities of the fuel cell of present embodiment 1～4.
Fig. 2 means the various CO in processed water 2r under concentration cland C clthe figure of relation.
Fig. 3 means the various CO in processed water 2r under concentration cland C clthe figure of relation.
Fig. 4 is the R under various hydrogen ionexponents (pH) agand C agthe figure of relation.
In figure, 10 water treatment facilities, 12 fuel cells, 14 processed water pipelines, 16 condensation water tanks, 18 pumps, 20 condensing water conduits, 22 process waterpipe, 24 fuel feed pipe roads, 26 air supply pipes, 28 heat exchangers.
Embodiment
Below, embodiments of the present invention are described.Present embodiment is only to implement an example of the present invention, and the present invention is not limited by present embodiment.
(execution mode 1)
The water treatment facilities 10 of the fuel cell shown in Fig. 1 possesses the cylindrical shell (cartridge) that is filled with ion exchange resin.Cylindrical shell can have one or more.The ion exchange resin of filling in cylindrical shell is the mixed bed resin of anion exchange resin or anion exchange resin and cation exchange resin.Wherein, the water treatment facilities 10 of fuel cell can be filled with outside the cylindrical shell of ion exchange resin, the more additional cylindrical shell that is filled with active carbon etc. that arranges.
The water treatment facilities 10 of the fuel cell of present embodiment is mainly with the foreign ion removed in the water of supplying with to fuel cell 12.The condensed water that the water of processing as the water treatment facilities 10 by fuel cell can be running water (municipal water supply), pure water, generated by the electric power generation reaction of fuel cell 12 etc.
The municipal water supplies such as running water are delivered to the water treatment facilities 10 of fuel cell through processed water pipeline 14.In addition, the condensed water of discharging from fuel cell 12 for example temporarily is stored in condensation water tank 16, and is supplied to the water treatment facilities 10 of fuel cell from condensing water conduit 20 by pump 18.Then, the foreign ion of being removed in water by the water treatment facilities 10 of fuel cell.
The foreign ion contained in water comprises, such as carbanion, bicarbonate ion, chloride ion, sulfate ion etc.Contain a lot of carbonic acid in the condensed water of fuel cell, and remove micro-anion (chloride ion, sulfate ion etc.) from the condensed water that contains a large amount of carbonic acid, it is more difficult utilizing common anion exchange resin.Especially because chloride ion is 1 valency anion, therefore compared with multivalent anions such as sulfate ions, poor by the adsorption efficiency of anion exchange resin absorption, thus be difficult to reduce the chloride ion in water.
Use in present embodiment in the total exchange capacity of anion exchange resin of initial condition that the shared ratio of chloride ion is below 10%, the preferred anion exchange resin below 1%.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion surpasses 10%, anion exchange resin is easy to be sidelong out chloride ion to processing water, rather than, by the foreign ions such as carbanion absorption contained in water, be difficult to effectively reduce the chloride ion of processing in water.
In addition, when anion exchange resin comprises the trimethyl ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion is preferably below the value by obtaining with following formula (1).Thus, when processing water contains a large amount of carbonic acid, also can reduce chloride ion to the ratio of emitting of processing the water side, can effectively reduce the chloride ion of processing in water.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbanion, the bicarbonate ion that in processed water, dissolve are scaled to CO 2after CO 2concentration (ppm)
In addition, at anion exchange resin, comprise the dimethyl ethanol ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is preferably below the value by obtaining with following formula (2).Thus, chloride ion can be reduced to the ratio of emitting of processing the water side, the chloride ion of processing in water can be effectively reduced.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbonic acid dissolved in processed water is scaled to CO 2after CO 2concentration (ppm)
Above formula (1) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 2 of relation calculate.Above formula (2) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 3 of relation calculate.Known from above formula, as to dissolve in the little or processed water of the target chloride ion concentration in processing water CO 2in the large situation of concentration, need to obtain very little by the shared ratio setting of chloride ion in the total exchange capacity of the described anion exchange resin of initial condition.
In addition, the anion exchange resin that the water treatment facilities of fuel cell uses be except reducing chloride ion, also needs to possess thermal endurance and can miniaturization etc.For example, in Unexamined Patent 11-204123 communique, the example that uses the anion exchange resin with a plurality of alkyl in order to improve thermal endurance is disclosed.In addition, for example in Unexamined Patent 8-17457 communique, disclose in order to make equipment miniaturization, made the optimized example of amount of the cation exchange resin of filling in the mixed bed resin post.And in the present embodiment, the preferred carbonate of circulation ammonium bicarbonate etc. and after being transformed to calcareous type in anion exchange resin, used as the anion exchange resin of initial condition.But, because the anion exchange resin of calcareous type can't be removed carbonic acid, when needs are removed carbonic acid, be preferably in after-stage and carry out decarbonate processing (utilize degassing film or utilize the decarburization acid tower that adopts the air contact).Relatively, under identical exchange capacity, its resin volume is relatively little for the anion exchange resin of the anion exchange resin of calcareous type and OH type etc.That is, the anion exchange resin of OH type is replaced into to calcareous type, the resin smaller volume.In addition, the anion exchange resin of calcareous type is higher than thermal endurance with the anion exchange Ion Phase of OH type etc.Therefore, for example, even the higher processed water (40～80 ℃) of the such temperature of the condensed water of object fuel cell is processed, the decomposition of the ion exchange resin that also can suppress to be caused by heat, suppress TOC to the stripping of processing in water.
In the calcareous type anion exchange resin of present embodiment, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion is below 10%, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of carbanion preferably, more than 70%, is more preferably more than 90%.In addition, in the situation that become calcareous type, the most handy bicarbonate ion (bicarbonate ion) displacement, rather than carbanion.This be because, under the condition of fuel cell, bicarbonate ion than carbanion in more stable state.
In the water treatment facilities 10 of the fuel cell of present embodiment, the processed water (such as running water, condensed water etc.) of supplying with to above-mentioned anion exchange resin preferably adopts direction from the top down to flow.Lower direction by processed water flows, can be by the anion exchange resin extruding get Geng Mi filled in cylindrical shell.Its result, processed water can be in resin Uniform Flow, improved handling property.
As mentioned above, by the water treatment facilities 10 of the fuel cell of present embodiment, processed and the processing water (pure water) that reduced the concentration of foreign ion, especially chloride ion is supplied to fuel cell 12 from processing waterpipe 22.Wherein, this fuel cell 12 is Solid Oxide Fuel Cell, and in this example, the water be supplied to is for being modified as carbon monoxide (CO) and hydrogen (H by gas etc. 2).
Even the such water that contains a large amount of carbonic acid of condensed water for discharging from Solid Oxide Fuel Cell, utilize the water treatment facilities 10 of the fuel cell of present embodiment also can effectively remove in this water a small amount of chloride ion existed.Therefore, the water treatment facilities 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 processed, and this processing water is supplied to Solid Oxide Fuel Cell is recycled, also can realize the running of fuel cell steady in a long-term.In addition, in the situation that recycle condensed water, can supply with running water or pure water in the start of run stage of fuel cell.And, in the situation that recycle condensed water, preferably at the gas discharging by contained in condensed water to after in atmosphere, utilize water treatment facilities 10 to be processed and be supplied to fuel cell.
In addition, SUS304 as one of common used material, when even other chloride ion of ppm level exists, also can, according to different conditions, cause stress corrosion cracking, this is the known fact, therefore, in order to make fuel cell, under condition steady in a long-term, turn round, the chloride ion of processing in water need to be reduced to below 100ppb, preferably be reduced to below 50ppb, more preferably be reduced to below 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 pipe road 24 and air supply pipeline 26 respectively, and the hydrogen or the carbon monoxide that by the modified-reaction by fuel, obtain generate electricity with reacting of 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 condensed water and running water carry out heat exchange and supply with warm water.
(execution mode 2)
In the water treatment facilities 10 of the fuel cell shown in Fig. 1, there is the cylindrical shell that has been filled ion exchange resin.It can be also a plurality of that cylindrical shell can be 1.The ion exchange resin be filled in cylindrical shell is anion exchange resin, or the mixed bed resin of anion exchange resin and cation exchange resin.In addition, the water treatment facilities 10 of fuel cell, on the basis of the cylindrical shell that is filled with ion exchange resin, can also add the cylindrical shell be filled with active carbon etc. is set.The water treatment facilities of fuel cell need to possess thermal endurance and can miniaturization.For example, in Unexamined Patent 11-204123 communique, the example that uses the anion exchange resin with a plurality of alkyl in order to improve thermal endurance is disclosed.In addition, for example in Unexamined Patent 8-17457 communique, disclose in order to make equipment miniaturization, made the optimized example of amount of the cation exchange resin of filling in the mixed bed resin post.
And in the present embodiment, the carbonate such as the ammonium bicarbonate that first circulates in anion exchange resin and, after being transformed to calcareous type, the anion exchange resin that is re-used as initial condition is used, thus thermal endurance improved, realize miniaturization.Relatively, under identical exchange capacity, its resin volume is relatively little for the anion exchange resin of the anion exchange resin of calcareous type and OH type etc.That is, the anion exchange resin of OH type is replaced into to calcareous type, the resin smaller volume.Thereby, but the miniaturization of implement device.In addition, to compare thermal endurance high for the anion exchange resin of calcareous type and the anion exchange resin of OH type etc.Therefore, for example, even resemble the processed water that the condensed water equitemperature of fuel cell is higher (40～80 ℃), the decomposition of the ion exchange resin that also can suppress to be caused by heat, suppress TOC to processing stripping in water.
In the calcareous type anion exchange resin of present embodiment, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of carbanion preferably, more than 70%, is more preferably more than 90%, and especially preferably 100%.The calcareous type here refers to calcareous type and heavy carbonic type.In the situation that become calcareous type, preferably with bicarbonate ion (bicarbonate ion) displacement, rather than carbanion.This be because, under the condition of fuel cell, bicarbonate ion than carbanion in more stable state.In addition, consider the performance of removing foreign ion, compare with weak-base anion-exchange resin, the anion exchange resin of calcareous type is strong-base anion-exchange resin more preferably.
In addition, due to the anion exchange resin with the calcareous type of present embodiment only, can't remove carbonic acid, therefore, when needs are removed carbonic acid, be preferably in after-stage and carry out decarbonate processing (the decarburization acid tower that utilizes degassing film or utilize the employing air to contact).
In the present embodiment, in the situation of the mixed bed resin that uses anion exchange resin and cation exchange resin, the average grain diameter of cation exchange resin is preferably more than 0.2mm, and is below 80% of average grain diameter of anion exchange resin.As mentioned above, the proportion of cation exchange resin and anion exchange resin is different, therefore (ordinary circumstance, cation exchange resin is more great than the ratio of anion exchange resin), if use the cation exchange resin of above-mentioned extraneous particle diameter, two kinds of ion exchange resin can separate due to the vibration caused in the processes such as the conveyance at water treatment facilities, installation, running, cause the stripping material that is derived from two kinds of ion exchange resin to be captured, can't fully remove the TOC in the water of supplying with to fuel cell.In addition, if the average grain diameter of cation exchange resin is less than 0.2mm, the pressure loss of cylindrical shell increases, cause processing cost to improve, if and surpass anion exchange resin average grain diameter 80%, the poor of final speed during water flowing becomes large, causes cation exchange resin easily to separate with anion exchange resin.
The mixed bed resin of cation exchange resin particle diameter that used the such control of present embodiment, just be achieved the separation of two kinds of ion exchange resin that inhibition causes by vibration, make removal stable foreign ion become possibility.
In addition, the particle diameter of anion exchange resin is not particularly limited, but the volume of the anion exchange resin in the mixed bed resin of present embodiment 1.5～5 times of volume of cation exchange resin preferably.In addition, if above-mentioned volume ratio is converted into to exchange capacity, the total exchange capacity of anion exchange resin is 0.85～3 times of total exchange capacity of cation exchange resin.Wherein, if the volume of anion exchange resin is less than 1.5 times of volume of cation exchange resin, the ratio of unnecessary cation exchange resin increases, sometimes can't fully remove the anion in water, if and the volume of anion exchange resin is greater than 5 times of volume of cation exchange resin, be derived from the TOC composition stripping of anion exchange resin, the TOC that sometimes causes processing in water increases.
The foreign ion contained in water such as carbanion, bicarbonate ion, chloride ion, sulfate ion etc.Contain a lot of carbonic acid in the condensed water of fuel cell, remove micro-anion (chloride ion, sulfate ion etc.) from the condensed water that contains a large amount of carbonic acid, it is more difficult utilizing common anion exchange resin.Especially when chloride ion be the anion of 1 valency, therefore with the multivalent anions such as sulfate ion, compare, poor by the adsorption efficiency of anion exchange resin absorption, be difficult to reduce the chloride ion in water.
Using the shared ratio of chloride ion in the total exchange capacity of anion exchange resin of initial condition in present embodiment is below 10%, preferably at the anion exchange resin below 1%.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion surpasses 10%, anion exchange resin is easy to be sidelong out chloride ion to processing water, rather than, by the foreign ions such as carbanion absorption contained in water, be difficult to effectively reduce the chloride ion of processing in water.
In addition, at anion exchange resin, comprise the trimethyl ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (1).Thus, when processing water contains a large amount of carbonic acid, also can reduce chloride ion to the ratio of emitting of processing the water side, can effectively reduce the chloride ion of processing in water.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbanion, the bicarbonate ion that in processed water, dissolve are scaled to CO 2the time CO 2concentration (ppm)
In addition, at anion exchange resin, comprise the dimethyl ethanol ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (2).Thus, chloride ion can be reduced to the ratio of emitting of processing the water side, the chloride ion of processing in water can be effectively reduced.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbonic acid dissolved in processed water is scaled to CO 2the time CO 2concentration (ppm)
Above formula (1) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 2 of relation calculate.Above formula (2) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 3 of relation calculate.Known from above formula, as to dissolve in the little or processed water of the target chloride ion concentration in processing water CO 2in the large situation of concentration, need to obtain very little by the shared ratio setting of chloride ion in the total exchange capacity of the described anion exchange resin of initial condition.
In the water treatment facilities 10 of the fuel cell of present embodiment, the circulation of the processed water (such as running water, condensed water etc.) of supplying with to above-mentioned anion exchange resin is preferably used lower direction to flow.Lower direction by processed water flows, can be by the anion exchange resin extruding get Geng Mi filled in cylindrical shell.Its result, processed water can be in resin Uniform Flow, improved handling property.
As mentioned above, by the water treatment facilities 10 of the fuel cell of present embodiment, processed and the processing water (pure water) that reduced foreign ion, especially chloride ion concentration is supplied to fuel cell 12 from processing waterpipe 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 to carbon monoxide (CO) and hydrogen (H 2).
Even the such water that contains a large amount of carbonic acid of condensed water of discharging from Solid Oxide Fuel Cell, utilize the water treatment facilities 10 of the fuel cell of present embodiment also can effectively remove in this water a small amount of chloride ion existed.Therefore, the water treatment facilities 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 processed, and this processing water is supplied to Solid Oxide Fuel Cell is recycled, also can realize the running of fuel cell steady in a long-term.Simultaneously, when recycling condensate, can supply with running water or pure water in the start of run stage of fuel cell.In addition, if recycle condensate, be preferably in the gas that will comprise in condensate discharged to after atmosphere, processed by water treatment facilities 10, then the feed fuels battery.
In addition, as the SUS304 of one of versatile material when other chloride ion of ppm level exists, according to different conditions, also can cause stress corrosion cracking, this is the known fact, therefore, for fuel cell is turned round under condition steady in a long-term, the chloride ion of processing in water need to be reduced to below 100ppb, preferably be reduced to below 50ppb, more preferably be reduced to below 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 pipe road 24 and air supply pipeline 26 respectively, and are reacted with oxygen and generated electricity by hydrogen or the carbon monoxide that the modified-reaction of fuel obtains.Such Solid Oxide Fuel Cell is generated electricity under 600～1000 ℃ of high temperature, therefore, preferably by heat exchanger 28, heat extraction and running water is carried out supplying with warm water after heat exchange.
(execution mode 3)
In the water treatment facilities 10 of the fuel cell shown in Fig. 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 be filled in cylindrical shell, although be mainly the mixed bed resin of anion exchange resin and cation exchange resin, but, if one side also arranges cylindrical shell at upper reaches, can be also other anion exchange resin, or single of cation exchange resin etc.In addition, the water treatment facilities 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 active carbon etc. that arranges.In the mixed bed resin of the cation exchange resin of present embodiment and anion exchange resin, the average grain diameter of cation exchange resin is preferably more than 0.2mm, and below 80% of average grain diameter of anion exchange resin preferably.As explained above, due to the proportion of cation exchange resin and anion exchange resin different (proportion of general cation exchange resin is greater than the proportion of anion exchange resin), if therefore use the cation exchange resin of the particle diameter outside above-mentioned scope, two kinds of ion exchange resin can be due to the vibration caused in the processes such as the conveyance at water treatment facilities, installation, running, heavy cation exchange resin moves to bottom, the anion exchange resin that proportion is little moves to top, and two kinds of ion exchange resin separate.If separated like this mixed bed resin is used under high temperature, low discharge, likely stripping from cation constituents such as the trimethylamines of anion exchange resin and from the anion components such as polystyrolsulfon acid of cation exchange resin.Its result, the TOC processed in water increases.In addition, if the average grain diameter of cation exchange resin is less than 0.2mm, the pressure loss of cylindrical shell increases, cause processing cost to improve, if and surpass anion exchange resin average grain diameter 80%, the poor of final speed during water flowing becomes large, causes cation exchange resin easily to separate with anion exchange resin.
Present embodiment has been used the mixed bed resin of controlling the particle diameter of cation exchange resin, the separation of two kinds of ion exchange resin that just suppressed to be caused by vibration, therefore dissolved element cation constituents such as () trimethylamines of having realized being derived from anion exchange resin is caught by cation exchange resin, and dissolved element anion components such as () polystyrolsulfon acids that is derived from cation exchange resin is caught by anion exchange resin.Its result, can reduce and take the TOC that above-mentioned dissolved element is principal component, realized the steady removal of foreign ion.
In addition, the particle diameter of anion exchange resin is not particularly limited, but the volume of the anion exchange resin in the mixed bed resin of present embodiment 1.5～5 times of volume of cation exchange resin preferably.In addition, if above-mentioned volume ratio is converted into to exchange capacity, the total exchange capacity of anion exchange resin is 0.85～3 times of total exchange capacity of cation exchange resin.If the volume of anion exchange resin is less than 1.5 times of volume of cation exchange resin, the ratio of unnecessary cation exchange resin increases, sometimes can't fully remove the anion in water, if and the volume of anion exchange resin is greater than 5 times of volume of cation exchange resin, be derived from the TOC composition stripping of anion exchange resin, the TOC that sometimes causes processing in water increases.
The foreign ion contained in water such as carbanion, bicarbonate ion, chloride ion, sulfate ion etc.Contain a lot of carbonic acid in the condensed water of fuel cell, remove micro-anion (chloride ion, sulfate ion etc.) from the condensed water that contains a large amount of carbonic acid, it is more difficult utilizing common anion exchange resin.Especially when chloride ion be the anion of 1 valency, therefore with the multivalent anions such as sulfate ion, compare, poor by the adsorption efficiency of anion exchange resin absorption, be difficult to reduce the chloride ion in water.
Using the shared ratio of chloride ion in the total exchange capacity of anion exchange resin of initial condition in present embodiment is below 10%, preferably at the anion exchange resin below 1%.Can effectively reduce the chloride ion in the water that contains a large amount of carbonic acid like this.If in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion surpasses 10%, anion exchange resin is easy to be sidelong out chloride ion to processing water, rather than, by the foreign ions such as carbanion absorption contained in water, be difficult to effectively reduce the chloride ion of processing in water.
In addition, at anion exchange resin, comprise the trimethyl ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion is preferably by below the value of obtaining with following formula (1).Thus, when processing water contains a large amount of carbonic acid, also can reduce chloride ion to the ratio of emitting of processing the water side, can effectively reduce the chloride ion of processing in water.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbanion, the bicarbonate ion that in processed water, dissolve are scaled to CO 2cO 2concentration (ppm)
In addition, at anion exchange resin, comprise the dimethyl ethanol ammonium in return during the strong-base anion-exchange resin of base, in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is preferably below the value by obtaining with following formula (2).Thus, chloride ion can be reduced to the ratio of emitting of processing the water side, the chloride ion of processing in water can be effectively reduced.
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 anion exchange resin (eq/L-R)
C cl: process the target chloride ion concentration (ppb) in water
CO 2: the carbonic acid dissolved in processed water is scaled to CO 2cO 2concentration (ppm)
Above formula (1) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 2 of relation calculate.Above formula (2) is according to the various CO that mean processed water 2r under concentration cland C clbetween Fig. 3 of relation calculate.From above formula, the CO dissolved in the little or processed water of the target chloride ion concentration in processing water 2in the large situation of concentration, need to obtain very little by the shared ratio setting of chloride ion in the total exchange capacity of the described anion exchange resin of initial condition.
In addition, the anion exchange resin that the water treatment facilities of fuel cell uses be except reducing chloride ion, also needs to possess thermal endurance and can miniaturization etc.For example, in Unexamined Patent 11-204123 communique, the example that uses the anion exchange resin with a plurality of alkyl in order to improve thermal endurance is disclosed.In addition, for example in Unexamined Patent 8-17457 communique, disclose in order to make equipment miniaturization, made the optimized example of amount of the cation exchange resin of filling in the mixed bed resin post.And in the present embodiment, the preferred circulation carbonate such as ammonium bicarbonate and after being transformed to calcareous type in anion exchange resin, used as the anion exchange resin of initial condition.But, because the anion exchange resin of calcareous type can't be removed carbonic acid, therefore, when needs are removed carbonic acid, be preferably in after-stage and carry out decarbonate processing (the decarburization acid tower that utilizes degassing film or utilize the employing air to contact etc.).The anion exchange resin of the anion exchange resin of calcareous type and OH type etc. compares, under identical exchange capacity, and its resin volume less.That is, the anion exchange resin of OH type is replaced into to calcareous type, the resin smaller volume.Therefore, miniaturization that can implement device.In addition, the anion exchange resin of calcareous type is higher than thermal endurance with the anion exchange Ion Phase of OH type etc.Therefore, even for example,, as the treatment temperature higher (, 40～80 ℃) of the condensate of the fuel cell of processed water etc., also can suppress the decomposition of heat to ion exchange resin, and be suppressed TOC liquate in processing water.
In the calcareous type anion exchange resin of present embodiment, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of chloride ion is below 10%, in the total exchange capacity of the anion exchange resin of initial condition, the shared ratio of carbanion is preferably more than 70%, being more preferably more than 90%, is most preferably 100%.Here said calcareous type, comprise calcareous type and heavy carbonic type.During calcareous type, not by carbonate if, and comparatively suitable by heavy carbonate (bicarbonate) displacement.This is due under the condition of fuel cell, the reason that bicarbonate ion is more in stable condition than carbanion.
In the water treatment facilities 10 of the fuel cell of present embodiment, to by above-mentioned anion exchange resin processed water (such as running water, condensed water etc.), preferably adopt lower direction to flow.Lower direction by processed water flows, and can make the anion exchange resin of filling in cylindrical shell be squeezed and become closeer.Its result, processed water can be in resin Uniform Flow, improved handling property.
As mentioned above, by the water treatment facilities 10 of the fuel cell of present embodiment, processed and the processing water (pure water) that reduced the concentration of foreign ion, especially chloride ion is supplied to fuel cell 12 from processing waterpipe 22.Wherein, this fuel cell 12 is Solid Oxide Fuel Cell, and in this example, the water conservancy be supplied to is for being modified as carbon monoxide (CO) and hydrogen (H by gas etc. 2).
Even the such water that contains a large amount of carbonic acid of condensed water of discharging from Solid Oxide Fuel Cell, utilize the water treatment facilities 10 of the fuel cell of present embodiment also can effectively remove in this water a small amount of chloride ion existed.Therefore, the water treatment facilities 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 processed, and this processing water is supplied to Solid Oxide Fuel Cell is recycled, also can realize the running of fuel cell steady in a long-term.In addition, in the situation that recycle condensed water, running water or pure water are as long as supply with in the start of run stage of fuel cell.And, in the situation that recycle condensed water, preferably in the gas by containing in condensed water is released to atmosphere after, utilize water treatment facilities 10 to be processed and be supplied to fuel cell.In addition, if recycle condensate, be preferably in after airborne release goes out the gas comprised in condensate, processed by water treatment facilities 10, then the feed fuels battery.
In addition, as the SUS304 of one of versatile material when other chloride ion of ppm level exists, difference according to condition, also can cause stress corrosion cracking, this is the known fact, therefore, for fuel cell is turned round under condition steady in a long-term, the chloride ion of processing in water need to be reduced to below 100ppb, preferably be reduced to below 50ppb, more preferably be reduced to below 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 pipe road 24 and air supply pipeline 26 respectively, and then are reacted with oxygen and generated electricity by hydrogen or the carbon monoxide that the modified-reaction of fuel obtains.At such soild oxide shape fuel cell, under 600～1000 ℃ of high temperature, generated electricity, so, after preferably the heat extraction of heat exchanger 28 and running water being carried out to heat exchange, supply with warm water.
(execution mode 4)
The water treatment facilities 10 of the fuel cell shown in Fig. 1, have 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 cylindrical shell, is anion exchange resin, cation exchange resin, or the mixed bed resin of anion exchange resin and cation exchange resin.The ion exchange resin used in present embodiment by circulation contain in silver, copper and zinc at least one solution and by the ion exchange of ion exchange resin, be at least one the ion exchange resin (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) in the middle of silver ion, copper ion and zinc ion.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, even sneak into bacterium in the water treatment facilities of fuel cell, also can suppress its breeding, realize using for a long time.
The time that circulation contains at least any one the solution (make contact) in silver, copper and zinc in ion exchange resin, temperature etc., as long as select to make the shared ratio of silver ion (copper ion, zinc ion) 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 to reach the optimum 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 type, the shared ratio of silver ion (copper ion, zinc ion) is preferably in 0.01%～90% scope, more preferably in 0.1%～70% scope.If the proportion of the silver-based ion-exchange resin (copper type Zinc type is also the same) of the total exchange capacity of silver ions is less than 0.01%, it can not sufficiently suppress the growth of bacteria is mixed to the fuel cell the water treatment apparatus, and if it is 90 % or more, sometimes silver ions (copper ions, zinc ions) to the dissolution of the treated water from the fuel cell exhaust treatment apparatus will increase.This is likely and shows acidity because sometimes contain a lot of carbonic acid in the condensed water of fuel cell, if and during the ion exchange resin that by the water of such acidity, contains a lot of hydrionic current logical silver-colored type, copper type or zinc type, and be attached to silver ion, copper ion or zinc ion on ion-exchange group and react and cause.And, if having the processing water of silver ion etc. to supply with to fuel cell stripping, may affect its long-term use.
In the situation that ion exchange resin is cation exchange resin, as at least any one solution contained in the middle of silver, copper and zinc, preferably select in the middle of nitrate solution (liquor argenti nitratis ophthalmicus, copper nitrate solution, zinc nitrate solution etc.), sulfate liquor (silver sulfate solution, copper-bath, solution of zinc sulfate etc.), hydrochloride solution (silver chlorate solution, copper chloride solution, liquor zinci chloridi etc.), complex salt solution (silver-colored complex salt solution, copper complex salt solution, zinc complex salt solution etc.) at least any one.
In addition, in the situation that ion exchange resin is storng-acid cation exchange resin, as at least any one solution contained in the middle of silver, copper and zinc, preferably select in the middle of nitrate solution, sulfate liquor, hydrochloride solution, complex salt solution at least any one.
Further, in the situation that ion exchange resin is storng-acid cation exchange resin, its degree of cross linking is preferably more than 12%.If the degree of cross linking of storng-acid cation exchange resin is less than 12%, the processing water that stripping of silver ion (copper ion, zinc ion) meeting is sometimes discharged to the water treatment facilities from fuel cell.
Simultaneously, as the solution that contains in silver, copper and zinc at least one, when ion exchange resin is anion exchange resin, complex salt solution preferably.In addition, consider the removal capacity of foreign ion, anion exchange resin is preferably by the trimethyl ammonium strong-base anion-exchange resin of base in return.
In present embodiment, use cation exchange resin at ion exchange resin, in the situation of anion exchange resin (especially use with trimethyl amido in return the strong basic ion exchange resin of base), in ion exchange resin, can circulate (make contact) contain silver, at least any one complex salt solution in copper and zinc, thereby be silver ion by the ion exchange of ion exchange resin, at least one in the middle of copper ion and zinc ion, then to silver ion, copper ion, zinc ion reduces processing, thereby silver is separated out in surface and inside at ion exchange resin, at least one in the middle of copper and zinc.Like this, by reduce processing after carrying out ion-exchange, even adopt the ion exchange resin that silver, copper, zinc are separated out, also can suppress to sneak into the breeding of the bacterium in the water treatment facilities of fuel cell.Its result, can be used the water treatment facilities for fuel cell for a long time.
Although processing, reduction can pass through H 2the reducibility gas such as gas contact with ion exchange resin and carry out, but use the reduction of reducibility gas to process and need to carry out for a long time at higher temperature.Therefore, preferably employing can be processed under comparatively gentle condition in the wet type reduction of short time processing.The wet type reduction is processed, and for example can in ion exchange resin, circulate by the solution that will be dissolved with reducing agent (contact) carried out.
Reducing agent can be used hydrazine, hydrogen peroxide, ascorbic acid, sodium ascorbate, formaldehyde, formic acid, sodium formate, sodium borohydride etc.
While separating out silver, copper, zinc and the time of contact solution that contains reducing agent, temperature, pH etc. can suitably set according to the kind of the ion of separating out, the kind of reducing agent etc.In addition, when the ion-exchange of only carrying out silver ion, copper ion, zinc ion and reduction, process can not obtain the amount of separating out of enough silver, copper, zinc the time, preferably repeatedly carry out ion-exchange and reduction is processed, until obtain the amount of separating out of expectation.
In the present embodiment, in the situation of the mixed bed resin that uses storng-acid cation exchange resin and strong-base anion-exchange resin, the average grain diameter of storng-acid cation exchange resin is below 80% of average grain diameter of strong-base anion-exchange resin preferably.This is because cation exchange resin is different with anion exchange resin proportion (usually, cation exchange resin compared with anion exchange resin than great), if use the storng-acid cation exchange resin of above-mentioned extraneous particle diameter, two kinds of ion exchange resin can separate due to the vibration caused in the processes such as the conveyance at water treatment facilities, installation, running, cause the stripping material that is derived from two kinds of ion exchange resin to be captured, can't fully remove the TOC in the water of supplying with to fuel cell.
In present embodiment, in the situation that use storng-acid cation exchange resin, the value (R that in the total exchange capacity of the storng-acid cation exchange resin of initial condition, the shared ratio of the complex ion of silver ion or argentiferous is preferably obtained by following formula (1) ag) below.In addition, formula (1) is according to being illustrated in the R under 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 agthe target silver concentration that the water treatment facilities outlet side of fuel cell is processed water, (C wherein agthe scope of=0.001～10ppb), pH is the hydrogen ionexponent (the wherein scope of pH=4～6) that the water treatment facilities entrance side of fuel cell is processed water, R agthe middle silver ion of total exchange capacity (eq/L-R) of storng-acid cation exchange resin or the shared ratio (%) of complex ion (eq/L-R) of argentiferous.)
If the ion exchange resin that water treatment facilities uses has surpassed the value (R obtained by formula (1) ag), the silver ion the processing water of discharging from the water treatment facilities of fuel cell more than easy stripping aimed concn.
As mentioned above, in the water treatment facilities of the fuel cell of present embodiment, even sneak into bacterium in the water treatment facilities of fuel cell, the bactericidal action of silver ion that also can be by being adsorbed by ion exchange resin, copper ion, zinc ion and the breeding of anti-bacteria guarantees the long-term use of water treatment facilities.That is, the condensate produced because of the electric power generation reaction of fuel cell can be processed by the fuel cell water treatment facilities of present embodiment, this is processed to water feed fuels battery, recycling, can make that fuel cell is long-term, runs steadily.In addition, if while recycling condensate, preferably, after atmosphere is emitted the gas comprised in condensate, by water treatment facilities 10, processed, resupplied fuel cell 12.
(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 the device shown in Fig. 1 to carry out water treatment to the condensed water of discharging from Solid Oxide Fuel Cell.The CO dissolved in condensed water 2concentration is approximately 250ppm, and chloride ion concentration is approximately 150ppb.The ion exchange resin of filling in cylindrical shell has been used with trimethyl amido in return the strong-base anion-exchange resin 30mL of base and the mixed bed resin of storng-acid cation exchange resin 10mL.The anion exchange resin of embodiment 1 is, at chlorine-based strong alkali anion exchange resin, (Rohmand Hass company manufactures, AMBERJET4002C1) 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 anion exchange resin (below, sometimes only be called R cl) at the anion exchange resin below 1%.The anion exchange resin of embodiment 2 is, the anion exchange resin of embodiment 1 and the anion exchange resin that is not transformed to the OH type are mixed, and makes R clbe 10% anion exchange resin.The cation exchange resin of embodiment 1,2 is AMBERJET1024H (manufacture of the Rohm and Hass company) cation exchange resin of Hydrogen.
In embodiment 1,2, the circulation of the processed water in ion exchange resin has all adopted downward circulation style.Under this condition, after turning round 24 hours, the processing water by anion exchange resin process is sampled and has been measured chloride ion concentration.Table 1 has gathered its result.
(comparative example 1)
R except the anion exchange resin that uses clbe beyond 20%, comparative example 1 is identical with embodiment 1.
Table 1
Water quality before 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 in the embodiment 2 of 10% anion exchange resin, chloride ion concentration is lowered to below 50ppb.In addition, use R clbe in the embodiment 1 of the anion exchange resin below 1%, chloride ion concentration is lowered to and is less than 10ppb, has shown the chloride ion removal capacity higher than embodiment 2.On the contrary, use R clbe that in the comparative example 1 of 20% anion exchange resin, chloride ion concentration is 110ppb, could not fully remove chloride ion.
At R cl=4 * C cl/ CO 2 0.53formula in the CO of substitution processed water 2chloride ion concentration 50ppb in concentration 250ppm, processing water, draw R clbe 10.7%.That is, if by CO 2the processed water of concentration 250ppm is processed, and the chloride ion concentration that make to process in water reaches below 50ppb, needs to make the shared ratio of chloride ion in the total exchange capacity of anion exchange resin below 10.7%.And below the value that the value of above-described embodiment 1,2 is calculated at above-mentioned formula.If can make to process chloride ion concentration in water below 50ppb, can make fuel cell turn round long-term and stably.
(embodiment 3,4)
Use the device shown in Fig. 1 to carry out water treatment to the condensed water of discharging from Solid Oxide Fuel Cell.The CO dissolved in condensed water 2concentration is approximately 250ppm, and chloride ion concentration is approximately 150ppb.The ion exchange resin of filling in cylindrical shell has been used with dimethyl ethanol amido in return the strong basicity Ag+-exchanged resin 30mL of base and the mixed bed resin of storng-acid cation exchange resin 10mL.The anion exchange resin of embodiment 3 is that in chlorine-based strong alkali anion exchange resin (Rohm and Hass company manufactures, AMBERLITE IRA410C1), the NaOH aqueous solution 1500mL of circulation 7%, be transformed to the OH type, makes R clat the ion exchange resin below 1%.The anion exchange resin of embodiment 4 is, the anion exchange resin of embodiment 3 and the anion exchange resin that is not transformed to the OH type mixed, and make R clbe 5% ion exchange resin.The cation exchange resin of embodiment 3,4 is the AMBERJET1024H (manufacture of Rohm and Hass company) of Hydrogen.
In embodiment 3,4, the circulation of the processed water in ion exchange resin has all adopted downward circulation style.Under such condition, after turning round 24 hours, the processing water by anion exchange resin process is sampled and has been measured chloride ion concentration.Table 2 has gathered its result.
(comparative example 2)
R except the anion exchange resin that uses clbe set as beyond 20%, comparative example 2 is identical with embodiment 3.
Table 2
Water quality before 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 in the embodiment 4 of 5% anion exchange resin, chloride ion concentration is lowered to below 50ppb.In addition, use R clbe that in the embodiment 3 of the anion exchange resin below 1%, chloride ion concentration is lowered to below 10ppb, shown the chloride ion removal capacity higher than embodiment 4.On the contrary, use R clbe that in the comparative example 2 of 20% anion exchange resin, chloride ion concentration is 210ppb, could not fully remove chloride ion.
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, processing water, draw R clbe 5.4%.That is, if by CO 2the processed water of concentration 250ppm is processed, and the chloride ion concentration that make to process in water reaches below 50ppb, needs to make the shared ratio of chloride ion in the total exchange capacity of anion exchange resin below 5.4%.And above-described embodiment 3,4 is lower than the value of being calculated by above formula.
(embodiment 5,6)
Use the device shown in Fig. 1 to carry out water treatment to the condensed water of discharging from Solid Oxide Fuel Cell.The ion exchange resin of filling in cylindrical shell has been used the trimethyl amido strong-base anion-exchange resin of base in return that is equivalent to 0.13eq with exchange capacity.The anion exchange resin of embodiment 5,6 is that (Rohm and Hass company manufactures, AMBERJET4002OH) middle circulation 4L ammonium bicarbonate (sodium acid carbonate NaHCO at OH type strong-base anion-exchange resin 3) (1 regulation), make the shared ratio (RCl) of chloride ion in the total exchange capacity of anion exchange resin below 1%, the ratio of carbanion (below, sometimes referred to as R-carbonic acid) more than 90%, 70% anion exchange resin.
Supply with the condensed water (approximately 60 ℃) that the Solid Oxide Fuel Cell from having the 1kW energy output generates in the water treatment facilities of embodiment 5,6, turned round 24 hours.The circulation of the processed water in ion exchange resin has all adopted downward circulation style.Table 3 has gathered the volume of the anion exchange resin of embodiment 5,6 and has processed the result that the TOC concentration in water is measured.
(comparative example 3)
Except the R-carbonic acid of the anion exchange resin that uses is 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, in embodiment 5,6, by making ion exchange resin become calcareous type, realized and the OH type Ion Exchange Resin Phase ratio of comparative example 3, in the situation that do not damage ion exchange capacity, reduced the resin volume.Especially R-carbonic acid is compared with comparative example 3 at the embodiment 5 more than 90%, and the resin volume has reduced by 20%.In addition, though in the calcareous type ion exchange resin of embodiment 5,6 condensed water of 60 ℃ of circulations and being processed, the TOC processed in water is also below 0.1ppm, therefore the decomposition of the known resin caused by heat is suppressed.In contrast, if in the OH of comparative example 3 type ion exchange resin the condensed water of 60 ℃ of circulations and being processed, in processing water, can detect the TOC of 0.5ppm, and this is likely what the decomposition of the resin caused by heat caused.
As mentioned above, by the anion exchange resin by initial condition, be transformed in advance calcareous type, can reduce the space that arranges of device, the decomposition of the resin that can suppress to be caused by heat, reduce the stripping of TOC simultaneously.
(embodiment 7)
Except the circulating direction of the processed water by ion exchange resin is changed into the circulation style that makes progress, embodiment 7 is identical with embodiment 1.Under this condition, the processing water by ion exchange resin treatment is sampled, and measured the concentration of chloride ion.Table 4 has gathered its result (in addition,, for ease of relatively, also having listed the result of embodiment 1 in table 4).
Table 4
Water quality before 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
At the circulating direction by processed water, be made as in the embodiment 7 of upwards circulation, resin is not extruded and becomes closely knit, has only observed a bit and has flowed.Therefore, in embodiment 7, short-circuit flow occurred, the chloride ion concentration of processing in water is compared and has been risen a bit than the embodiment 1 circulated downwards.Hence one can see that, as embodiment 1, adopts downward circulation style to carry out water treatment.
(embodiment 8)
Made the anion exchange resin of average grain diameter 0.7mm (real density 1080kg/m 3) and cation exchange resin (the real density 1140kg/m of average grain diameter 0.5mm 3) with 3: 1 (=anion exchange resin: the cylindrical shell (diameter 40mm * height 200mm) of the mixed bed resin that ratio cation exchange resin) is filled of volume ratio.It has been shaken 24 hours.Speed circulation pure water to the cylindrical shell after shaking with 10mL/min, then measured the TOC that processes water.Whether table 5 situation and the TOC concentration of the separation of ion exchange resin occurs after having meaned to shake.
(comparative example 4)
In comparative example 4, except using anion exchange resin (the real density 1080kg/m of average grain diameter 0.7mm 3) and cation exchange resin (the real density 1140kg/m of average grain diameter 0.7mm 3) outside, under the condition identical with embodiment 3, test.Table 5 has or not situation and the TOC concentration of the separation of ion exchange resin after having concluded and having shaken.
Table 5
Figure GSB00000964376000241
As known from Table 5, in embodiment 8, even shake 24 hours afterwards by observing, do not observe separating of anion exchange resin and cation exchange resin, and the TOC of the processing water after the circulation pure water is below 0.1ppm.By comparison, in comparative example 4, shake after 24 hours and can observe the bottom that about 80% cation exchange resin gathers cylindrical shell, can confirm to separate.And the TOC in the processing water under this state after the circulation pure water is 0.5ppm.
(embodiment 9)
Use the device shown in Fig. 1, the condensed water of discharging from Solid Oxide Fuel Cell has been carried out to water treatment.The CO dissolved in condensed water 2concentration is about 250ppm.Water treatment facilities has used the cylindrical shell (diameter 40mm * height 200mm) of the mixed bed resin of anion exchange resin 30mL and cation exchange resin 10mL mixing filling.The TOC concentration that has gathered the processing water after turning round 24 hours in table 6.
(comparative example 5,6)
Only fill the cylindrical shell of anion exchange resin 40mL in comparative example 5 except use, and comparative example 6 is tested except using the cylindrical shell (diameter 40mm * height 200mm) that mixes the mixed bed resin of filling anion exchange resin 36mL and cation exchange resin 4mL under the condition identical with embodiment 9.The TOC concentration that has gathered the processing water after turning round 24 hours in table 6.
Table 6
Water quality before 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 concentration ＜1ppb ＜1ppb 450ppb ＜1ppb
Polystyrolsulfon acid concentration ＜1ppb ＜1ppb ＜1ppb 38ppb
As known from Table 6, the rate control of anion exchange resin and cation exchange resin is at the embodiment 9 of appropriate value, with the comparative example 5 of only filling anion exchange resin, with the comparative example 6 of filling male ion-exchange resin only, compares, and TOC is lowlyer suppressed.Only fill in the comparative example 5 of anion exchange resin, from process water, detected the Trimethylamine that probably is derived from the functional group of anion exchange resin.In addition, only, in the comparative example 6 of filling male ion-exchange resin, from processing water, detected the polystyrolsulfon acid that probably is derived from the functional group of cation exchange resin.In addition, from described embodiment 8,9 result is known, the ratio of anion exchange resin and cation exchange resin is set in to proper range and mixes, even in the conveying of resin cylindrical shell, cause the vibration or after installation by the vibration etc., also can suppress separating of cation exchange resin and anion 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 the device shown in Fig. 1, carried out the water treatment of the condensate of being discharged by Solid Oxide Fuel Cell.The about 16ppm of CO2 concentration dissolved in condensate, the about 100ppb of chloride ion concentration, the pH of condensate is 5.The ion exchange resin that is filled into cylindrical shell used by the trimethyl amido in return the strong-base anion-exchange resin 30mL of base mix the ion exchange resin of filling with storng-acid cation exchange resin 10mL.The strong-base anion-exchange resin of embodiment 10,11, used the strong-base anion-exchange resin (Amberjet4002 (OH)) of OH type.Simultaneously, the storng-acid cation exchange resin of embodiment 10, use the cation exchange resin (Amberjet1024 (H)) of the degree of cross linking 12%, make the AgNO3 aqueous solution 1500mL of 0.15ppb by this resin, make it convert the Ag type to, the ratio of the silver ion occupied in the CEC of cation exchange resin adjusts to 9%.The storng-acid cation exchange resin of embodiment 11, its degree of cross linking cation exchange resin of 12% (Amberjet1024 (H)), this resin is done to the AgNO3 aqueous solution 1500mL circulation of 10g/L, convert the Ag type to, the ratio of the silver ion occupied in the CEC of cation exchange resin is adjusted to more than 90%.
By the processed water of ion exchange resin, all circulations downwards in embodiment 10,11.And, after turning round 10 days, the processing water that sampling is crossed by ion exchange resin treatment, measure concentration of silver ions, chloride ion concentration, investigated having or not of bacterium.Its result is summarized in table 7.
(comparative example 7)
Comparative example 7, do not convert to the storng-acid cation exchange resin of Ag type except having used, identical with examples of implementation 10.
Table 7
Figure GSB00000964376000261
According to table 7, can judge, used in 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, in the CEC by cation exchange resin, the shared ratio of silver ion is adjusted in the examples of implementation 11 more than 90%, process the silver ion that comprises about 1000ppb in water, but, in the CEC by cation exchange resin, the silver ion proportion is adjusted in 9% embodiment 10, is able to the silver ion of processing in water is suppressed at below 10ppb.In addition, in embodiment 10,11 and comparative example 7, the chloride ion concentration of processing in 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 agbecome 9.4%.That is, the processed water that to process pH be 5, want the concentration of silver ions of processing in water is made as below 10ppb, need to establish the ratio that in the CEC of anion exchange resin, silver ion occupies is below 9.4%.And it is below the value calculated by above-mentioned numerical expression that above-described embodiment 10 meets.Therefore, clear and definite embodiment 10 is more suitable for long-term utilization than embodiment 11.
(embodiment 12)
In embodiment 12, use the storng-acid cation exchange resin (Amberjet1024 (H)) of the degree of cross linking 8%, with the AgNO3 aqueous solution of 1500mL0.27ppb this resin that circulates, convert the Ag type to, adjust to 9% except the ratio silver ion accounts in the CEC of cation exchange resin, carried out the test same with embodiment 10.And, after turning round 10 days, the processing water that sampling is crossed by ion exchange resin treatment, measure concentration of silver ions, and investigated having or not of bacterium.Table 8 has been concluded its result.
[table 8]
Embodiment 10 Embodiment 12
Having or not of bacterium Nothing Nothing
Concentration of silver ions ＜10ppb 17ppb
Can judge from table 8, use the embodiment 12 of the storng-acid cation exchange resin of the degree of cross linking 8%, compare with the embodiment 10 of the storng-acid cation exchange resin that has used the degree of cross linking 12%, increase to the silver ion of processing liquate in water.Therefore, to processing liquate silver ion in water, preferably adopt the exchanger resin of the degree of cross linking at the highly acidic cation more than 12% in order to suppress.

Claims (4)

1. the water treatment facilities of a fuel cell, the water treatment facilities of this fuel cell makes spent ion exchange resin, it is characterized in that: described ion exchange resin comprises anion exchange resin, in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is below 10%, described anion exchange resin comprises the trimethyl ammonium strong-base anion-exchange resin of base in return, and in the total exchange capacity of the described anion exchange resin of initial condition, the shared ratio of chloride ion is for being less than or equal to the value (R obtained by following formula (1) cl):
R Cl＝4×C Cl/CO 2 0.53…(1)
Wherein, R clshared ratio (%), the C of chloride ion (eq/L-R) in the total exchange capacity (eq/L-R) of anion exchange resin cltarget chloride ion concentration (ppb), the CO processed in water 2the CO be dissolved in processed water 2concentration (ppm).
2. the water treatment facilities of fuel cell as claimed in claim 1 is characterized in that: the anion exchange resin of described initial condition is to be transformed to the anion exchange resin of calcareous type by circulation carbonate.
3. the water treatment facilities of fuel cell as claimed in claim 1 is characterized in that: the processed water of the described anion exchange resin of flowing through adopts lower direction circulation style to carry out.
4. the water treatment facilities of fuel cell as claimed in claim 1, it is characterized in that: contain the condensed water by the electric power generation reaction generation of fuel cell in the processed water by described anion exchange resin, described processed water after by described anion exchange resin process, is reused in described fuel cell.
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JP2004206899A (en) * 2002-12-24 2004-07-22 Mitsubishi Chemicals Corp Filter medium for fuel cell and filter for fuel cell as well as porous ion exchanger
CN1519968A (en) * 2003-01-30 2004-08-11 松下电器产业株式会社 High-molecular electrolyte fuel cell
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