KR20180096042A - The fuel cell system for submarine - Google Patents

Abstract

A fuel cell system for a submarine is provided. The fuel cell system for a submarine comprises: a reactant storage tank for storing a reactant for a hydrolysis reaction for generating hydrogen; a reactor receiving the reactant from the reactant storage tank and generating hydrogen through a hydrolysis reaction; a separator for receiving a synthesis gas from the reactor to separate hydrogen; a fuel cell for receiving hydrogen separated in the separator to convert chemical energy into electric energy; a reaction water collection tank for recovering and collecting reaction water present in an exhaust gas discharged from the fuel cell; a byproduct storage tank for storing a byproduct generated in the reactor; and a cooler for storing a coolant supplied to the fuel cell. The coolant passing through the fuel cell through a coolant line is supplied to the reactor to maintain a temperature of the reactor within a predetermined range.

Description

[0001] The fuel cell system for submarine [

The present invention relates to a fuel cell system for a submarine. More particularly, the present invention relates to a fuel cell system for a submarine capable of maintaining the temperature of a reactor provided in a fuel cell system within a predetermined range to prevent an exothermic reaction caused by reaction byproducts from being disturbed.

Recently, a fuel cell system has been developed to solve the problems caused by the use of fossil fuels. Fuel cells have less air pollutant emission than conventional fossil fuels, and have a low fuel consumption due to high efficiency, The stability of vibration is also high, so much research and development are being done.

A fuel cell is a fuel cell that uses the chemical reaction energy of hydrogen and oxygen contained in a hydrocarbon-based material such as LNG (liquefied natural gas), LPG (liquefied petroleum gas), methanol (CH3OH), ethanol (C2H5OH) The electric power is converted into direct electric energy. Electrochemical reaction, which is the reduction reaction of oxygen, which is an oxidizer, is performed on the cathode and the oxidation reaction of hydrogen, which is a fuel, is performed on the anode, generates electricity, heat and water .

The fuel cell is classified into a phosphoric acid type fuel cell, a molten carbonate type fuel cell, a solid oxide type fuel cell, a polymer electrolyte membrane type or an alkaline type fuel cell depending on the kind of electrolyte used, and each of these fuel cells is fundamentally the same Although it is operated by the principle, the kind of the fuel used, the suitable operating temperature range of the fuel cell, the catalyst, the electrolyte and the like are different.

The phosphoric acid fuel cell operates at 150-200 ° C, the molten carbonate fuel cell operates at 600-700 ° C, and the solid oxide fuel cell operates at 1000 ° C or higher , The polymer electrolyte membrane type fuel cell operates at a temperature of from room temperature to 100 ° C or less.

Korean Patent Laid-Open No. 10-2012-0114983 (Publication date October 17, 2012)

SUMMARY OF THE INVENTION The object of the present invention is to provide a process for producing hydrogen by hydrolyzing stable NaBH ₄ in a hydride, And to provide a fuel cell system for a submarine capable of increasing the yield.

It is to be understood, however, that the technical scope of the present invention is not limited to the above-described embodiments, but may be variously modified without departing from the technical spirit and scope of the present invention.

According to an aspect of the present invention, there is provided a sub fuel cell system for a submarine, comprising: a reactant storage tank for storing a reactant for a hydrolysis reaction for generating hydrogen; A separator for separating hydrogen by receiving a synthesis gas from the reactor, a fuel cell for converting chemical energy into electrical energy by receiving hydrogen separated from the separator, A reaction water collection tank for collecting and collecting the reaction water present in the exhaust gas, a byproduct storage tank for storing the byproducts generated in the reactor, and a cooler for storing the cooling water supplied to the fuel cell, The cooling water passing through the fuel cell is supplied to the reactor, It maintains the temperature within a predetermined range.

In an embodiment according to the present invention, the reactant storage tank may store an aqueous NaBH ₄ solution.

In an embodiment according to the present invention, the reactant storage tank stores a liquid aqueous HCl solution, and the reactor may store solid NaBH ₄ .

In an embodiment according to the present invention, the temperature of the reactor can be maintained within a temperature range that prevents gel formation of the by-product as a result of the hydrolysis reaction.

In an embodiment according to the present invention, the reactivity can be improved by providing a metal catalyst into the reactor.

In an embodiment according to the present invention, seawater is supplied to the cooler so that the temperature of the coolant stored in the cooler can be kept within a predetermined range.

In an embodiment according to the present invention, the apparatus may further comprise a valve for providing fresh water to the reactor and a control device for controlling the valve.

In an embodiment according to the present invention, the control device may open the valve at the time of the temperature rise at the rear end of the reactor to supply clean water to the reactor.

In an embodiment according to the present invention, the control device can measure the temperature of the rear end of the reactor, the rear end of the fuel cell, and the rear end of the cooler.

Other specific details of the invention are included in the detailed description and drawings.

It is necessary to generate hydrogen for supply to the fuel cell in the submarine using the fuel cell. According to the present invention, the temperature of the reactor provided in the fuel cell system is maintained within a predetermined range to stably generate hydrogen .

Further, according to the present invention, it is possible to prevent the reaction rate and the yield from lowering due to by-products of the hydrolysis reaction.

However, the effects of the present invention are not limited to the above effects, and can be variously extended without departing from the spirit and scope of the present invention.

1 is a schematic block diagram of a fuel cell system according to an embodiment of the present invention.
2 is a schematic block diagram of a fuel cell system according to another embodiment of the present invention.
3 is a schematic block diagram of a fuel cell system according to another embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and the manner of achieving them, will be apparent from and elucidated with reference to the embodiments described hereinafter in conjunction with the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. It is noted that the terms "comprises" and / or "comprising" used in the specification are intended to be inclusive in a manner similar to the components, steps, operations, and / Or additions.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The same reference numerals are used for the same constituent elements in the drawings and redundant explanations for the same constituent elements are omitted.

A chemical cell is a device that converts energy changes when a chemical change occurs into electrical energy. Generally, a chemical cell performs a chemical reaction by putting an electrode and an electrolyte into a container. However, the cell continuously supplies hydrogen and oxygen from the outside and continuously generates electric energy.

This is similar to burning a mixture of fuel and air into the engine. A chemical cell similar to the combustion of fuel is called a fuel cell. The hydrogen supplied to the fuel cell is not burned, but the oxidation / reduction reaction for exchanging electrons in the aqueous solution proceeds, and hydrogen and oxygen are converted into water in the process. The energy at this time is converted into electric energy.

The present invention relates to a fuel cell system using a solid fuel containing a hydrogen atom, which generates hydrogen through a hydrolysis reaction between a solid fuel and water, cooling the heat generated by the hydrolysis reaction, And more particularly to a fuel cell system having a reactor capable of maintaining a high temperature.

In order to maximize the confidentiality of a submarine, it is necessary to have a capability of long-term submersion. A conventional submarine is a combination of a battery, a diesel engine, and a generator. However, since submarines using air independent propulsion (AIP) have a longer diving time than a submarine, have.

These airless systems (AIPs) include various energy conversion devices such as MESMA, sterling, and fuel cells. Among them, fuel cells are devices that convert the chemical energy of hydrogen into electrical energy and are often applied to submarines because they are more energy efficient than other devices.

A method of storing and supplying hydrogen, which is a fuel applied to the fuel cell, is a problem. Examples of methods for storing hydrogen include high pressure compression storage, liquefaction storage, hydrogen storage alloy, and hydride storage method.

Compressed storage of high pressure requires a high storage pressure of over 350 atmospheres. However, there is a safety problem to be applied to sealed submarines. Liquefaction storage has a high storage density, but has a high energy consumption for liquefaction at a low temperature of -252.7 degrees A separate device for treating or preventing boil-off gas, which is generated continuously during storage, is required.

Hydrogen storage alloys have a high hydrogen mass ratio per volume, but they are heavier than other systems. On the other hand, the hydride storage method has a hydrogen content of 10.8 wt% and can be stored in a stable state in a basic solution and has a characteristic of easily generating hydrogen through a catalyst or an acidic solution, Do.

1 is a schematic block diagram of a fuel cell system according to an embodiment of the present invention.

1, a fuel cell system according to an embodiment of the present invention includes a reactant storage tank 10, a reactor 20, a separator 30, a fuel cell 40, a reaction water collection tank 50, A byproduct storage tank 60, and a cooler 70.

The present invention utilizes NaBH ₄ , which can be used as a stable fuel among hydrides. These NaBH ₄ reacts in liquid form and solid form to generate hydrogen.

The reactant storage tank 10 stores a reactant for the hydrolysis reaction to generate hydrogen. The reactor 20 receives the reactant from the reactant storage tank 10 and generates hydrogen through a hydrolysis reaction. The separator 30 receives synthesis gas from the reactor 20 to separate the hydrogen. The fuel cell 40 receives the separated hydrogen from the separator 30 and converts chemical energy into electric energy. The reaction water collection tank 50 collects and collects the reaction water present in the exhaust gas discharged from the fuel cell 40. The byproduct storage tank (60) stores the byproducts generated in the reactor (20). The cooler 70 stores cooling water supplied to the fuel cell 40.

The present invention is characterized in that the cooling water that has passed through the fuel cell 40 through the cooling water line is supplied to the reactor 20 to maintain the temperature of the reactor 20 within a predetermined range. This is because the hydrolysis reaction in the reactor 20 is an exothermic reaction and therefore it is necessary to keep the temperature within a predetermined range for controlling the reaction rate.

Here, the reagent stored in the reagent storage tank 10 is NaBH ₄ Aqueous solution. When NaBH ₄ is stored in a liquid form, NaBH ₄ is stored in a stable form together with the basic solution and reacts with water as follows to generate an exothermic reaction and produce hydrogen and byproducts.

NaBH ₄ + 2H ₂ O → NaBO ₂ + 4H ₂ + Heat

At this time, when the catalyst is reacted with water without water, only 35% of the theoretical amount of hydrogen is generated, but a noble metal catalyst such as Ru, Pd, Pt or Pt-Pd or a transition metal catalyst such as CO-B or Ni-B And the yield can be increased by increasing the reactivity.

Thus, in the reactor 20, a noble metal catalyst or a transition metal catalyst may be provided to improve the reactivity.

The exothermic reaction occurs in the forward direction when the ambient temperature is lowered by the Le Chatlie's law, but the by-product generated in the reaction exists in the form of a gel, and the by-product obstructs the contact between the reactant and the catalyst, thereby hindering the exothermic reaction. In order to prevent this, the internal temperature of the reactor 20 is maintained within a predetermined temperature range in which gel formation can be prevented.

2 is a schematic block diagram of a fuel cell system according to another embodiment of the present invention.

2, the fuel cell system according to another embodiment of the present invention includes a reactant storage tank 10, a reactor 20, a separator 30, a fuel cell 40, a reaction water collection tank 50, A byproduct storage tank 60, and a cooler 70. Hereinafter, the overlapping description with the constituent elements described above will be omitted.

The reactants stored in the reactant storage tank 10 may be HCl aqueous solutions. In the reactor 20, solid state NaBH ₄ can be stored. In this case, an acidic solution is added to NaBH ₄ to proceed the reaction to produce hydrogen and by-products as follows.

NaBH ₄ + (HCl + 3H ₂ O) - > NaCl + H ₃ BO ₃ + 4H ₂ + Heat

Since the reaction is an exothermic reaction, in order to control the reaction rate, the temperature in the reactor 20 must be maintained within a predetermined range, and a cooler 70 is required for this purpose.

The exothermic reaction occurs in the forward direction when the ambient temperature is lowered by the Lechardlier's law, but the by-product generated in the reaction is in the form of a gel, thereby preventing the byproduct from contacting the reactant, the catalyst and the acidic substance It inhibits the exothermic reaction. In order to prevent this, the internal temperature of the reactor 20 is maintained within a predetermined temperature range in which gel formation can be prevented.

Although the fuel cell 40 has various types such as a PEMFC, an MCFC, and an SOFC, the operating temperature must be constant for the fuel cell 40 to operate stably. Accordingly, the cooling water is supplied to the fuel cell 40, and the cooling water supply temperature is kept close to the operating temperature of the fuel cell 40.

The submarine supplies cooling water that is 5 to 7 degrees lower than the operating temperature of the fuel cell (40). The cooling water heated after the cooling of the fuel cell 40 can transmit heat energy to a place where a heat source is required as well as supplying the heat source necessary for the hydrogen storage alloy of the submarine.

Thus, the heated cooling water after the cooler (70) necessary to constitute the fuel cell system of the NaBH ₄ according to the present invention, the fuel cools the fuel cell 40 in conjunction with the fuel cell 40 NaBH ₄ singer The reaction temperature and the gelation of the by-products can be prevented, so that the reaction rate and the yield can be increased.

3 is a schematic block diagram of a fuel cell system according to another embodiment of the present invention.

Referring to FIG. 3, the fuel cell system according to another embodiment of the present invention includes a reactant storage tank 10, a reactor 20, a separator 30, a fuel cell 40, a reaction water collection tank 50, A byproduct storage tank 60, a cooler 70, a valve 80, and a control device 90. Hereinafter, the overlapping description with the constituent elements described above will be omitted.

The reactants stored in the reactant storage tank 10 may be HCl aqueous solutions. In the reactor 20, solid state NaBH ₄ can be stored. In this case, an acidic solution is added to NaBH ₄ to proceed with the reaction to produce hydrogen and by-products as follows.

NaBH ₄ + (HCl + 3H ₂ O) - > NaCl + H ₃ BO ₃ + 4H ₂ + Heat

Since the reaction is an exothermic reaction, in order to control the reaction rate, the temperature in the reactor 20 must be maintained within a predetermined range, and a cooler 70 is required for this purpose.

The exothermic reaction occurs in the forward direction when the ambient temperature is lowered by the Lechardlier's law, but the by-product generated in the reaction is in the form of a gel, thereby preventing the byproduct from contacting the reactant, the catalyst and the acidic substance It inhibits the exothermic reaction. In order to prevent this, the internal temperature of the reactor 20 is maintained within a predetermined temperature range in which gel formation can be prevented.

The valve 80 provides pure water to the reactor 20. The control device 90 controls the valve 80 and controls the opening / closing of the valve 80 to regulate the fresh water supplied to the reactor 20.

Specifically, the control device 90 can open the valve 80 at the time of the temperature rise at the rear end of the reactor 20 to supply the fresh water to the reactor 20. The control device 90 can also measure the temperature of the downstream end of the reactor 20, the downstream end of the fuel cell 40, and the downstream end of the cooler 70 and controls the operation of the valve 80 based on the measured temperature .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And the like.

10: Reactant storage tank
20: Reactor
30: separator
40: Fuel cell
50: Reaction water collection tank
60: Byproduct storage tank
70: cooler
80: Valve
90: Control device

Claims (9)

A reactant storage tank for storing a reactant for the hydrolysis reaction to generate hydrogen;
A reactor for receiving the reactant from the reactant storage tank and generating hydrogen through a hydrolysis reaction;
A separator for separating hydrogen by receiving synthesis gas from the reactor;
A fuel cell that converts the chemical energy into electric energy by receiving hydrogen separated from the separator;
A reaction water collection tank for collecting and collecting reaction water present in the exhaust gas discharged from the fuel cell;
A byproduct storage tank for storing byproducts generated in the reactor; And
And a cooler for storing cooling water supplied to the fuel cell,
Wherein the cooling water passing through the fuel cell is supplied to the reactor through a cooling water line to maintain the temperature of the reactor within a predetermined range. The method according to claim 1,
The reaction storage tank, the fuel cell system for storing the NaBH ₄ solution in a liquid state, and submarines. The method according to claim 1,
The reactant storage tank stores an aqueous solution of HCl in a liquid state,
Wherein the solid-state NaBH ₄ is stored in the reactor. The method according to claim 1,
Wherein the temperature of the reactor is maintained within a temperature range that prevents gel formation of byproducts due to the hydrolysis reaction. The method according to claim 1,
Wherein the metal catalyst is provided in the reactor to improve reactivity. The method according to claim 1,
Wherein the cooler is supplied with seawater to maintain the temperature of the coolant stored in the cooler within a predetermined range. The method according to claim 1,
Further comprising a valve for providing clean water to the reactor and a control device for controlling the valve. 8. The method of claim 7,
Wherein the control device opens the valve at the time of temperature rise at the rear end of the reactor to supply clean water to the reactor. 9. The method of claim 8,
Wherein the controller measures the temperature of the rear end of the reactor, the rear end of the fuel cell, and the rear end of the cooler.

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