JP2003288935A - Fuel cell power generating system receiving supply of hydrogen gas from hypochlorite producing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell power generating system receiving supply of purified hydrogen gas from a hypochlorite producing device. <P>SOLUTION: This fuel cell power generating system is equipped with the hypochlorite producing device 102 generating byproduct gas containing hydrogen gas as the main component inside an electrolytic bath 106 by an electrolytic process, a gas purifier 86 removing impurities from the byproduct gas sent from the hypochlorite producing device 102 and passing the hydrogen gas, and a fuel cell 104 generating electric power by electrochemical reaction of oxidizing agent gas 25 and the hydrogen gas sent from the gas purifier 86. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell power generation system which is supplied with hydrogen gas from a hypochlorite generator. In particular, hypochlorite (NaClO)
After refining the gas whose main component is hydrogen, which is a by-product in the process of producing hydrogen, it is supplied to the fuel cell, and the electric power generated from the fuel cell is generated by the electrochemical reaction of the hydrogen and oxygen in the atmosphere. The present invention relates to a fuel cell power generation system that supplies all or part of the electric power required by a hypochlorite generator.

[0002]

2. Description of the Related Art A conventional fuel cell power generation system, which is supplied with hydrogen gas from a hypochlorite generator, has, for example, as shown in FIG. It is composed of an alkaline solution storage tank 2, an electrolysis power source 3, and a hypochlorite-containing solution storage tank 4.

A solution prepared by preparing an alkali chloride salt 8 and raw water 7 is supplied from an alkali chloride solution storage tank 2 to an electrolytic cell 1 via a liquid transport pump 5, and is electrolyzed by direct current power of an electrolysis power source 3 to generate hypochlorous acid. A salt-containing solution is generated and sent to the hypochlorite-containing solution storage tank 4.

In the hypochlorite-containing solution storage tank 4, the solution is circulated and stored by the liquid circulation pump 6 and the hypochlorite-containing solution circulation system 9, and is sent from the hypochlorite-containing solution liquid supply system 10 to the load side. To be On the other hand, the hydrogen gas 22 that has been solid-liquid separated in the electrolytic tank 1 and the hypochlorite-containing solution storage tank 4 is sent to the fuel cell power generation system via the demister 24 that separates the particulate entrained liquid.

The fuel cell power generation system comprises a polymer electrolyte fuel cell 21 and an air blower 23. Hydrogen gas 22 is provided on the fuel chamber side and oxidant gas 25 is provided on the oxidant chamber side via an air blower 23. The air is supplied as described above to output the recovered power 26 of the DC power, and at the same time, the high-level exhaust heat 27 of the fuel cell is used as the heat source of the sludge treatment device.

Further, the hydrogen gas 22 solid-liquid separated in the electrolytic cell 1 and the hypochlorite-containing solution storage tank 4 is sent to the fuel cell power generation system via a demister 24 for separating a particulate entrained liquid. It was

As shown in FIG. 13, a conventional alkaline chloride aqueous solution electrolyzer comprises an electrolytic bath 30, an alkaline chloride solution storage bath 40, and a hypochlorite storage bath 54. Saturated salt water is delivered from the alkali chloride solution storage tank 40 having a salt solution dissolving tank and a saturated salt water tank to the electrolytic cell 30 via a salt water pump 44 and a line 66. Water supply to the electrolyzer 30 includes a water supply path 32 for supplying raw water, a water supply device 34 for reforming raw water into soft water, a water supply tank 36 for storing soft water, a water supply pump 38,
Soft water is supplied to the electrolytic cell 30 through the line 65.

The hypochlorite solution delivered from the electrolytic cell 30 is temporarily stored in the hypochlorite receiving tank 54 via lines 68 and 69, and the hypochlorite solution circulation pump 52,
A circulation line for returning to the electrolytic cell 30 via the cooler 50, a pump 56, a line 71 for liquid delivery to the hypochlorite storage tank 58, and a hypochlorite solution supply line for hypochlorite according to demand. The hypochlorite solution 62 is supplied to the outside via the salt solution injection pump 60.

The electrolytic cell 30 produces a by-product gas containing hydrogen gas as a main component when producing a hypochlorite solution by electrolysis. This by-produced gas is passed through the water-sealing safety device 46, diluted by the gas dilution fan 48, and then piped 53.
It was exhausted through and released into the atmosphere.

FIG. 14 is a block diagram of an electrolytic cell of a conventional diaphragm electrolysis method. The electrolytic cell 30 has the anode 7 with the diaphragm 78 interposed therebetween.
4 and a pair of electrodes of the cathode 76 are arranged, a sodium chloride (NaCl) solution 80 is supplied to the anode 74 side, a water (H ₂ O) solution 82 is supplied to the cathode 76 side, and sodium chloride and water are mixed. High concentration of hypochlorites (NaC
10) is produced. In this process, the by-product gas 84 containing hydrogen (H ₂ ) as a main component was generated.

[0011]

[Patent Document 1] Republished Patent WO00 / 59825 (first
(Page 4, Page 15, Figure 10)

[0012]

However, as described above, the conventional hypochlorite aqueous solution production equipment and water treatment equipment pass the by-product gas generated during the hypochlorite production process to the demister. The by-product gas generated from the hypochlorite generator also contains components harmful to the fuel cell, such as chlorine (Cl ₂ ) or sodium chloride (NaCl). There is.

Further, it is necessary to maintain the oxygen (0 ₂ ) concentration and humidity suitable for the electrochemical reaction of the fuel cell. Furthermore, it is expected that a highly efficient combination power generation system of a hypochlorite generator and a fuel cell, which recovers hot exhaust heat from the cooling system of the fuel cell and utilizes it effectively.

In view of the above situation, it is an object of the present invention to provide a fuel cell power generation system which is supplied with hydrogen gas from a combined hypochlorite generator.
Further, it is intended to reuse a large number of products containing energy and substances generated from the fuel cell in the hypochlorite generation device.

Further, according to the present invention, the cooling exhaust heat of the hypochlorite generator is used to supply hydrogen gas from the hypochlorite generator in combination with an operation method using natural energy or night power. It is intended to provide a fuel cell power generation system for receiving the same.

[0016]

In order to achieve the above object, a fuel cell power generation system which receives hydrogen gas from a hypochlorite generator according to the present invention comprises:
For example, as shown in FIG. 1 or FIG. 10, a hypochlorite generation device 102 that generates a by-product gas containing hydrogen gas as a main component in the electrolytic cell 106 by an electrolysis process, and a hypochlorite generation device. Electric power is generated by an electrochemical reaction between the gas scrubber 86 that removes impurities from the by-product gas sent from the apparatus 102 and allows hydrogen gas to pass through, the oxidant gas 25, and the hydrogen gas sent from the gas scrubber 86. Fuel cell 104
And

Here, the gas scrubber has a water seal part at the bottom as a wet system in addition to the dry type gas scrubber 86a, and the circulating liquid and the by-product gas contact with water-soluble chlorine by gas-liquid contact. A gas scrubber 86 that removes chloride containing sodium chloride and volatile substances other than hydrogen generated from the electrolytic cell 106 can be used. Further, the oxidant gas 25 can use oxygen or air. Further, the fuel cell 104
A polymer electrolyte fuel cell or a phosphoric acid fuel cell can be used. The circulating liquid may be water of the cathode electrolyte, basic liquid (NaOH) of the anode electrolyte, or saline depending on the removal concentration.

With this structure, hydrogen gas from which impurities (chlorine, sodium chloride, etc.) have been removed is used as the fuel cell 10.
4, the fuel cell is not deteriorated, the power generation efficiency is improved, and the life is extended.

In order to achieve the above object, a fuel cell power generation system which is supplied with hydrogen gas from a hypochlorite generator according to claim 1 according to the invention of claim 2 is
For example, as shown in FIG. 1, an oxygen concentration adjuster 114 arranged between the gas scrubber 86 and the fuel cell 104 and adjusting the oxygen concentration of the by-product gas is further included.

Here, the oxygen concentration adjuster 114 may be a catalytic reactor for reacting oxygen and hydrogen in the by-product gas with a catalyst to convert oxygen into water and remove oxygen. Further, an adsorption device filled with an oxygen adsorbent such as zeolite morikiller sieves, activated carbon, or a metal complex can be used.

With this configuration, hydrogen gas from which oxygen has been removed can be supplied to the fuel cell 104, and hydrogen suitable for the fuel cell 104 and the oxidant gas 25 can be generated by an electrochemical reaction. Thus, the power generation efficiency can be improved and the life can be extended without deteriorating the fuel cell 104.

In order to achieve the above object, a fuel cell power generation system which receives hydrogen gas from the hypochlorite generator according to claim 1 or 2 according to the invention of claim 3 is, for example, as shown in FIG. As shown in, the DC voltage output from the output terminal 105 of the fuel cell 104 is used as the power source of the hypochlorite generation device 102.

According to this structure, the DC voltage is taken out from the output terminal 105 of the fuel cell 104 while the AC power having a fixed frequency is supplied to the system power supply 206.
The power conversion efficiency can be improved as compared with the DC voltage conversion in which the DC converter 202 and the grid interconnection inverter 204 are used for rectification.

In order to achieve the above object, a fuel cell power generation system which receives hydrogen gas from the hypochlorite generator according to claim 1 or 2 according to the invention of claim 4 is, for example, as shown in FIG. As shown in FIG. 5, the cathode electrolytic solution in the electrolytic bath 106 is sent to the gas cleaning device 86 and used as a gas cleaning solution.

With this structure, the cathode electrolytic solution in the electrolytic cell 106 can be utilized and can be circulated and used in the system.

In order to achieve the above object, a fuel cell power generation system receiving hydrogen gas from a hypochlorite generator according to claim 2 according to the invention of claim 5 is
For example, as shown in FIG. 1, it further has humidity adjusters 120 and 122 arranged between the oxygen concentration adjuster 114 and the fuel cell 104 and adjusting the humidity of hydrogen gas.

Here, the humidity adjusters 120 and 122 are made of a hygroscopic material, for example, a material that adsorbs and desorbs moisture such as silica gel.

With this structure, hydrogen gas from which water has been removed can be supplied to the fuel cell 104, and hydrogen having an appropriate humidity for the fuel cell 104 and the oxidant gas 25 can be generated by an electrochemical reaction. Fuel cell 104
The power generation efficiency can be improved and the life can be extended without deteriorating.

In order to achieve the above object, a fuel cell power generation system receiving hydrogen gas from a hypochlorite generator according to claim 5 according to the invention of claim 6 is
For example, as shown in FIG. 3 and FIG. 5, the humidity adjuster has first and second humidity adjusters, and the first humidity adjuster 120
In the state in which the second humidity adjuster 122 is operated by suspending the above, the regeneration heat source for recovering the function of the first humidity adjuster 120 is supplied from the exhaust heat of the fuel cell 104.

Here, as shown in FIG. 3, the means for activating the second humidity adjuster 122 while suspending the first humidity adjuster 120 is a valve for supplying the heated regenerated gas 154 supplied from the regenerated gas heater 144. 148, via line 155 to the first humidity controller 120. On the other hand, the second humidity adjuster 122 is supplied with purified hydrogen gas via the valve 118, and can perform normal humidity adjustment. Further, the exhaust heat of the fuel cell 104 is generated by the output line 18 of the fuel cell.
6 (see FIG. 5), which is hot exhaust heat supplied to the heat exchanger 180 (see FIG. 5) via the input line 152 of the regeneration gas heater, and the fuel via the output line 153 of the regeneration gas heater. Collect in batteries.

According to this structure, while the fuel power generation system is being operated by the second humidity adjuster 122, the regenerated gas that has undergone heat exchange from the heat exhaust heat of the fuel cell 104 is continuously supplied to the first humidity adjuster 120. Deliver and regenerate the humidity conditioner,
Can be reused.

In order to achieve the above object, a fuel cell power generation system receiving hydrogen gas from a hypochlorite generator according to claim 5 according to the invention of claim 7 is
For example, as shown in FIG. 3 and FIG. 4, the humidity adjuster has first and second humidity adjusters, and the first humidity adjuster 120
In a state in which the second humidity adjuster 122 is operated by suspending the above, the regeneration heat source for recovering the function of the first humidity adjuster 120 is supplied from the cooling exhaust heat of the electrolytic cell 30.

Here, as shown in FIG. 3, the means for suspending the first humidity adjuster 120 and operating the second humidity adjuster 122 is a valve 148 for heating the regenerated gas supplied from the regenerated gas heater 144. , To the first humidity controller 120 via line 155. On the other hand, the second humidity controller 1
22 is supplied with purified hydrogen gas through the valve 118, and can be normally adjusted in humidity. The cooling exhaust heat of the electrolyzer 30 is the hot exhaust heat supplied from the cooler 50 to the input line 152 of the regeneration gas heater, and the line 153.
Collect via.

With this configuration, while the fuel power generation system is being operated by the second humidity adjuster 122, the regenerated gas that has undergone heat exchange from the cooling exhaust heat of the cooler 50 that cools the electrolytic cell 30 is continuously made into the first gas. The humidity adjusting agent can be sent to the humidity adjusting device 120, and the humidity adjusting agent can be regenerated and reused.

In order to achieve the above-mentioned object, a fuel cell power generation system to which hydrogen gas is supplied from a hypochlorite generator according to the invention of claim 8 is, for example, as shown in FIG. 1 and FIG. A hypochlorite generator 102 and a hypochlorite generator 102 that generate a by-product gas containing hydrogen gas as a main component in the electrolytic cell 106 by an electrolysis process.
A gas scrubber 86 that removes impurities from the by-product gas delivered from the gas and allows hydrogen gas to pass through, and a fuel cell 104 that generates electricity by an electrochemical reaction between the oxidant gas 25 and hydrogen gas
And the pure water generated from the fuel cell 104 is supplied to the electrolytic cell 106.
And a water supply device for supplying water to.

Here, the water supply device is, as shown in FIG.
The generated water as pure water is supplied from the fuel cell 104 to the line 184.
And 185 to supply water to the electrolytic cell 106 in the hypochlorite generator 102.

In order to achieve the above object, a fuel cell power generation system to which hydrogen gas is supplied from a hypochlorite generator according to claim 8 according to the invention of claim 9 is:
For example, as shown in FIG. 1, an oxygen concentration adjuster 114 arranged between the gas scrubber 86 and the fuel cell 104 and adjusting the oxygen concentration of the by-product gas is further included.

Here, the oxygen concentration adjuster 114 may be a catalytic reactor for reacting oxygen and hydrogen in the by-product gas with a catalyst to convert oxygen into water and remove oxygen. Further, an adsorption device filled with an oxygen adsorbent such as zeolite morikiller sieves, activated carbon, or a metal complex can be used.

With this configuration, hydrogen gas from which oxygen has been removed can be supplied to the fuel cell 104, and hydrogen suitable for the fuel cell 104 and the oxidant gas 25 can be generated by an electrochemical reaction. Thus, the power generation efficiency can be improved and the life can be extended without deteriorating the fuel cell 104.

In order to achieve the above object, a fuel cell power generation system to which hydrogen gas is supplied from a hypochlorite generator according to a tenth aspect of the invention is, for example, as shown in FIG. A hypochlorite generator 102 for generating hydrogen gas from the electrolytic cell by means of an oxidant gas 2
5 and a fuel cell 104 for generating electricity by an electrochemical reaction between hydrogen gas sent from the hypochlorite generator 102.
And a first electric power 174 converted from a natural energy source including wind power or solar light and a second electric power 188 generated from the fuel cell 104, which is selectively supplied to the hypochlorite generation device 102. And a switching device 111.

Here, the first power converted from wind power is the power generated from the wind power generation facility 172, and the first power converted from sunlight is the power generated from the solar power generator 170. Further, the power switching device 111 can use an electromagnetic relay or a semiconductor switching device controlled by the control device 113 including a computer.

With this configuration, the electric power converted from the natural energy source and the electric power generated from the fuel cell 104 can be switched or used together and supplied to the hypochlorite generation device 102.

In order to achieve the above object, a fuel cell power generation system to which hydrogen gas is supplied from a hypochlorite generator according to the invention of claim 11 is, for example, as shown in FIG. 1 and FIG. A hypochlorite generation device 102 that generates hydrogen gas from the electrolytic cell by an electrolysis process, and a hydrogen storage device 190 that reacts with hydrogen gas sent from the hypochlorite generation device 102 and stores hydrogen, The fuel cell 104 that generates electricity by an electrochemical reaction between the oxidant gas 25 and the hydrogen gas taken out from the hydrogen storage device 190, and the hypochlorite generation device 102 that operates with commercial power at night.
Hydrogen discharged from the hydrogen storage device 190 is stored in the hydrogen storage device 190, and hydrogen gas is taken out from the hydrogen storage device 190 and supplied to the fuel cell 104 to generate electric power at times other than nighttime.
Control device 113 (see FIG. 5) that supplies the electric power output from 04 to the hypochlorite generation device 102.

Here, as the hydrogen storage material of the hydrogen storage device 190, TiFe series, MmNi5 series, or Z
It is possible to use a hydrogen storage alloy having a ternary or higher composition in which a part of Zr and Ni is replaced with another element based on the rNi alloy. Further, the control device 113 can use a computer or a microprocessor to process the control of the power generation system throughout the day and night.

According to this structure, the hydrogen stored in the hydrogen storage device 190 is stored in the hydrogen storage device 190 by operating the hypochlorite production device 102 from the commercial power at night, and the hydrogen is stored during the daytime hours other than nighttime. Hydrogen gas can be extracted from the storage device 190 and supplied to the fuel cell 104 to generate electric power, and the electric power output from the fuel cell 104 can be supplied to the hypochlorite generation device 102.

In order to achieve the above object, a fuel cell power generation system to which hydrogen gas is supplied from the hypochlorite generator according to claim 11 according to the invention of claim 12 is shown in FIG. 7, for example. As described above, the hydrogen storage device 190
Includes a hydrogen storage alloy that reacts with hydrogen gas to absorb hydrogen, and a heat source for extracting hydrogen from the hydrogen storage alloy is used as an electrolyzer 3.
It is supplied from zero cooling exhaust heat.

Here, the cooling exhaust heat is the warm exhaust heat supplied from the cooler 50 arranged adjacent to the electrolytic cell 30.

According to this structure, the hydrogen absorbed in the hydrogen storage device 190 at night can be taken out by the heat source supplied from the cooling exhaust heat of the electrolytic cell 30 during the daytime to generate electricity from the fuel cell 104, thus generating electricity. Electric power can be supplied to the hypochlorite generator 102.

In order to achieve the above object, a fuel cell power generation system to which hydrogen gas is supplied from a hypochlorite generator according to claim 11 according to the invention of claim 13 is shown in FIG. 6, for example. As described above, the hydrogen storage device 190
Includes a hydrogen storage alloy that reacts with hydrogen gas to absorb hydrogen, and supplies a heat source for extracting hydrogen from the hydrogen storage alloy from exhaust heat of the fuel cell 104.

Here, the exhaust heat of the fuel cell 104 is the hot exhaust heat supplied from the output line 186 of the fuel cell 104 to the heat exchanger 180 inside the hydrogen storage device 190.

With this structure, the hydrogen absorbed in the hydrogen storage device 190 at night can be taken out by the heat source supplied from the exhaust heat of the fuel cell 104 during the daytime and supplied to the fuel cell 104 to generate electric power. The generated electric power can be supplied to the hypochlorite generator 102.

[0052]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. 1 to 11 show an example of an embodiment of the invention. In the drawings, parts denoted by the same or similar reference numerals as those in the drawings represent the same or corresponding parts, and duplicate explanations will be omitted.

FIG. 1 is a system diagram of a fuel cell power generation system according to a first embodiment of the present invention. The fuel cell power generation system includes a fuel cell 104, a sodium hypochlorite generator 102 as a hypochlorite generator, and a gas arranged between the fuel cell 104 and the sodium hypochlorite generator 102. And a refining device 100.

The sodium hypochlorite generator 102 comprises:
An electrolytic tank 106, a hypochlorite receiving tank 108, and a pump 121 for liquid-sending hypochlorite are provided, and water and sodium chloride are electrolyzed in the electrolytic tank 106, and a tank on the side of the anode 130. The sodium hypochlorite generated in 1 is sent from the line 136 to the steam separator 139 and temporarily stored in the hypochlorite receiving tank 108 via the line 137.

The hypochlorite receiving tank 108 supplies the hypochlorite with the pump 121 to the outside according to the demand of the treated water for the hypochlorite solution treatment. Also, the electrolytic cell 10
The basic liquid existing on the side of the cathode 132 of No. 6 is the line 138.
The liquid is sent to the cleaning liquid tank 126 in the gas purifying apparatus 100 via.

The gas refining apparatus 100 includes a gas blower 109.
And a gas scrubber 86 disposed downstream of the gas blower 109
And a demister 110 arranged downstream of the gas scrubber 86.
And the activated carbon adsorption tower 11 arranged downstream of the demister 110
2, an oxygen concentration adjuster 114 arranged downstream of the activated carbon adsorption tower 112, a cooling device 116 arranged downstream of the oxygen concentration adjuster 114, and humidity adjusters 120 and 122 arranged downstream of the cooling device 116, A hydrogen storage device 124 arranged downstream of the humidity controller and a cleaning liquid tank 126 are provided, and the absorption liquid is liquid-fed from the cleaning liquid tank 126 to the upper part of the gas cleaning device 86 by a pump 128.

Further, the gas purifying apparatus 100 removes the oxygen concentration, humidity and moisture of the by-produced hydrogen gas to a state suitable for the electrochemical reaction for the fuel cell 104, and removes the oxygen concentration, humidity and moisture as fuel. Purify to a state suitable for the battery 104.

In this embodiment, the gas purifier 100 is composed of the gas scrubber 86, the oxygen concentration adjuster 114, and the humidity adjusters 120 and 122, and the sodium hypochlorite (NaClO) generator 102 is a sub-device. The generated by-product gas is passed through the line 136, sucked by the gas blower 109, and transferred to the gas cleaning device 86 having a water sealing portion at the bottom.

The gas scrubber 86 produces chlorine (C) when water or soft water as a circulating liquid is brought into gas-liquid contact with the byproduct gas.
₁₂ ) or sodium hydroxide to remove water-soluble impurities. Since the gas scrubber 86 mainly aims to remove acidic components, the absorbing liquid is preferably a basic liquid. As shown in the drawing, from the cathode 132 side inside the electrolytic cell 106 or from the vicinity of the outlet of the cathode 132, it is preferable to use all or part of the cathode electrolytic solution as an absorbing solution in the gas cleaner 86.

A basic liquid (NaOH) tank (not shown) is prepared separately from the electrolytic bath 106, and the basic liquid (NaO) is used.
H) The absorbent may be supplied to the gas scrubber 86 from the tank. After that, the solution used for cleaning is the anode 1 of the electrolytic cell 106.
You may collect it in the tank on the 30 side. Alternatively, the electrolytic cell 106
It may be used for water supply.

The fuel cell 104 generates direct current electricity by an electrochemical reaction between hydrogen gas supplied from the gas purification apparatus 100 via a line 142 and air or oxygen as the oxidant gas 25.

Here, as the fuel cell 104 using hydrogen as a fuel used in the present embodiment, there are alkaline type, phosphoric acid type, molten carbonate type, solid oxide type, and solid polymer type fuel cells. Therefore, it is desirable to use a phosphoric acid fuel cell or a polymer electrolyte fuel cell, which is relatively small, on-site, and easy to maintain.

The fuel cell 104 uses oxygen or air as the oxidant gas 25 and is operated at atmospheric pressure to about 3 atmospheres. The operating temperature of the fuel cell 104 is from room temperature to 80 ° C. for the solid polymer type and from 190 ° C. to 220 ° C. for the phosphoric acid type.

The solid polymer type is easy to operate and maintain near room temperature, whereas the phosphoric acid type has a relatively high exhaust heat temperature of the fuel cell of about 170 ° C. due to its relatively high temperature. Is expected to be effectively used. Further, since the fuel cell is a direct current power generator, it can be used as a power source for electrolysis of the sodium hypochlorite generator 102 through an output from the fuel cell 104 or via a DC / DC converter.

The sodium hypochlorite generator 102 comprises:
It is a device that produces hypochlorite (NaClO) at the disinfection site, which is used for disinfecting waterworks and sewers. The so-called on-site sodium hypochlorite generation device 102 uses NaCl and H ₂ O =
By the chemical reaction of NaClO + H ₂ , hypochlorite (Na
ClO) is produced. Hydrogen gas is generated as a by-product in the process of this chemical reaction.

Although the by-product generated in the electrolytic cell 106 is hydrogen in terms of chemical reaction, it is actually the electrolytic cell 106.
Even if the diaphragm 178 is disposed in the fuel cell 104, chlorine (Cl ₂ ) or sodium chloride (NaCl) as impurities generated in the process of generating hypochlorite (NaClO) in the electrolytic cell 106 is harmful to the fuel cell 104. Ingredients are also included.

The operation of the gas purifying apparatus 100 will be described with reference to FIG. A demister 110 is appropriately provided downstream of the gas scrubber 86 via a line 140, and an activated carbon adsorption tower 112 is installed downstream of the demister 110. The demister 110 is used to separate the solid-liquid separated hydrogen gas in the form of fine particles. In addition, the activated carbon adsorption tower 112 is used to adsorb impurities accompanying hydrogen gas.

From sodium hypochlorite generator 102
Oxygen (0 _Two) Is included
It In the gas scrubber 86 and the activated carbon adsorption tower 112, the fuel cell is used.
By-product gas can be adjusted to the appropriate oxygen concentration for 104
Therefore, the oxygen concentration using an oxidation catalyst, etc. is used further downstream.
The degree adjuster 114 is installed. The oxygen concentration adjuster 114 is
By reacting oxygen and hydrogen in the by-product gas with a catalyst, oxygen is converted to water.
Can be used to convert the
It

As the oxygen concentration adjuster 114, an adsorption device filled with an oxygen adsorbent such as zeolite morikiller sieves, activated carbon, or a metal complex can be used.
As another means for adsorbing oxygen, a metal complex of cobalt Schiff base may be formed into a complex composed of a conjugated ligand and a low oxidation number metal ion to reversibly adsorb and desorb oxygen molecules.

Further, the cooling device 116 provided downstream of the oxygen concentration adjuster 114 cools the by-produced hydrogen gas whose temperature is raised by the catalytic reaction inside the oxygen concentration adjuster 114. Twin type or multi type humidity adjusters 120 and 122 may be provided downstream of the cooling device 116.
As described above, the humidity adjuster 1 corresponding to the humidity of the by-product gas
20 can function effectively.

The hydrogen storage device 124 disposed downstream of the humidity controllers 120 and 122 introduces the dehumidified by-product hydrogen gas from the line 141 and stores it therein. The stored hydrogen gas is appropriately passed through the line 142 to the fuel cell 1
04, the fuel cell 104 generates DC power by an electrochemical reaction with hydrogen gas and air 25 as an oxidant gas.

FIG. 2 is a schematic system diagram of the gas scrubber 86 used in the fuel cell power generation system according to the first embodiment of the present invention. In this embodiment, water may be used instead of the basic liquid (cleaning liquid) based on the concentration of chlorine or sodium hydroxide removed from the by-product gas. For example, after the softened raw water is stored in the water supply tank 36, the gas scrubber 8 is supplied via the water supply pump 38 and the supply line 72.
Water can be supplied from the upper shower nozzle 6 as well.

The gas scrubber 86 liquid-feeds the soft water stored in the water supply tank 36 by the water supply pump 38 and receives the water supply through the line 72. The by-product hydrogen gas blown into the bottom liquid reservoir of the gas scrubber 86 is supplied from the gas blower 109 through the line 88 and rises inside the gas scrubber 86. Soft water that has absorbed chlorine (Cl ₂ ) or sodium hydroxide in gas-liquid contact with the by-product gas inside the gas scrubber 86 naturally flows down inside the line 135 via the bottom liquid reservoir, and then flows into the electrolytic cell 106 (see FIG. 1). ) Is collected. On the other hand, the by-product hydrogen gas from which chlorine (Cl ₂ ) or sodium hydroxide has been removed is sent from the upper part of the gas scrubber 86 to the demister 110 (see FIG. 1) via the line 140.

FIG. 3 is a schematic system diagram of the humidity controller used in the fuel cell power generation system according to the first embodiment of the present invention. The humidity controller has at least a first dehumidifier for performing a continuous dehumidification operation of the by-product gas passing through the inside.
It is desirable to adopt a twin system or a multi system including the humidity controller 120 and the second humidity controller 122.

The line 150 is a valve 1 as a three-way valve.
A line 18 branches into two lines, which are connected to the inlets of the humidity adjuster 120 and the humidity adjuster 122, respectively.
A valve 148 as a three-way valve is branched from the line 150 on the upstream side of the valve 118 and is connected to the regeneration gas heater 114.
It is connected to the.

The line 151 is branched into two lines 155 and 156 by the valve 148.
5 and the line 156 respectively join the lines branched from the valve 118 and connected to the humidity controllers 120 and 122.

A line 152 for introducing a heat source for heating the regenerated gas and a line 153 for delivering the heat source are connected to the regenerated gas heater 144.

Line 159 is valve 1 as a three-way valve.
A line 46 branches into two lines 157 and 158, which are respectively connected to the outlets of the humidity adjuster 120 and the humidity adjuster 122. A line 141 that joins the line branched from the line 157 and the line branched from the line 158 is connected to the outlet sides of the humidity adjusters 120 and 122.

The valve 118 is operated to stop the inflow of the byproduct gas into the first humidity adjuster 120, and the byproduct gas is passed through the second humidity adjuster 122 to operate the dehumidification process. Change the passage route. And the first
The heat source for regeneration of the dehumidifying agent filled in the humidity controller 120 can be obtained from the exhaust heat of the fuel cell.

The exhaust heat of the fuel cell is generated by the regeneration gas heater 144.
Is introduced through a line 152, the heat exchanger 144 is passed through, and the heat is recovered via a line 153. The purified gas is sent from the cooling device 116, introduced into the regeneration gas heater 144 via the lines 150 and 151, and exchanges heat with the exhaust heat of the fuel cell.

The heated refined gas passes through the line 151 as the regenerated gas 154, and passes through the valve 148 and the line 155.
It is introduced into the inside of the first humidity adjuster 120 via.
The regeneration gas heats the humidity adjusting agent with which the first humidity adjuster 120 is filled to recover the hygroscopicity. Regenerated gas is delivered to the gas blower inlet (not shown) via output line 158, valve 146, and line 159.

During the regeneration process of the first humidity controller 120,
The second humidity adjuster 122 performs a normal humidity adjusting operation. That is, the purified gas sent from the cooling device 116 is introduced into the second humidity adjuster 122 via the valve 118, and the humidity is adjusted to remove the humidity. The purified gas whose humidity has been adjusted is sent to the hydrogen storage device via the output line 141.

In the above embodiment, the first humidity controller is the humidity controller 120 and the second humidity controller is the humidity controller 122, but the first and second humidity controllers are switched. Thus, the first humidity adjuster may be the humidity adjuster 122 and the second humidity adjuster may be the humidity adjuster 120.

In this case, the dehumidifying effect can be restored by switching the valve 118 and the valve 148 and introducing the heated purified gas as the regenerated gas 154 into the first humidity controller 122.

Further, in order to increase the operating rate of the gas purifying apparatus 100, the valve 118 and the valve 148 are switched so that the purified gas delivered from the cooling device 116 is adjusted to the first humidity controller 120 and the second humidity controller. The humidity of the by-produced hydrogen gas can be removed by simultaneously supplying it to the container 122 to adjust the humidity.

FIG. 4 is a schematic system diagram of a sodium hypochlorite generator according to the second embodiment of the present invention. In the above-mentioned embodiment, the exhaust heat of the fuel cell is used as the regeneration heat source of the humidity controller, but in the present embodiment, the electrolytic cell 30 is used.
The hot exhaust heat of the cooler 50 for cooling the is used.

The sodium hypochlorite produced from the electrolytic cell 30 is supplied to the gas-liquid separator 139a through the line 68,
A reflux path for temporarily storing in the hypochlorite receiving tank 54 via the line 69 after gas-liquid separation and returning to the electrolytic tank 30 via the hypochlorite solution circulation pump 52 and the cooler 50. Circulate.

The cooling device 50 introduces the cooling liquid from the cooling liquid tank 160 by the pump 162 via the line 51, and heat-exhausts heat to the above-mentioned regeneration gas heater 144 (see FIG. 3) via the output line 164. Of the by-product hydrogen gas and after exchanging heat with the by-product hydrogen gas, the cooling liquid is recovered to the cooling liquid tank 160 via the line 168. In this way, the electrolytic cell 30
The cooling waste heat of can be used as a regeneration heat source for recovering the function of the humidity controller.

The illustrated sodium hypochlorite generator comprises an electrolytic cell 30, an alkali chloride solution storage tank 40, a hypochlorite receiving tank 54, and a hypochlorite storage layer 58, which is saturated with a salt solution decomposing tank. Alkali chloride solution storage tank 40 having a salt water tank
The saturated salt water is sent to the electrolytic cell 30 through the salt water pump 44 and the line 66.

The driving control of the salt water pump 44 is based on the measurement value of the measuring meter 42 for measuring the amount of salt water in the saturated salt water tank, and the salt water pump 44 is driven according to the increase of the saturated salt water to the electrolytic cell 30. Is configured to supply. Further, the water supply to the electrolyzer 30 is performed by the water supply path 3 for supplying raw water.
2. The water supplier 34 for reforming raw water into soft water, the water tank 36 for storing soft water, the water supply pump 38, and the line 65 are used to supply the soft water to the electrolytic cell 30.

The sodium hypochlorite sent from the electrolytic cell 30 is supplied to the gas-liquid separator 139a via the line 68, and after the gas-liquid separation, is temporarily transferred to the hypochlorite receiving tank 54 via the line 69. And a circulation line for returning to the electrolytic cell 30 through the hypochlorite solution circulation pump 52 and the cooler 50, and a liquid delivery to the hypochlorite storage tank 58 through the pump 56 and line 71. A chlorite solution supply line supplies a hypochlorite solution 62 to the outside via a hypochlorite solution injection pump 60 according to demand.

The electrolytic cell 30 generates a by-product gas containing hydrogen gas as a main component when a hypochlorite solution is generated by electrolysis. This by-produced gas is configured to be supplied from the line 68 to the gas purification device by passing through the gas-liquid separator 139a and the line 143.

FIG. 5 is a system diagram of a fuel cell power generation system according to a third embodiment of the present invention. The fuel cell power generation system includes a sodium hypochlorite generator 102.
, The fuel cell 104, the gas purification device 100, and the generated power 1 as the first power converted from the natural energy source.
Second electric power 188 generated from the fuel cell 104 and the fuel cell 104
Power switching device 1 for selectively switching generated power
And 11.

In the present embodiment, commercial power is not transmitted. That is, even in an environment where commercial power cannot be used, the sodium hypochlorite generator 102 and the fuel cell 1
04 is combined to operate as a power generation system. At the time of starting the power generation system, the control device 11
The power source of 3 is a solar power generation facility 170 or a wind power generation facility 17
2 or a battery such as a charging / discharging system (not shown).

The required electric power of the sodium hypochlorite generator 102 is to use the first electric power 174 obtained by natural energy such as wind power or sunlight and the second electric power 188 generated from the fuel cell 104 in combination. You can That is, when the electrolysis power consumed by the sodium hypochlorite generator 102 is insufficient only with the DC voltage converted from the natural energy, the DC voltage generated from the fuel cell 104 is operated by operating the power switching device 111. Electric power can be supplementarily supplied to the sodium hypochlorite generator 102.

Here, during the daytime, when the solar power generation facility 170 can fully utilize the natural energy, the sodium hypochlorite producing apparatus is relied on the first electric power by utilizing the sunlight which is the natural energy. Hypochlorite (NaClO) is produced from 102.

By-product in the process of producing hypochlorite (NaClO) and by-product hypochlorite (NaCl)
O) and excess hydrogen are stored in the above-mentioned hypochlorite storage tank and hydrogen tank.

Disinfection hypochlorite (NaClO) is required all year round, but when natural sodium energy alone is insufficient to supply power to the sodium hypochlorite generator 102, the hypochlorite tank is used. The hypochlorite (NaClO) stored in is used.

Then, the stored hypochlorite (NaCl
When O) is consumed and the stored amount is insufficient, the stored hydrogen is used to generate electric power from the fuel cell 104 by an electrochemical reaction. The generated power can be supplied to the sodium hypochlorite generator 102 to drive the sodium hypochlorite generator 102, generate hypochlorite (NaClO), and start the disinfection. The DC power obtained from the fuel cell 104 can also be supplied to the battery for recharging.

The sodium hypochlorite generator 102 comprises:
It is possible to produce hypochlorite with an effective chlorine amount of 10 kg / hour,
The electric power required for effective chlorine production is 4.5 kWh / kg. The current efficiency of available chlorine production averages 65%. At this time, the amount of hydrogen gas generated from the cathode is about 4.8 Nm ³ / hour.

Using the by-produced hydrogen gas generated from the sodium hypochlorite generator 102, DC power of about 5.6 kW was obtained as the output of the fuel cell 104, and about 12% of the power consumed in the electrolytic cell was obtained. % Can be recovered as electric energy.

Further, the produced water is recovered by the electrochemical reaction of the fuel cell 104, and the sodium hypochlorite producing apparatus 1
It is supplied to the electrolytic cell in 02.

As described above, the power generation facilities 170 and 172 using natural energy such as wind power and sunlight of appropriate scale, the sodium hypochlorite generation device 102, and the fuel cell 104.
It is possible to provide a fuel cell power generation system that combines a self-contained hypochlorite generator that does not require a commercial power source at all by cooperating with each other.

Furthermore, in addition to electric power, exhaust heat and pure water can be taken out as the products of the fuel cell 104. Therefore, in the present embodiment, the self-contained sodium hypochlorite generator 1 is used.
It is possible to provide a fuel cell power generation system that is combined with the fuel cell system No. 02. In this embodiment, the self-contained system is a sodium hypochlorite generator 102 and a fuel cell 1.
04 products, for example, hot exhaust heat, water, electric power, hydrogen fuel, etc., are mutually supplied, and the system can be maintained without relying on external replenishment.

The fuel cell 104 uses the sodium hypochlorite generator 1 to generate water produced from hydrogen and oxygen as fuels.
02 Used as water supply for the electrolyzer inside. Fuel cell 10
The produced water of No. 4 can be sent to the sodium hypochlorite producing apparatus 102 via lines 185 and 184 and used as an electrolyte on the cathode side. Further, makeup water is supplied from the water supply port of the line 184 to the sodium hypochlorite generator 102.
It is also possible to send it to and make up for the shortfall.

FIG. 6 is a system diagram of a hydrogen storage device applied to a fuel cell power generation system according to a fourth embodiment of the present invention. The hydrogen storage device 190 is provided with a hydrogen storage alloy inside, the line 191 is connected upstream, the fuel cell 104 is connected downstream via the line 192, and the fuel cell 10 is connected.
There is a circulation path for recovering the line 186 as the exhaust heat path of No. 4 to the fuel cell 104 via the heat exchanger 180. In addition, the hydrogen storage device 190 can introduce the purified gas (by-product hydrogen gas) sent from the humidity controller and store the purified gas in the internal hydrogen storage alloy.

As the material of the hydrogen storage alloy, for example, T
iFe-based, MmNi5-based, or ZrNi alloy as a base, with Zr and Ni partially substituted with other elements 3
A hydrogen storage material having a composition higher than that of the original system and having a CrB structure as its crystal structure can be used.

The absorbed hydrogen is the exhaust heat of the fuel cell 104 from the line 186 to the heat exchanger 1 inside the hydrogen storage device 190.
80, and hydrogen gas is taken out from the hydrogen storage alloy.
The taken out hydrogen gas is passed through the line 192 to the fuel cell 1
It is possible to generate direct current by the electrochemical reaction between the hydrogen gas and the oxidant gas 25.

To illustrate the operation pattern of the power generation system including the sodium hypochlorite generator 102 (see FIG. 5), the gas purifier 100 (see FIG. 5) and the fuel cell 104, the relatively inexpensive nighttime electric power is used. Gas purifier 1
00 and the fuel cell 104, a hydrogen storage device 190 is arranged, and hydrogen generated at night is stored in the hydrogen storage device 190.

The hydrogen stored in the hydrogen storage device 190 is supplied to the fuel cell 104 in the daytime, that is, in the daytime to generate electricity by an electrochemical reaction. The generated electric power can supply all electric power or auxiliary electric power required by the sodium hypochlorite generator 102 in the daytime.

The hydrogen storage device 190 uses a hydrogen storage alloy, and the heat source necessary for releasing hydrogen from the hydrogen storage alloy is a sodium hypochlorite generation device 102 (see FIG. 5).
The cooling exhaust heat of the cooler 50 that cools the internal electrolytic cell 30 or cools the electrolytic solution circulating in the electrolytic cell 30 is used (see FIG. 4).

FIG. 7 is a schematic system diagram of a sodium hypochlorite generator which is a fourth embodiment of the present invention. The saturated salt water system, the water supply system, the electrolytic bath 30, and the hypochlorite storage bath 58 can use the same devices as those in the above-mentioned embodiment, and therefore, duplicated description will be omitted.

The cooler 50 is connected to the sodium hypochlorite receiving tank 54 via the hypochlorite solution circulation pump 52, is connected to the electrolytic tank 30 via the line 67, and is connected to the cooling liquid tank 198 and the pump 201. And a line 196, and the hydrogen storage device 190 is connected via a line 194.

Pump the coolant from the coolant tank 198 to pump 2
01 to the cooler 50 via line 196,
The introduced cooling liquid is supplied from the line 194 to the hydrogen storage device 190.
And is circulated to the cooling liquid tank 198 via. Further, the cooler 50 cools the hypochlorite solution injected from the hypochlorite receiving tank 54 via the hypochlorite solution circulation pump 52, and then to the electrolytic cell 30 via the line 67. It has a circulation line for supplying the hypochlorite solution.

Line 194 connecting to the output of cooler 50
Sends warm exhaust heat to the hydrogen storage device 190, exchanges heat, and then collects the cooling liquid in the cooling liquid tank 198.
The cooling exhaust heat of the electrolytic cell 30 can be used as a heat source for taking out hydrogen from the hydrogen storage device 190.

FIG. 8 is a system diagram of a fuel cell unit used in the fifth embodiment of the present invention. The fuel cell unit 200 includes a gas purification device 100, a fuel cell 104 connected to the gas purification device 100, a DC / DC converter 202 connected to the fuel cell 104, and a grid interconnection inverter 204 connected to the DC / DC converter 202. With.

In the fuel cell unit 200, the by-product hydrogen gas containing hydrogen is introduced from the input line 183, the by-product gas is purified by the gas purification device 100, and then the hydrogen gas is supplied to the fuel cell 104 through the line 142. Then, the DC power is generated by the electrochemical reaction with the air 214 as the oxidant gas.

The fuel cell 104 is connected to the load 2 via the DC / DC converter 202 and the grid interconnection inverter 204.
Electric power of a fixed frequency is supplied to the system power supply 206 connected to 08. The output of the fuel cell 104 is a DC voltage of about 50 volts.

The electric power required for electrolysis of the electrolytic cell is
Directly from the output terminal 105 of the fuel cell 104 or DC / D
It can be supplied via a C converter. In this case, the power loss for rectifying the AC voltage output to DC through the DC / DC converter 202 and the DC / AC inverter as the system interconnection inverter 204 can be reduced, and the power conversion efficiency is excellent. A combine system of the sodium chlorate generation device 102 and the fuel cell unit 200 can be provided.

FIG. 9 is a system diagram of the oxygen concentration adjuster 114 applied to the fuel cell power generation system according to the embodiment of the present invention. The oxygen concentration adjuster 114 is used in the pretreatment process unit 11
7 and a precious metal catalyst 119, oxygen is removed from the by-product gas sent from the activated carbon adsorption tower 112 via the pump 115, and hydrogen gas is sent to the cooling device 116.
Oxygen in hydrogen gas as a fuel of No. 04 is removed to adjust the oxygen concentration.

Pretreatment process section 1 in the oxygen concentration adjuster 114
Reference numeral 17 includes a filter and a residual heat portion, and the byproduct gas is heated to a high temperature of about 700 ° C. or higher by the pretreatment process section 117 using a combustion burner or an electric heater to oxidize and decompose the byproduct gas to reduce the oxygen concentration. Can be lowered.

Further, in the present embodiment, a noble metal catalyst 119 such as platinum or palladium can be used,
In the above-mentioned pretreatment process section 117, for example, a preheat treatment of about 300 ° C. may be performed, and then a noble metal catalyst 119 may be passed through to perform an adjustment treatment for similarly reducing the oxygen concentration. In this case, the combustion process of the precious metal catalyst 119 has a low running cost and a high catalyst activation, so the oxygen concentration adjuster 114
Can be miniaturized.

Further, as an oxygen gas adsorbent used in the oxygen concentration adjuster 114, a copolymer of vinyl aromatic amino and an alkyl acrylate or an alkyl methacrylate, and mesothtetra (α, α, α, α-o- A polymer complex composed of a pivalamidophenyl) porphinato metal (II) complex can also be used in a honeycomb structure.

The noble metal catalyst 119 has a round or square honeycomb structure in its outer shape, and purifies the preheated by-product hydrogen gas, that is, removes oxygen and allows hydrogen to pass, and is also preheated. Instead, it is possible to apply an alternating voltage to the noble metal catalyst 119 to use an electrically heated superheated catalyst.

In this embodiment, a wide range of by-product gas flow rates or gas temperatures can be accommodated, and a large amount of by-product gas is passed through the noble metal catalyst 119 to reduce the oxygen concentration, or a method of controlling humidity is used. A method in which a high by-product gas is heated by a sheath heater and then passed through the noble metal catalyst 119, or a method in which an electric current is directly passed through the noble metal catalyst 119 to cause self-heating to promote the catalytic action can be adopted. In particular, the method of directly supplying an electric current to the precious metal catalyst 119 is
Since the thermal efficiency is high and the reaction efficiency is high, it is advantageous when the oxygen removal treatment of the by-product gas having low humidity is performed.

A cooling device 116 is appropriately provided downstream of the oxygen concentration adjuster 114 to lower the temperature of the by-product gas sent from the oxygen concentration adjuster 114.

FIG. 10 is a system diagram of a fuel cell power generation system according to a sixth embodiment of the present invention. The fuel cell power generation system can use the same configurations of the fuel cell 104 and the sodium hypochlorite generation device 102 as those of the above-described embodiment, and thus duplicate description will be omitted.

The gas purifying apparatus 100 comprises a gas scrubber 86a, a demister 110, an activated carbon adsorption tower 112, in the order in which the fuel gas supplied from the line 136 moves.
An oxygen concentration adjuster 114, a cooling device 116, humidity adjusters 120 and 122, and a hydrogen storage device 124 are provided.

The sodium hypochlorite generator 102 comprises:
As described above, this is a device that produces hypochlorite (NaClO) used for disinfection of waterworks and sewers at the disinfection site. The so-called on-site sodium hypochlorite generation device 102 uses sodium chloride and water as raw materials to generate NaC.
Hypochlorite (NaClO) is produced by the chemical reaction of 1 + H ₂ O = NaClO + H ₂ , and hydrogen gas is generated as a by-product in the process of this chemical reaction.

The by-product is hydrogen in terms of chemical reaction,
Actually, even if the diaphragm 78 is arranged in the electrolytic cell 106, chlorine (Cl ₂ ) or sodium chloride (NaCl) as impurities generated in the process of generating hypochlorite (NaClO) in the electrolytic cell 106, etc. It also contains components that are harmful to the fuel cell 104 of FIG.

Further, in the present embodiment, the oxygen concentration, humidity and humidity of hydrogen gas are removed to a state suitable for the electrochemical reaction for the fuel cell 104, and the oxygen concentration, humidity and moisture are removed. To a suitable state for

Here, the gas purifier 100 is used as a gas scrubber 86a, an oxygen concentration adjuster 114, and a humidity adjuster 12.
0,122, hypochlorite (NaClO)
The by-product gas by-produced from the generator 102 is transferred to the gas scrubber 86a.

The gas scrubber 86a has a cylindrical or cube-shaped container erected in the vertical direction, and has the polymeric functional material 9 inside.
It functions as a dry processing type gas scrubber that fills 1. For example, an inorganic ion exchanger such as zeolite or an organic ion exchanger such as an ion exchange resin can be used as the polymer functional material.

Further, the heat resistance of the organic ion exchanger is lower than that of the inorganic ion exchanger. Therefore, when performing gas cleaning at high temperature, it is preferable to use an inorganic ion exchanger having high heat resistance. However, the present invention is not limited thereto, and for example,
Dry processing type gas scrubber 8 by arbitrarily selecting various ion-exchange groups having high absorption capacity for chlorine gas contained in by-product hydrogen
6a can be used.

Further, among the organic ion exchangers, the organic ion-exchange group produced by the radiation graphite polymerization method is a non-woven fabric or a woven fabric, or an aggregate of the non-woven fabric and the non-woven fabric, as compared with the conventional ion-exchange beads. Since it can be introduced into a polymer molding such as a void material, it is suitable for removing chlorine gas.

The above-mentioned ion-exchange groups are suitable, for example, because quaternary ammonium groups and lower amino groups below the tertiary amino group react directly with chlorine gas, but quaternary ammonium groups and tertiary amino groups are preferred. Ion-exchange groups containing both groups are also effective in removing chlorine gas.

Typically, an ion-exchange group obtained by introducing triethylenediamine into a chloromethylstyrene polymer can be used, and a cation-exchange group such as a sulfonic acid group, a phosphoric acid group, and a carboxyl group also has a high absorption of chlorine gas. It can be used as an agent. This cation exchange group can be formed into a metal salt type such as sodium (Na) or potassium (K) and reacted with chlorine gas (Cl ₂ ) to be fixed and removed as a metal chloride.

Furthermore, either anion exchange group or cation exchange group in which the above metal oxide is supported on an ion exchanger can be used. For example, an exchange group in which manganese oxide is supported on an anion exchanger can be used.

As described above, the dry processing type gas scrubber 8 is used.
6a is a line 136 and a gas blower 1 from the electrolytic cell 106.
09, a polymeric functional material 91 that removes chlorine gas from a mixed gas of hydrogen gas and chlorine gas supplied via 09 is made of, for example, a non-woven fabric, and the chlorine gas is adsorbed only by filling the inside with the downstream demister 110. Hydrogen gas can be supplied to the structure, and the structure is simple as compared with the wet processing method.

In addition, the cleaning liquid tank 126 and the liquid feed pump 1
Since no additional equipment such as 28 is required, neither the pump drive power for feeding the cleaning liquid for removing the chlorine gas nor the installation area of the cleaning liquid tank 126 are necessary.

Therefore, the gas cleaner 8 of the dry processing system is used.
6a is easy to install and can simplify facility maintenance management. For example, it suffices to replace the non-woven fabric in order to recover the absorption of chlorine gas.

As described above, the hydrogen gas by-produced from the sodium hypochlorite generator 102 contains oxygen. This by-produced hydrogen gas has an increased oxygen concentration when the sodium hypochlorite generator 102 is restarted after being stopped for a long time, or when the electrodes and the ion exchange membrane in the electrolytic cell 106 are deteriorated. There are cases. When the oxygen concentration in the by-product hydrogen gas reaches a value of several percent or more, the explosion limit is exceeded, and therefore it is necessary to avoid operating the system in such an oxygen concentration state for safety.

In the present embodiment, in order to prevent the system from operating in such a predetermined oxygen concentration state, the gas purifying apparatus 100 uses the byproduct hydrogen gas from the electrolytic cell 106 in the line 136, the gas blower 109, and the gas scrubber 86a. , A demister 110, an activated carbon adsorption tower 112, and a mainstream path for supplying the oxygen concentration adjuster 114, and the hydrogen gas whose oxygen concentration is adjusted from the oxygen concentration adjuster 114.
6. A circulation path 97 that circulates to a suction port of the gas blower 109 via the control valve 93, and bypasses a part of oxygen-removed hydrogen gas transferred from the oxygen concentration adjuster 114 via the cooling device 116. Then, the by-produced hydrogen gas containing a high concentration of oxygen gas is mixed and supplied to the suction port of the gas blower 109.

With such a configuration, the gas purifying apparatus 100 reduces the oxygen concentration in the by-product hydrogen gas passing through each of the gas blower 109, the gas scrubber 86a, the demister 110, and the activated carbon adsorption tower 112. Can
It is possible to avoid situations in which the explosion limit is exceeded.

In the circulation path 97, even if the oxygen concentration in the by-product hydrogen gas fluctuates, the absolute value of the oxygen concentration can be maintained at a low value of a predetermined level. Prevent situations in which the explosion limit is exceeded.

Therefore, in this embodiment, when the sodium hypochlorite generator 102, which is implemented in the system not including the circulation path 97, is restarted after being stopped for a long period of time, the oxygen concentration in the by-product hydrogen gas is reduced. The amount of power generation is reduced by stopping the supply of by-produced hydrogen gas to the fuel cell 104 during environmentally unfavorable situations, such as releasing the by-produced hydrogen gas to the outside of the system until That disadvantage can be eliminated.

Further, the gas purifying apparatus 100 includes a drive motor 95 for opening and closing the control valve 93 and a gas blower 109.
Further comprises an oxygen concentration detector 107 for detecting the oxygen concentration in the by-produced hydrogen gas by the oxygen sensor 103 provided in the inlet pipe of the control valve 93 based on the oxygen concentration in the by-produced hydrogen gas. The amount of hydrogen gas from which oxygen has been removed passing through the above circulation path 97 is variably controlled to reduce the oxygen concentration in the mainstream path.

Since the opening / closing degree of the control valve 93 is controlled according to the output signal output from the oxygen concentration detector 107, the electrodes and the ion exchange membrane in the electrolytic cell 106 are deteriorated and the oxygen concentration in the main flow path is increased. If so, the oxygen concentration detector 10 is not stopped without stopping the sodium hypochlorite generator 102.
7 to detect the oxygen concentration in the by-product hydrogen gas by the oxygen sensor 103 provided in the inlet pipe of the gas blower 109,
The opening / closing control of the control valve 93 is performed while comparing with the preset oxygen concentration upper limit value (a value sufficiently lower than the explosion limit).

That is, when the oxygen concentration in the by-product hydrogen gas is high, the opening / closing degree of the control valve 93 is increased to increase the amount of hydrogen gas passing through the circulation path 97, and the oxygen concentration in the by-product hydrogen gas is low. In this case, the variable control is executed so as to reduce the degree of opening / closing of the control valve 93 and reduce the amount of hydrogen gas passing through the circulation path 97.

Even when the oxygen concentration detector 107 requires a response time of several tens of seconds or more until it receives a detection signal from the oxygen sensor 103 and outputs an output signal for opening and closing the control valve 93. By presetting the above oxygen concentration upper limit to a value sufficiently lower than the explosion limit,
The oxygen concentration in the mainstream route can be controlled so as not to exceed the explosion limit.

The setting of the oxygen concentration upper limit value depends on the oxygen concentration fluctuation speed in the by-product hydrogen gas and the response speed of the oxygen concentration detector 107, but at least the circulation path 97 is provided as in the present embodiment. Therefore, the rate of increase in the oxygen concentration in the mainstream route is moderated, and the time until the oxygen concentration in the mainstream route exceeds the explosion limit can be extended.

Further, since the oxygen concentration detector 107 receives the detection signal from the oxygen sensor 103 and controls to open / close the control valve 93, the oxygen concentration of the by-product hydrogen gas drawn into the gas blower 109 is kept constant. Can be kept at

The oxygen concentration detector 107 requires a response speed of several tens of seconds, and the oxygen concentration upper limit value is set with a margin so that the oxygen concentration in the main flow path does not exceed the explosion limit. By constantly monitoring the oxygen concentration in the mainstream route,
The response speed of the oxygen concentration detector 107 can be complemented.

In this embodiment, the oxygen concentration adjuster 114 is used.
Temperature detectors 85 and 89 for detecting the temperature of the by-produced hydrogen gas passing through the upstream side 81 and the downstream side 83, respectively, and output signals from the upstream side temperature detector 85 and the downstream side temperature detector 89. Based on the above, a calculator 87 for calculating the temperature difference between the upstream side and the downstream side is provided. An oxygen concentration monitoring system having improved responsiveness is constituted by the temperature detectors 85 and 89.

The temperature change of the noble metal catalyst such as platinum or vanadium filled in the oxygen concentration adjuster 114 is proportional to the oxygen concentration. The noble metal catalyst reacts with oxygen in the by-product hydrogen gas passing through the oxygen concentration adjuster 114 and exhibits a highly responsive temperature change. Therefore, by-product hydrogen passing through the upstream side and the downstream side of the oxygen concentration adjuster 114. The oxygen concentration can be measured simply by detecting the gas temperature.

The temperature change of the catalyst may change over time due to long-term operation of the system due to deterioration of the catalyst or the like. In this case, the oxygen concentration adjuster 11
The oxygen concentration in the by-produced hydrogen gas passing through the upstream side and the downstream side of No. 4 is detected, the correlation between the by-produced hydrogen gas temperature during passage and the oxygen concentration is taken, and the calibration work is carried out periodically and the calculator 87
The accuracy of oxygen concentration detection can be maintained by re-entering the calibration data. For example, the oxygen concentration in the by-product hydrogen gas is detected by a galvanic electrode type oxygen detector,
Carry out calibration work.

FIG. 11 is a system diagram of a humidity controller applied to the fuel cell power generation system according to the seventh embodiment of the present invention. The humidity adjuster is preferably configured in a twin system or a multi system including at least the first humidity adjuster 120 and the second humidity adjuster 122 so that the gas purifier 100 or the fuel cell power generation system can be continuously operated. .
In this case, the first humidity adjuster 120 is stopped and the oxygen concentration adjuster 114 is used as a heat source for regenerating the dehumidifying agent from about 400
C. gas can be obtained.

Line 150 is valve 1 as a three-way valve.
A line 18 branches into two lines, which are connected to the inlets of the humidity adjuster 120 and the humidity adjuster 122, respectively.

The line for supplying the high-temperature by-product hydrogen gas from the oxygen concentration adjuster 114 is branched into two lines 155 and 156 by the valve 148, and the line 155.
And the line 156 branch from the valve 118 and join the lines connected to the humidity controllers 120 and 122.

Similar to the above-mentioned embodiment, the line 159 is branched into two lines 157 and 158 by the valve 146 as a three-way valve, and each of the humidity adjuster 1
20 and the outlet of the humidity controller 122. A line branching from the line 157 and a line branching from the line 158 are connected to a valve 161 as a three-way valve on the outlet side of the humidity adjuster 120 and the humidity adjuster 122, and a line 141 is provided on the downstream side of the valve 161. It is connected.

The valve 118 is operated to stop the flow of the by-produced hydrogen gas into the first humidity adjuster 120, and the by-produced hydrogen gas is allowed to pass through the second humidity adjuster 122 so that the dehumidifying process is activated. Change the gas passage. Then, the heat source for regenerating the dehumidifying agent filled in the first humidity adjuster 120 can be obtained from the high temperature gas supplied from the oxygen concentration adjuster 114.

The gas delivered from the oxygen concentration adjuster 114 is introduced as regeneration gas into the first humidity adjuster 120 via the valve 148 and the line 155, and heats the humidity adjuster to recover the hygroscopicity. Let The regeneration gas is delivered to the gas blower suction (not shown) via the output line 158 and the valve 146. For example, in the gas blower suction, the regeneration gas can be recirculated using the suction port of the gas blower 109 (see FIG. 10) provided upstream of the gas scrubber 86a (see FIG. 10), and by the gas blower (not shown). The regeneration gas may be refluxed upstream of the oxygen concentration adjuster 114 (see FIG. 10).

During the regeneration process of the first humidity adjuster 120,
The second humidity adjuster 122 performs a normal humidity adjusting operation. That is, the purified gas sent out from the oxygen concentration adjuster 114 passes through the cooling device 116, the valve 118, and is introduced into the second humidity adjuster 122, where the humidity is adjusted. The purified gas whose humidity has been adjusted is sent to the hydrogen storage device via the output line 141 via the valve 161 as a three-way valve.

In the above embodiment, the first humidity adjuster is the humidity adjuster 120 and the second humidity adjuster is the humidity adjuster 122. However, the valves 118 and 14 are used.
8, valve 146, and valve 161 are switched to the first
And the second humidity controller are replaced with each other, the first humidity controller is the humidity controller 122, and the second humidity controller is the humidity controller 1.
It can also be configured as 20.

In this case, the gas delivered from the oxygen concentration adjuster 114 is used as the regeneration gas in the valve 148 and the line 1.
It is introduced into the first humidity adjuster 122 via 56 and heats the humidity adjuster to recover the hygroscopicity. Regenerated gas is output line 157, valve 146, output line 15
It is sent to the suction port of the gas blower 109 or the like via 9.

As described above, since the outlet gas temperature of the oxygen concentration adjuster 114 reaches a high temperature of about 400 ° C., this high temperature gas is used as a regeneration gas for the dehumidifying agent filled in the humidity adjuster 120 or 122. Therefore, a sufficient regeneration effect can be obtained without using the exhaust gas of the fuel cell 104 described above.

Further, in order to increase the operating rate of the gas purifying apparatus 100, the valves 118, 148, 1
46 and the valve 161 are switched to supply the by-produced hydrogen gas from the cooling device 116 to the first humidity adjuster 120 and the second humidity adjuster 122 to simultaneously exhibit the dehumidifying function and extend the life of the dehumidifying material. The humidity of the by-product gas can be adjusted.

As described above, according to the present embodiment, the by-product gas containing hydrogen as a main component, which is by-produced in the process of producing hypochlorite in the hypochlorite producing apparatus, is used in the fuel cell. Can be used as fuel.

By incorporating a power generator using natural energy such as wind and sunlight into the fuel cell power generation system that combines with this hypochlorite generator, not only an external power source is not required It is possible to provide a fuel cell power generation system that is supplied with hydrogen fuel from a self-contained hypochlorite generator.

Further, hypochlorites are dissolved in water and used as oxidizers such as bleaching agents and bactericides for water treatment, waste water treatment, disinfecting water used in hospitals and dental clinics, household kitchens, etc. It can be used in a wide range of fields such as and an aqueous solution for washing.

In particular, in recent years, chlorine gas or sodium hypochlorite has been used for chlorine treatment for disinfection and sterilization in a water purification plant which supplies drinking water and the like. Due to operational and management problems such as environmental harmony and chemical instability, the method of producing an on-site aqueous solution of sodium hypochlorite and using it is being adopted.

Although the hypochlorite solution production by electrolysis of the alkali chloride solution has low electrolysis efficiency, impurities are removed from the by-product gas generated from the hypochlorite production apparatus according to the present invention. By refining hydrogen gas and generating electric power from the fuel cell as fuel, deterioration of the fuel cell can be prevented and the life of the fuel cell can be extended.

Further, a hydrogen gas generated from the hypochlorite production apparatus is used as a fuel to drive a power generation unit such as a phosphoric acid fuel cell or a polymer electrolyte fuel cell to generate electric power in the hypochlorite production apparatus. It is possible to provide an on-site type hypochlorite solution generator and a fuel cell power generation system used as a power source for electrolysis.

The fuel cell power generation system to which hydrogen gas is supplied from the hypochlorite generator of the present invention is not limited to the above-mentioned illustrated examples, and is within a range not departing from the gist of the present invention. It goes without saying that various changes can be made in.

[0175]

As described above, the first aspect of the present invention is as described above.
According to the fuel cell power generation system in which hydrogen gas is supplied from the hypochlorite generator, the hydrogen gas generated from the hypochlorite generator is converted into a phosphoric acid fuel cell or a polymer electrolyte fuel cell. It is possible to exert an excellent effect of providing a fuel cell power generation unit that can be refined to such a degree that it can be used as a fuel.

Further, by incorporating a power generator using natural energy such as wind power or sunlight into a fuel cell power generation system which receives hydrogen gas from a hypochlorite generator, an external power source is not required It is possible to construct a self-contained hypochlorite generator and fuel cell power generation system in which the amount of waste is reduced.

[Brief description of drawings]

FIG. 1 is a system diagram of a fuel cell power generation system according to a first embodiment.

FIG. 2 is a schematic system diagram of a gas scrubber applied to the first embodiment.

FIG. 3 is a schematic system diagram of a humidity adjuster applied to the first embodiment.

FIG. 4 is a schematic system diagram of a sodium hypochlorite production device according to a second embodiment.

FIG. 5 is a system diagram of a fuel cell power generation system according to a third embodiment.

FIG. 6 is a system diagram of a hydrogen storage device applied to a fourth embodiment.

FIG. 7 is a schematic system diagram of an apparatus for producing sodium hypochlorite according to a fourth embodiment.

FIG. 8 is a system diagram of a fuel cell unit used in the fifth embodiment.

FIG. 9 is a system diagram of an oxygen concentration adjuster used in the embodiment of the present invention.

FIG. 10 is a system diagram of a fuel cell power generation system according to a sixth embodiment.

FIG. 11 is a schematic system diagram of a humidity adjuster used in the seventh embodiment.

FIG. 12 is a block diagram of a fuel cell power generation system that is supplied with hydrogen gas from a conventional hypochlorite generation device.

FIG. 13 is a block diagram of a fuel cell power generation system that is supplied with hydrogen gas from a conventional hypochlorite generator.

FIG. 14 is a block diagram of an electrolytic cell of a conventional hypochlorite generator.

[Explanation of symbols]

30 electrolyzer 50 cooler 54 Hypochlorite receiving tank 58 Hypochlorite storage tank 85 Temperature detector 86 Gas scrubber 86a Gas scrubber 87 arithmetic unit 89 Temperature detector 91 Polymer functional materials 100 gas purification equipment 102 Hypochlorite generator 104 fuel cell 106 electrolyzer 108 Hypochlorite receiving tank 110 demister 111 Electric power switching device 112 Activated carbon adsorption tower 113 control device 114 oxygen concentration adjuster 116 Cooling device 119 precious metal catalyst 120 humidity controller 122 Humidity controller 124 Hydrogen storage device 126 Cleaning solution tank 144 Regeneration Gas Heater 154 Heated regeneration gas 160 coolant tank 170 solar power generation equipment 172 Wind power generation equipment 180 heat exchanger 190 Hydrogen storage device 198 Coolant tank 200 fuel cell unit 202 DC / DC converter 204 grid-connected inverter 206 system power supply 208 load 214 air

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) // H01M 8/10 H01M 8/10 (72) Inventor Noboru Makita 11-1 Haneda Asahi-cho, Ota-ku, Tokyo Eri Co., Ltd. In-house (72) Inventor Su Keisen 11-1 Haneda-Asahi-cho, Ota-ku, Tokyo F-term in Ebara Corporation (reference) 4K021 AA01 AB07 BA02 BA03 DC03 DC15 5H026 AA06 5H027 AA02 BA11 BA14 BA16 MM26

Claims (13)

[Claims] 1. A fuel cell power generation system, which is supplied with hydrogen gas from a hypochlorite generation device; wherein by-product gas containing hydrogen gas as a main component is generated in an electrolytic cell by an electrolysis step. A chlorate generator; a gas scrubber that removes impurities from the by-product gas sent from the hypochlorite generator to pass hydrogen gas; an oxidant gas and a gas scrubber sent from the gas scrubber A fuel cell power generation system that receives a supply of hydrogen gas from a hypochlorite generator, the fuel cell generating power by an electrochemical reaction with hydrogen gas. 2. The hypochlorite generator according to claim 1, further comprising an oxygen concentration adjuster arranged between the gas scrubber and the fuel cell to adjust the oxygen concentration of the by-product gas. Fuel cell power generation system that receives hydrogen gas supply from the company. 3. The supply of hydrogen gas from the hypochlorite generator according to claim 1, wherein the DC voltage output from the output terminal of the fuel cell is used as a power source of the hypochlorite generator. Fuel cell power generation system. 4. The cathode cleaning solution in the electrolytic cell is sent to the gas cleaning device and used as a gas cleaning solution.
A fuel cell power generation system that receives the supply of hydrogen gas from the hypochlorite generator described in 1. 5. The hypochlorite generator according to claim 2, further comprising a humidity adjuster arranged between the oxygen concentration adjuster and the fuel cell to adjust the humidity of the hydrogen gas. Fuel cell power generation system that receives gas supply. 6. The humidity adjuster has first and second humidity adjusters, and the first humidity adjuster is stopped and the second humidity adjuster is stopped.
In the state in which the humidity controller of
6. The fuel cell power generation system which receives supply of hydrogen gas from the hypochlorite generation device according to claim 5, wherein a regeneration heat source for recovering the function of the humidity controller of claim 5 is supplied from exhaust heat of the fuel cell. 7. The humidity adjuster has first and second humidity adjusters, and the first humidity adjuster is stopped and the second humidity adjuster is stopped.
In the state in which the humidity controller of
The fuel cell power generation system which receives supply of hydrogen gas from the hypochlorite generation device according to claim 5, wherein a regeneration heat source for recovering the function of the humidity controller of claim 5 is supplied from cooling exhaust heat of the electrolytic cell. 8. A fuel cell power generation system, which is supplied with hydrogen gas from a hypochlorite generation device; a hypo-gas which mainly produces hydrogen gas in an electrolytic cell in an electrolysis step. A chlorate generator; a gas scrubber that removes impurities from the by-product gas sent from the hypochlorite generator and allows hydrogen gas to pass therethrough; an electrochemical of oxidant gas and hydrogen gas A fuel cell power generation system that receives supply of hydrogen gas from a hypochlorite generation device, comprising: a fuel cell that generates power by a reaction; and a water supply device that supplies pure water generated from the fuel cell to the electrolytic cell. 9. The hypochlorite generator according to claim 8, further comprising an oxygen concentration adjuster arranged between the gas scrubber and the fuel cell to adjust the oxygen concentration of the by-product gas. Fuel cell power generation system that receives hydrogen gas supply from the company. 10. A fuel cell power generation system that receives hydrogen gas supplied from a hypochlorite generator; a hypochlorite generator that generates hydrogen gas from an electrolytic cell in an electrolysis process; and an oxidizer. A fuel cell for generating electricity by an electrochemical reaction between gas and hydrogen gas delivered from the hypochlorite generator; first electric power converted from a natural energy source including wind or sunlight; and A fuel cell power generation system for receiving hydrogen gas from a hypochlorite generation device, the power switching device selectively supplying second power generated from the fuel cell to the hypochlorite generation device; system. 11. A fuel cell power generation system which is supplied with hydrogen gas from a hypochlorite generator; a hypochlorite generator which generates hydrogen gas from an electrolytic cell by an electrolysis step; A hydrogen storage device that reacts with hydrogen gas delivered from a chlorite generation device to store hydrogen; a fuel cell that generates electricity by an electrochemical reaction between an oxidant gas and hydrogen gas taken out from the hydrogen storage device Storing the hydrogen delivered from the hypochlorite generator operated by commercial power in the hydrogen storage device at night, extracting hydrogen gas from the hydrogen storage device at times other than the night time, and the fuel cell And a power supply for generating electric power from the fuel cell and supplying the electric power output from the fuel cell to the hypochlorite generator. Pond power generation system. 12. The hydrogen storage device includes a hydrogen storage alloy that absorbs hydrogen by reacting with the hydrogen gas, and supplies a heat source for extracting hydrogen from the hydrogen storage alloy from cooling exhaust heat of the electrolytic cell. 11. A fuel cell power generation system that receives supply of hydrogen gas from the hypochlorite generator according to item 11. 13. The hydrogen storage device according to claim 11, comprising a hydrogen storage alloy that absorbs hydrogen by reacting with the hydrogen gas, and supplies a heat source for extracting hydrogen from the hydrogen storage alloy from exhaust heat of a fuel cell. A fuel cell power generation system receiving hydrogen gas from the described hypochlorite generator.