CN102040260A - Water treatment device of fuel cell and water treatment method of fuel cell - Google Patents
Water treatment device of fuel cell and water treatment method of fuel cell Download PDFInfo
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- CN102040260A CN102040260A CN2010105098239A CN201010509823A CN102040260A CN 102040260 A CN102040260 A CN 102040260A CN 2010105098239 A CN2010105098239 A CN 2010105098239A CN 201010509823 A CN201010509823 A CN 201010509823A CN 102040260 A CN102040260 A CN 102040260A
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Abstract
The present invention provides a water treatment device of a fuel cell and a water treatment method of the fuel cell, wherein the carbonic acid gas which is contained in the treated water can be treated without ion exchange resin. In the water treatment device of fuel cell according to the invention, in which the ion exchange resin is used, a gas liquid separation part which comprises hydrophobic particles without ion exchange group is provided at an upstream side of the ion exchange resin.
Description
Technical field
The present invention relates to make the technology of 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.In addition, when cooled fuel cell or when the polymeric membrane to polymer electrolyte fuel cell carries out humidification etc., also need to make water.
As such water necessary in the running of fuel cell, for example, the water of condensation that can utilize the electric power generation reaction to fuel cell to produce is handled and the treating water (for example, with reference to patent documentations 1) such as (pure water) that obtains.
Contain foreign ions such as carbanion or bicarbonate ion (hereinafter referred to as carbanion etc. or only be called carbonic acid) in the water of condensation of from fuel cell, discharging.And, around temperature or the pressure etc. under the situation of changed condition or under the not good situation of gas-liquid separation, the carbonic acid in the water of condensation can become bubble (mainly being carbonic acid gas).
And, if in possessing the water treatment device of ion exchange resin, produce above-mentioned bubble, then can cause following problem.The first, if produce bubble at the ion exchange resin periphery, then bubble can hinder the contact between ion exchange resin and the water of condensation, and can not carry out ion exchange reaction fully.If this state, then water treatment device can't be brought into play the water treatmenting performance of regulation, might cause the deterioration of water quality treatment.The second, if in water treatment device, retain bubble, then can't can cause that flow reduces with outside the bubble extrusion system.In addition, though by supplying with the output raising of the pump of water of condensation to water treatment device, can be with outside the bubble extrusion system, but the general power consumption that makes of in fuel cell, wishing to do one's utmost to reduce the parts that in fuel cell, use in order to improve energy efficiency, therefore the output of supplying with the pump etc. of water of condensation is configured to very low, thus the output that can't improve pump.
Patent documentation 1: the spy opens flat 8-17457 communique
But fuel cell is that target is developed with long-term utilization, and the water treatment device that therefore same expectation is used for this fuel cell also can use for a long time.Yet, if in water treatment device, produce bubble, might produce the problems referred to above, can play bad influence to long-term utilization.
For this point, can consider generation at bubble, adopt increasing the loading level of ion exchange resin and remove methods such as the carbanion that becomes the reason that bubble produces, bicarbonate ion, but can cause the cost of water treatment to improve like this, is not basic countermeasure.
Summary of the invention
In view of the above problems, the object of the present invention is to provide a kind of ion exchange resin that can not rely on just can pack processing be contained in the water treatment device that is used for fuel cell of the carbonic acid gas in the processed water and the water treatment method of fuel cell.
The invention provides a kind of water treatment device that has used the fuel cell of ion exchange resin, its upstream side at described ion exchange resin is provided with the gas-liquid separation portion that comprises the hydrophobic particles with ion-exchange group.
In the water treatment device of described fuel cell, preferred described hydrophobic particles and the described ion exchange resin that does not have ion-exchange group is filled in the same packed tower.
In the water treatment device of described fuel cell, the preferred described hydrophobic particles that does not have an ion-exchange group is with in described ion exchange resin is filled in different packed towers respectively.
In the water treatment device of described fuel cell, the preferred described proportion that does not have the hydrophobic particles of ion-exchange group contains liquid light than carbonic acid gas.
In the water treatment device of described fuel cell, the preferred described true specific gravity that does not have the hydrophobic particles of ion-exchange group is below 1.04.
In the water treatment device of described fuel cell, the preferred described contact angle for water that does not have the hydrophobic particles of ion-exchange group is more than 68 °.
In the water treatment device of described fuel cell, the preferred described surface area/volume that does not have the hydrophobic particles of ion-exchange group is 0.5m
-1More than.
In the water treatment device of described fuel cell, the residence time of the processed water in the packed tower after the preferred described hydrophobic particles that does not have ion-exchange group is filled is 0.5 minute～100 minutes a scope.
In the water treatment device of described fuel cell, preferably have carrying out the refrigerative cooling body in the packed tower that has been filled the described hydrophobic particles that does not have an ion-exchange group.
The invention provides a kind of water treatment method that makes the fuel cell of spent ion exchange resin, its upstream side at described ion exchange resin is provided with the gas-liquid separation portion that comprises the hydrophobic particles with ion-exchange group, the water of condensation of discharging from fuel cell is after by described gas-liquid separation portion, by described ion exchange resin.
In addition, in the water treatment method of described fuel cell, preferred described hydrophobic particles and the described ion exchange resin that does not have ion-exchange group is filled in the same packed tower.
In addition, in the water treatment method of described fuel cell, the preferred described hydrophobic particles that does not have an ion-exchange group is with in described ion exchange resin is filled in different packed towers respectively.
In addition, in the water treatment method of described fuel cell, the preferred described proportion that does not have the hydrophobic particles of ion-exchange group contains liquid light than carbonic acid gas.
In the water treatment method of described fuel cell, the preferred described true specific gravity that does not have the hydrophobic particles of ion-exchange group is below 1.04.
In the water treatment method of described fuel cell, the preferred described contact angle for water that does not have the hydrophobic particles of ion-exchange group is more than 68 °.
In the water treatment method of described fuel cell, the preferred described surface area/volume that does not have the hydrophobic particles of ion-exchange group is 0.5m
-1More than.
In the water treatment method of described fuel cell, the residence time of the processed water in the packed tower after the preferred described hydrophobic particles that does not have ion-exchange group is filled is 0.5 minute～100 minutes a scope.
In the water treatment method of described fuel cell, preferably to cooling off in the packed tower that has been filled the described hydrophobic particles that does not have an ion-exchange group.
Adopt the present invention, can under not relying on the situation of ion exchange resin, handle the carbonic acid gas that contains in the processed water.
Description of drawings
Fig. 1 is the synoptic diagram of an example of structure of the fuel cell system of expression embodiments of the present invention.
Fig. 2 is the synoptic diagram of an example of structure of the fuel cell water treatment device of expression embodiments of the present invention.
Fig. 3 is expression other the synoptic diagram of an example of structure of filling tube (packed tower) of embodiment of the present invention.
Fig. 4 is expression other the synoptic diagram of an example of structure of filling tube (packed tower) of embodiment of the present invention.
Fig. 5 is expression other the synoptic diagram of an example of structure of filling tube (packed tower) of embodiment of the present invention.
Fig. 6 is expression other the synoptic diagram of an example of structure of filling tube (packed tower) of embodiment of the present invention.
Fig. 7 is expression other the synoptic diagram of an example of structure of filling tube (packed tower) of embodiment of the present invention.
Fig. 8 (A), (B) are the synoptic diagram of an example of the structure of expression filling tube.
Reference numeral
1 fuel cell system; 10 fuel cells; The water treatment device of 12 fuel cells;
14 heat exchangers; 16 condensation water tank 18a, 18b jet pump
20 handle water tank 22 air gives line 24 fuel feed lines altogether; 26a, 26b water supply line, 30 airborne release lines, 28 circular routes, 32 warm water supply lines, 34 ion-exchange portions
36 gas-liquid separation portions, 38 filling tubes, 40 gas relief lines, 42 connection sections
44 dividing plates, 46 cooling water lines
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.
Fig. 1 is the synoptic diagram of an example of structure of the fuel cell system of expression embodiments of the present invention.Fuel cell system 1 shown in Figure 1 possesses: fuel cell 10, the water treatment device 12 that makes the fuel cell of spent ion exchange resin, heat exchanger 14, condensation water tank (tank) 16, jet pump 18a, 18b, processing water tank 20, air supply line 22, fuel feed line 24, water supply line 26a, 26b, circular route 28, airborne release line 30 and warm water supply line 32.
On fuel cell 10, be connected with air supply line 22, fuel feed line 24 and water supply line 26a.Simultaneously, make water of condensation round-robin circular route 28 be connected to water supply line 26a from the condensed water discharge outlet (not shown) of fuel cell 10.Water supply line 26b is connected with the supplying opening of heat exchanger 14, and warm water supply line 32 is connected with the relief outlet of heat exchanger 14.
In circular route 28, be provided with in order: the water treatment device 12 of heat exchanger 14, condensation water tank 16, jet pump 18a, fuel cell, processing water tank 20, jet pump 18b from the upstream.Simultaneously, be connected with airborne release line 30 on heat exchanger 14 and the circular route 28 between the water tank 16 of being condensed.
Fig. 2 is the synoptic diagram of an example of structure of water treatment device of the fuel cell of expression embodiments of the present invention.As shown in Figure 2, the water treatment device 12 of fuel cell has the ion-exchange portion 34 that is made of ion exchange resin, the gas-liquid separation portion 36 that constitutes by the hydrophobic particles that does not have ion-exchange group, be filled the filling tube 38 (packed tower behind ion exchange resin etc., and gas relief line 40 cartridge).Constitute liquid separated part 36 and constitute ion-exchange portion 34 by the hydrophobic particles that does not have ion-exchange group and in filling tube 38, form by ion exchange resin.
In the water treatment device 12 of fuel cell shown in Figure 2, the hydrophobic particles and the ion exchange resin that do not have ion-exchange group are filled in the same filling tube 38, dispose gas-liquid separation portion 36 above the ion-exchange portion 34.In the present embodiment, between gas-liquid separation portion 36 and ion-exchange portion 34, dividing plate can be set, mixed in together with the hydrophobic particles and the ion exchange resin that prevent from not have ion-exchange group.Wherein, if this dividing plate is set, then need to be made into netted that processed water (water of condensation) can pass through.
The configuration that does not have the hydrophobic particles of ion-exchange group and ion exchange resin is not limited to the water treatment device 12 of fuel cell shown in Figure 2, as long as the gas-liquid separation portion 36 that is made of the hydrophobic particles that does not have ion-exchange group is configured in the upstream side of the ion-exchange portion 34 that is made of ion exchange resin.
In the present embodiment, circular route 28 and handle the connection section 42 of the supplying opening (not shown) of water tank 20 preferably is arranged on from the border of gas-liquid separation portion 36 and ion-exchange portion 34 to the scope (L shown in Fig. 2) of gas relief line 40 venting ports.If connection section 42 is set outside above-mentioned scope, the bubble that then is difficult to produce in gas-liquid separation portion is discharged to outside the system, cause sometimes that liquid level in the filling tube reduces or ion-exchange portion in the generation of bubble.
The action of fuel cell system 1 then, is described.Air (containing aerobic) and fuel gas (for example city gas) are supplied with to fuel cell 10 from air supply line 22 and fuel feed line 24 respectively.Simultaneously, tap water (and treating water of having been handled by the water treatment device 12 of fuel cell) is supplied with to fuel cell 10 from water supply line 26a.The water of supplying with to fuel cell 10 from water supply line 26a for example uses the cooling at fuel cell, under the situation of polymer electrolyte fuel cell, be used for the moistening etc. of polymeric membrane, under the situation of Solid Oxide Fuel Cell, be used for the city gas body is modified as carbon monoxide (CO) and hydrogen (H
2) operation etc.Like this, by to fuel cell 10 air supplies, fuel gas, water, and generate electricity, and from fuel cell 10 output powers.
The water of condensation that is produced by the generating of fuel cell 10 is by circular route 28, and the water tank 16 that temporarily is condensed is stored, and supplies with to the water treatment device 12 of fuel cell by jet pump 18a.In the water of condensation of water treatment device 12 supplies of fuel cell, for example contain carbonic acid (carbanion, bicarbonate ion), chloride ion, foreign ions such as sulfate ion.And the carbonic acid in the water of condensation can become bubble (mainly being carbonic acid gas) owing to the reason such as not good of the variation of situation around the temperature and pressure etc. and gas-liquid separation.
In the present embodiment, during by the gas-liquid separation portion 36 in the filling tube 38,, separate from water of condensation generation bubble at water of condensation.This is because the hydrophobic particles that does not have an ion-exchange group has the cause with the low hydrophobic function of the affinity of water.Promptly, do not have the hydrophobic particles of ion-exchange group and the affinity between the water and be lower than affinity with gas, when the hydrophobic particles that does not therefore have an ion-exchange group contacted with water of condensation, the oversaturated carbonic acid in the water of condensation was caught by the surface of hydrophobic particles, grows into big bubble.
After this, separated bubble is discharged to by gas relief line 40 outside the system of water treatment device 12 of fuel cell.On the other hand, removed the water of condensation of bubble by ion-exchange portion 34.After this, by constituting the ion exchange resin of ion-exchange portion 34, the foreign ion in the water of condensation is removed.In the present embodiment because the foreign ion in the water of condensation nearly all is removed, therefore, ion exchange resin and water of condensation contact the obstruction that is not subjected to bubble, thereby prevented the decline of the ion-exchange performance of ion exchange resin.
Then, the temporary transient processed water tank 20 of the water of condensation (treating water) that foreign ion has been removed is stored, and by jet pump 18b, is transported to water supply line 26a from circular route 28, supplies with to fuel cell 10.
In addition, fuel cell 10 is owing at high temperature generate electricity, therefore can make the tap water that is supplied to from the generating heat extraction of heat exchanger 14 and the water of condensation that is supplied to from circular route 28 or from water supply line 26b etc. carry out heat exchange, supply with warm water from warm water supply line 32.
Other examples of structure of the water treatment device 12 of fuel cell then, are described.
The synoptic diagram of an example of structure of the filling tube (packed tower) of other embodiment of the present invention is represented in Fig. 3～7th.In the filling tube 38 shown in Fig. 3,4, in filling tube 38, be provided with can make processed water pass through the open dividing plate 44 of mode of its underpart, upstream side disposes the gas-liquid separation portion 36 that is made of the hydrophobic particles that does not have ion-exchange group in the filling tube 38 that has been spaced, and the downstream side disposes the ion-exchange portion 34 that is made of ion exchange resin.But, mix for fear of hydrophobic particles that does not have ion-exchange group and ion exchange resin, and the proportion that makes the hydrophobic particles with ion-exchange group is than under the light situation of processed water (perhaps ion exchange resin), as shown in Figure 3, gas-liquid separation portion 36 preferred disposition are on the surface of ion-exchange portion 34.In addition, the proportion of the hydrophobic particles that does not have ion-exchange group than the heavy situation of processed water (perhaps ion exchange resin) under, as shown in Figure 4, if gas-liquid separation portion 36 is configured in the upstream side of ion-exchange portion 34, then also can on gas-liquid separation portion 36 surfaces, dispose ion-exchange portion 34.
Dispose a plurality of filling tubes 38 in the water treatment device 12 of fuel cell shown in Figure 5 side by side, and in the gas-liquid separation portion 36 that filling tube 38 configuration of upstream side is made of the hydrophobic particles that does not have ion-exchange group, the ion-exchange portion 34 that filling tube 38 configurations in the downstream side are made of ion exchange resin.In the water treatment device 12 of fuel cell shown in Figure 6, configured in series a plurality of filling tubes 38, and in the gas-liquid separation portion 36 that filling tube 38 configuration of upstream side is made of the hydrophobic particles that does not have ion-exchange group, the ion-exchange portion 34 that filling tube 38 configurations in the downstream side are made of ion exchange resin.
In above-mentioned any one example, water of condensation leads to the bottom from gas-liquid separation portion 36 tops that are made of the hydrophobic particles that does not have ion-exchange group, but is not limited to this.For example, as shown in Figure 7, in the structure of the filling tube 38 that has disposed side by side, water of condensation can be passed through to top from the bottom of the filling tube 38 (gas-liquid separation portion 36) of having filled the hydrophobic particles that does not have ion-exchange group.But, from the top of the gas-liquid separation portion 36 that constitutes by the hydrophobic particles that does not have ion-exchange group to the bottom by under the situation of water of condensation, the elimination performance of the bubble in the water of condensation is better.
In addition, can dispose the filling tube 38 shown in a plurality of Fig. 2～7 separately, also the filling tube 38 shown in Fig. 2～7 can be made up and disposes.Under the situation of the independent filling tube 38 shown in configuration a plurality of Fig. 2～7, preferably in the filling tube of original segment, fill at least and do not have the hydrophobic particles of ion-exchange group.
The ion exchange resin that uses in the present embodiment is the hybrid resin of anionite-exchange resin, Zeo-karb or anionite-exchange resin and Zeo-karb etc., can suitably select according to the kind of the foreign ion the water of condensation of discharging, concentration etc. from fuel cell 10.
The hydrophobic particles of using in the present embodiment that does not have ion-exchange group be with processed water in the foreign ion material that do not carry out ion-exchange, utilize the low such hydrophobic function of affinity with water, catch the micro-bubble in the water of condensation, make it to grow into bigger bubble, separate from water of condensation.As the hydrophobic particles that does not have ion-exchange group, can suitably use for example hydrophobic resin particle, derivative of fatty acid particle and inorganic oxide particle etc.As the hydrophobic resin particle, can enumerate for example polyethylene (PE), polypropylene (PP), the alkene of polyethylene terephthalate (PET) etc. is resin, polystyrene resin, the fluorine resin of tetrafluoroethylene etc., the polyvinyl chloride resin, polyester based resin, polyamide-based resin, the particle of polyethylene-based resin etc.As the derivative of fatty acid particle, can enumerate Zinic stearas, stearic amide etc.As inorganic oxide particle, can enumerate cerium oxide particles, Titanium particles, silica particle, aluminium oxide particles etc.
The true specific gravity of the hydrophobic particles of using in the present embodiment that does not have ion-exchange group is preferably light than water of condensation (containing carbonic acid gas).And the true specific gravity of hydrophobic particles that does not have ion-exchange group is preferably below 1.04, more preferably below 0.97.Simultaneously, the lower value of true specific gravity that does not have a hydrophobic particles of ion-exchange group is more than 0.9.By satisfying above-mentioned scope, can prevent the mixed in together of hydrophobic particles and ion exchange resin.On the other hand, if in filling tube shown in Figure 2 38, the border between gas-liquid separation portion 36 and ion-exchange portion 34 is provided for preventing the blended dividing plate of particle, then not necessarily needs to satisfy above-mentioned scope.In addition, for example such at filling tube 38 as shown in Figure 4, disposing on the gas-liquid separation portion 36 under the situation of ion-exchange portion 34, do not have the true specific gravity of hydrophobic particles of ion-exchange group when bigger than 1.04, more favourable for the mixing that prevents particle.
The contact angle of the hydrophobic particles of using in the present embodiment that does not have ion-exchange group (20 ℃/50%RH) be preferably more than 68 °, more preferably more than 73 °.If the contact angle of hydrophobic particles that does not have ion-exchange group is less than 68 °, then the affinity with water will uprise, and hydrophobic function can die down, and causes the bubble in the separating and condensing water from water of condensation fully.In addition, the higher limit of contact angle that does not have a hydrophobic particles of ion-exchange group is below 115 °.
The surface area/volume of the hydrophobic particles of using in the present embodiment that does not have ion-exchange group is preferably 0.5m
-1More than, 1m more preferably
-1More than.If the surface area/volume of hydrophobic particles that does not have ion-exchange group is less than 0.5m
-1, then the gas-liquid separation performance from the processed water separate bubbles might descend.In addition, the higher limit 90m preferably of surface area/volume that does not have the hydrophobic particles of ion-exchange group
-1Below.Do not surpass 90m because if do not have the surface area/volume of the hydrophobic particles of ion-exchange group
-1, then particle becomes vesicular (porous), so bubble rests in the gas-liquid separation portion 36 easily, causes bubble to be difficult to be discharged to outside the system of filling tube 38.
Using the shape of the hydrophobic particles that does not have ion-exchange group in the present embodiment, can be cubes, and sphere is cylindrical, hollow cylindrical, and plate shapes etc. are not particularly limited.
In the present embodiment, the residence time of the water of condensation in the filling tube 38 is preferably 0.5～100 minute scope.If the residence time of the water of condensation in the filling tube 38 is than 0.5 minute weak point, then the hydrophobic particles that can not do not had an ion-exchange group of the bubble in the water of condensation is fully removed sometimes.In addition, if the residence time of the water of condensation in the filling tube 38 is long than 100 minutes, water treatment efficiency variation then, cost of water treatment raising.
As mentioned above, in the water treatment device 12 of the fuel cell of present embodiment, owing to can remove bubble in the water of condensation with the hydrophobic particles that does not have ion-exchange group, therefore, after this not contacting of ion exchange resin and water of condensation can be hindered by bubble, and then can prevent the reduction of the ion-exchange performance of ion exchange resin.
In addition, for example, starting or stoping or extraneous gas temperature etc. of fuel cell can cause the temperature variation of water of condensation.And, if water temperature changes to high temperature from low temperature, contain then that solubleness also can descend in the water of gas of carbonic acid gas, and then cause bubble to be easy to generate.Produce in order to suppress this bubble, preferably the water temperature in the filling tube 38 is set at certain value, the temperature of the water of condensation in the special preferred filler tube 38 is lower than the temperature of the water of condensation in the circular route 28 of the inlet side of filling tube 38.As making the water of condensation in the filling tube 38 become cryogenic method, be not particularly limited, below enumerate an one example.
Fig. 8 (A) (B) is the synoptic diagram of an example of the structure of expression filling tube.In the filling tube 38 shown in Fig. 8 (A), the cooling water line 46 (cooling body) of flow of cooling water along the periphery of filling tube 38 than the length direction setting, in the filling tube 38 shown in Fig. 8 (B), the cooling water line 46 (cooling body) of flow of cooling water is arranged on the periphery of filling tube 38 with spirrillum.In addition, cooling water line 46 does not then have above-mentioned restriction as long as be provided with in the mode that can cool off filling tube 38.Mobile water coolant in cooling water line 46 is considered with viewpoint that can the simplification device structure, preferably uses the water coolant (tap water etc.) that uses in the heat exchanger 14 of Fig. 1.If make heat exchanger 14 and filling tube 38 shared water coolants like this, then preferably water supply line 26b is connected to the inlet of cooling water line 46, and, between the outlet of cooling water line 46 and heat exchanger 14, connect water supply line 26b, at first filling tube 38 is cooled off in cooling, secondly cooling heat exchanger 14.Thus, the temperature of the water coolant in the filling tube 38 can be lower than the temperature of the water coolant in the heat exchanger 14, and the temperature of water of condensation is low in heat exchanger 14 outlets in filling tube 38 internal ratios.
The cooling-water flow direction does not limit especially, but preferred shown in Fig. 8 (A), (B), flows from the filling tube bottom to top.If the bottom at filling tube produces bubble, this bubble is difficult to break away from from filling tube 38, but by water coolant is circulated to top from the bottom of filling tube, can cool off the bottom of filling tube better, therefore can be suppressed at the risk that the filling tube bottom produces bubble.
(embodiment)
Below, enumerate embodiment and comparative example, more specifically describe the present invention in detail, but the present invention is not limited to following examples.
(embodiment 1)
Use the device of Figure 1 and Figure 2, the water of condensation of discharging from Solid Oxide Fuel Cell has been carried out water treatment.The concentration of dissolved chloride ion is about 100ppb in the water of condensation.In addition, be dissolved with carbonic acid in the water of condensation, the pH of water of condensation is owing to the existence of carbonic acid becomes 5.As the ion exchange resin that is filled in the filling tube (internal diameter 40mm * height 120mm) that in water treatment device, uses, used to mix and filled strongly basic anion exchange resin 75mL that the trimethylammonium ammonium is in return basic and the ion exchange resin of storng-acid cation exchange resin 15mL.Strongly basic anion exchange resin has used Amberjet4002 (OH).In addition, storng-acid cation exchange resin has used Amberjet1024 (H).And,, filled the polypropylene of 20mL as the hydrophobic particles that does not have ion-exchange group on this resin top.Polyacrylic shape is the cubes of 1 limit for about 1mm, and the value of surface area/volume is 6m
-1In addition, this polyacrylic contact angle is 91 °, and true specific gravity is 0.90.
In embodiment 1, the flowing water of the processed water in the filling tube adopts and flows downward, and flow is 10mL/min, and flow velocity is 0.13mm/s.After this, turn round after 10 days, measured the chloride ion concentration in (range estimation is confirmed), liquid level poor (case of the water level in the filling tube-filling tube outlet connects height) and the treating water of having or not of bubble in the ion-exchange portion.Table 1 has been summed up its result.
(comparative example 1)
In the comparative example 1,, identical with embodiment 1 except in filling tube not the filled polypropylene.
Table 1
As known from Table 1, filled among the embodiment 1 of the hydrophobic particles that does not have ion-exchange group, can prevent the generation of the bubble in the ion-exchange portion.On the other hand, in the comparative example 1, the water level in the filling tube rises, and the liquid level difference is than big in embodiment 1.This may be because the bubble that produces in resinbed causes air pocket (air lock), the cause that causes the part of water flowing to be hindered.
(embodiment 2)
Among the embodiment 2, as the different hydrophobic particles that does not have ion-exchange group of contact angle, used polyvinyl chloride (68 ° of contact angles), polyethylene terephthalate (69 ° of contact angles), high specific gravity polyethylene (73 ° of contact angles), low-gravity polyethylene (81 ° of contact angles), polystyrene (84 ° of contact angles), polypropylene (91 ° of contact angles), tetrafluoroethylene: PFA (115 ° of contact angles) in addition, under the condition identical, tested with embodiment 1.Then, turn round after 10 days, the having or not of bubble in the ion-exchange portion confirmed in range estimation, and table 2 has been summed up its result.
Table 2
| Contact angle | Having or not of bubble | |
| Polyvinyl chloride | 68° | Minute quantity |
| Polyethylene terephthalate | 69° | Minute quantity |
| The high specific gravity polyethylene | 73° | Do not have |
| The low-gravity polyethylene | 81° | Do not have |
| Polystyrene | 84° | Do not have |
| Polypropylene | 91° | Do not have |
| PFA | 115° | Do not have |
As known from Table 2, can suppress on the bubble this point (comparing with comparative example), the contact angle of hydrophobic particles that does not have ion-exchange group is preferably more than 68 °, more preferably more than 73 °.In addition, contact angle also may suppress bubble more than 115 °, still, owing to cause material cost to increase, therefore, not too has practical value.
(embodiment 3)
Among the embodiment 3, as the different hydrophobic particles that does not have ion-exchange group of true specific gravity, used polypropylene (true specific gravity 0.9), low-gravity polyethylene (true specific gravity 0.92), high specific gravity polyethylene (true specific gravity 0.97), polystyrene (true specific gravity 1.04), polyethylene terephthalate (true specific gravity 1.38), polyvinyl chloride (true specific gravity 1.50), tetrafluoroethylene: PFA (true specific gravity 2.1) have been made water treatment device in addition under the condition identical with embodiment 1.And, the filling tube of this device has been vibrated 24 hours.After this, confirmed whether to exist the diffusion of hydrophobic particles in ion-exchange portion with ion-exchange group by range estimation in filling tube, table 3 has been summed up its result.
Table 3
| True specific gravity | Diffusion to ion-exchange portion | |
| Polypropylene | 0.90 | Do not have |
| The low-gravity polyethylene | 0.92 | Do not have |
| The high specific gravity polyethylene | 0.97 | Do not have |
| Polystyrene | 1.04 | Minute quantity |
| Polyethylene terephthalate | 1.38 | Have |
| Polyvinyl chloride | 1.50 | Have |
| PFA | 2.1 | Have |
As known from Table 3, on this point of the diffusion of hydrophobic particles in ion-exchange portion that suppresses not have ion-exchange group, the true specific gravity that does not preferably have the hydrophobic particles of ion-exchange group is below 1.04, more preferably below 0.97.If the hydrophobic particles that does not have ion-exchange group, then produces the short-circuit flow that is caused by the hydrophobic particles that does not have ion-exchange group that spreads to ion-exchange portion internal diffusion, can not give full play to the handling property of water treatment device here.
(embodiment 4)
Among the embodiment 4, except the value to the polyacrylic shape used as the hydrophobic particles that does not have ion-exchange group and surface area/volume changes, under the condition identical, test with embodiment 1.And, after running 10 days, confirmed the having or not of bubble in the ion-exchange portion by range estimation, table 4 has been summed up its result.
Table 4
As known from Table 4, do not have the value of surface area/volume of the hydrophobic particles of ion-exchange group, be preferably more than 0.5, more preferably more than 1 on the point of bubble suppressing.But, do not surpass 90 if do not have the value of surface area/volume of the hydrophobic particles of ion-exchange group, then promptly enable from the water of condensation separate bubbles, the amount that rests on the bubble in the filling tube also might be a lot.
(embodiment 5)
Among the embodiment 5, the residence time of the processed water in the filling tube is changed into 0.5,1,10,100 minutes respectively.Simultaneously, corresponding with each residence time, used the different filling tube of size.In addition, under the condition identical, test with embodiment 1.After this, after running 10 days, confirmed the having or not of bubble in the ion-exchange portion by range estimation, table 5 has been summed up its result.
Wherein, loading level is obtained according to following formula.
The residence time (branch) of the processed water in loading level (mL)=filling tube * by flow (mL/ branch)
Table 5
| Loading level (mL) | 5 | 10 | 100 | 1000 |
| By flow (mL/min) | 10 | 10 | 10 | 10 |
| Residence time (minute) | 0.5 | 1 | 10 | 100 |
| Having or not of bubble | Minute quantity | Do not have | Do not have | Do not have |
As known from Table 5, on inhibition bubble this point, the residence time of the processed water in the filling tube is preferably at 0.5 minute, more preferably more than 1 minute.If the residence time surpasses 100 minutes, then the quantitative change of the ion exchange resin of filling in the filling tube etc. is many, the space is set becomes big, thus impracticable.
(embodiment 6)
Among the embodiment 6, use the water treatment device identical with embodiment 1, after diameter, the flow velocity of influx (connection section of circular route and filling tube) of position, filling tube of connection section that makes circular route and handle the supplying opening (not shown) of water tank changes, carried out the running of water treatment device.
Its result, under the situation of the scope (L that Fig. 2 represents) till circular route and the connection section of handling the supplying opening (not shown) of water tank not being arranged on from the border of gas-liquid separation portion and ion-exchange portion to the venting port of gas relief line, perhaps under the situation of the diameter of the influx of filling tube less than 6mm, be difficult to discharge the bubble that the gas-liquid separation portion in filling tube produces, cause the generation of the bubble in interior liquid level reduction of filling tube or the ion-exchange portion.
And flow velocity is super to be 1mm/s, the tendency that then has the bubble generation in filling tube to increase.In addition, under flow velocity is situation below the 0.1mm/s, though also the loading level with ion exchange resin is relevant, when using with flow velocity during identical loading level above 1mm/s, resin packing height step-down, water quality treatment variation.
Hence one can see that, and the flow velocity that the diameter of the scope (L that Fig. 2 represents) till preferably circular route and the connection section of handling the supplying opening (not shown) of water tank being arranged on from the border of gas-liquid separation portion and ion-exchange portion to the venting port of gas relief line, the influx of filling tube is arranged on the scope of the external diameter of 6mm～filling tube, supply to the processed water of filling tube is made as the scope of 0.01～1mm/s.
(embodiment 7)
Adopt the water treatment device identical with embodiment 1 among the embodiment 7, externally gas is 30 ℃, during 20 ℃ of following running water treatment device of water temperature, filling tube is carried out water cooling, turn round after 10 days, confirmed the having or not of bubble in the ion-exchange portion by range estimation, its result is illustrated in the table 6.
(comparative example 2)
In the comparative example 2, except not carrying out the water cooling of filling tube, test under the condition identical with embodiment 7, turn round after 10 days, confirmed the having or not of bubble in the ion-exchange portion by range estimation, its result is illustrated in the table 6.
Table 6
As known from Table 6, in the comparative example 2, be subjected to extraneous gas temperature and the influence that contacts with exchange resin tower, the condensate temperature of filling tube outlet is higher than the filling tube inlet, has caused the generation of bubble.On the other hand, in embodiment 7, because filling tube is carried out water cooling, therefore the temperature of the water of condensation of the inlet of filling tube, outlet can be remained on certain low temperature, not find the generation of bubble.In addition, also can make liquid level poor (case of the water level in the filling tube-filling tube outlet connects height) very little.By such combination cooling body, obtained good effect.
Claims (18)
1. the water treatment device of a fuel cell, it makes spent ion exchange resin, it is characterized in that,
Upstream side at described ion exchange resin is provided with the gas-liquid separation portion that comprises the hydrophobic particles with ion-exchange group.
2. the water treatment device of fuel cell as claimed in claim 1 is characterized in that,
Described hydrophobic particles and the described ion exchange resin that does not have ion-exchange group is filled in the same packed tower.
3. the water treatment device of fuel cell as claimed in claim 1 is characterized in that,
The described hydrophobic particles that does not have an ion-exchange group is with in described ion exchange resin is filled in different packed towers respectively.
4. the water treatment device of fuel cell as claimed in claim 2 is characterized in that,
It is also light that the described proportion that does not have the hydrophobic particles of ion-exchange group contains liquid than carbonic acid gas.
5. the water treatment device of fuel cell as claimed in claim 4 is characterized in that,
The described true specific gravity that does not have the hydrophobic particles of ion-exchange group is below 1.04.
6. as the water treatment device of any described fuel cell in the claim 1～5, it is characterized in that,
The described contact angle for water that does not have the hydrophobic particles of ion-exchange group is more than 68 °.
7. as the water treatment device of any described fuel cell in the claim 1～6, it is characterized in that,
The described surface area/volume that does not have the hydrophobic particles of ion-exchange group is 0.5m
-1More than.
8. as the water treatment device of any described fuel cell in the claim 2～7, it is characterized in that,
The residence time of having filled the processed water in the packed tower of the described hydrophobic particles that does not have an ion-exchange group is 0.5 minute～100 minutes a scope.
9. as the water treatment device of any described fuel cell in the claim 2～8, it is characterized in that,
Have carrying out the refrigerative cooling body in the packed tower of having filled the described hydrophobic particles that does not have an ion-exchange group.
10. the water treatment method of a fuel cell is to use the water treatment method of the fuel cell of ion exchange resin, it is characterized in that,
Comprise the gas-liquid separation portion of the hydrophobic particles with ion-exchange group in the upstream side setting of described ion exchange resin, the water of condensation of discharging from fuel cell is after by described gas-liquid separation portion, by described ion exchange resin.
11. the water treatment method of fuel cell as claimed in claim 10 is characterized in that,
Described hydrophobic particles and the described ion exchange resin that does not have ion-exchange group is filled in the same packed tower.
12. the water treatment method of fuel cell as claimed in claim 10 is characterized in that,
The described hydrophobic particles that does not have an ion-exchange group is with in described ion exchange resin is filled in different packed towers respectively.
13. the water treatment method of fuel cell as claimed in claim 11 is characterized in that,
It is also light that the described proportion that does not have the hydrophobic particles of ion-exchange group contains liquid than carbonic acid gas.
14. the water treatment method of fuel cell as claimed in claim 13 is characterized in that,
The described true specific gravity that does not have the hydrophobic particles of ion-exchange group is below 1.04.
15. the water treatment method as any described fuel cell in the claim 10～14 is characterized in that,
The described contact angle for water that does not have the hydrophobic particles of ion-exchange group is more than 68 °.
16. the water treatment method as any described fuel cell in the claim 10～15 is characterized in that,
The described surface area/volume that does not have the hydrophobic particles of ion-exchange group is 0.5m
-1More than.
17. the water treatment method as any described fuel cell in the claim 10～15 is characterized in that,
The residence time that has been filled the processed water in the packed tower of the described hydrophobic particles that does not have an ion-exchange group is 0.5 minute～100 minutes a scope.
18. the water treatment method as any described fuel cell in the claim 11～17 is characterized in that,
To cooling off in the packed tower that has been filled the described hydrophobic particles that does not have an ion-exchange group.
Applications Claiming Priority (4)
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| JP2009239103 | 2009-10-16 | ||
| JP2009-239103 | 2009-10-16 | ||
| JP2010-180753 | 2010-08-12 | ||
| JP2010180753A JP5588266B2 (en) | 2009-10-16 | 2010-08-12 | Fuel cell water treatment device and fuel cell water treatment method |
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| CN102040260A true CN102040260A (en) | 2011-05-04 |
| CN102040260B CN102040260B (en) | 2014-02-19 |
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Cited By (1)
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|---|---|---|---|---|
| CN112400247A (en) * | 2019-03-05 | 2021-02-23 | 株式会社东芝 | Fuel cell system and cooling method thereof |
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