JP5148164B2 - Liquid fuel processing apparatus and fuel cell power generation system - Google Patents

Description

  The present invention relates to a liquid fuel processing apparatus having a desulfurization apparatus and a reformer, and a fuel cell power generation system using the same.

  Desulfurization equipment for polymer electrolyte fuel cell power generation systems that use liquid fuel containing sulfur such as kerosene performs desulfurization treatment before introducing liquid fuel into the reforming catalyst, and the sulfur content in liquid fuel is below the allowable concentration Need to be removed. Without this desulfurization treatment, the reforming catalyst that performs the reforming reaction for purifying hydrogen is exposed to the sulfur content in the liquid fuel, resulting in sulfur poisoning, the reforming performance is degraded, and the life is shortened.

  Generally, there is a suitable operating temperature range for the desulfurization process and the desulfurizing agent is heated to this temperature range. Furthermore, in this temperature range, a part of the liquid fuel is vaporized and the flow control of the liquid fuel becomes unstable. Therefore, it is necessary to pressurize the liquid fuel so as not to vaporize and maintain a high pressure state.

  As a method of keeping the desulfurization vessel in an appropriate temperature range, a method of heating the desulfurization vessel itself with an electric heater, or as disclosed in Patent Document 1, heating the desulfurization vessel using burner combustion exhaust gas, Methods have been proposed to maintain the temperature range.

Further, before the liquid fuel is distributed to the desulfurization vessel, the liquid fuel preheater is heated by an electric heater or burner combustion exhaust gas, and is supplied to the desulfurization vessel, thereby maintaining the liquid fuel in an appropriate temperature range. For example, Patent Document 2 proposes a method in which a pipe through which liquid fuel flows is attached so as to surround a desulfurization vessel and preheated together with the desulfurization vessel with an electric heater or heated steam.
JP 2005-255896 A JP 2004-263118 A

  In order to improve the desulfurization performance, the desulfurization vessel of the desulfurization apparatus needs to maintain a high temperature and high pressure state during operation. Conventionally, it is heated by an electric heater or a burner exhaust gas from a reformer.

  In the method of directly heating the liquid fuel desulfurization vessel with an electric heater, the temperature distribution in the desulfurization vessel tends to be increased, and when the temperature rises locally above the appropriate temperature range, hydrogen is used as a by-product of the desulfurization reaction. Gases such as methane and methane are produced, resulting in a two-phase state with desulfurized liquid kerosene. If the pressure is reduced before flowing into the reformer, the gas such as hydrogen and methane expands and the flow rate of the liquid fuel fluctuates. Therefore, the flow rate control becomes unstable and stable operation is possible. It can be difficult.

  Also, when heating with the exhaust gas from the reformer of the fuel cell power generation system, the temperature distribution is uniform, but the proper operating temperature of the desulfurization device from normal temperature, such as when starting the fuel cell power generation system, etc. It takes a long time to heat up to 2 because the amount of heat is insufficient.

  There is also a method of raising the temperature of the desulfurization vessel by heating the exhaust gas with an electric heater, but the exhaust gas at a higher temperature than the exhaust gas temperature that was conventionally discharged will eventually be discharged, so the energy efficiency is poor. Become.

  In view of the above problems, an object of the present invention is to provide a liquid fuel processing apparatus that can be operated in a state where the flow control of liquid fuel is more stable and that is excellent in energy efficiency, and a fuel cell power generation system that uses the liquid fuel processing apparatus. It is to be.

In order to achieve the above object, a liquid fuel processing apparatus according to the present invention includes a desulfurization apparatus that desulfurizes liquid fuel, and a reformer that reforms the fuel desulfurized by the desulfurization apparatus to be rich in hydrogen. In the apparatus, the desulfurization apparatus includes a desulfurization unit that stores a desulfurization agent that desulfurizes sulfur contained in the liquid fuel, and an electric heater that is disposed upstream of the desulfurization unit and preheats the liquid fuel , A preheating part integrally formed with the desulfurization part, and a heating container that is arranged so as to surround at least the desulfurization part of the desulfurization container and circulates a heating medium for heating the desulfurization part. To do.
The liquid fuel processing apparatus according to the present invention includes a desulfurization apparatus that desulfurizes the liquid fuel, and a reformer that reforms the fuel desulfurized by the desulfurization apparatus to be rich in hydrogen. The apparatus includes a desulfurization unit that contains a desulfurization agent that desulfurizes sulfur contained in the liquid fuel, a preheating unit that is disposed upstream of the desulfurization unit and includes an electric heater that preheats the liquid fuel, and the desulfurization unit. And a desulfurization container that collectively accommodates the preheating part, and a heating container that is disposed so as to surround at least the desulfurization part of the desulfurization container and circulates a heating medium for heating the desulfurization part. A container surrounds the preheating part, the heating medium is configured to preheat the liquid fuel, and the desulfurization part is arranged to surround the preheating part.

The fuel cell power generation system according to the present invention includes a desulfurization device that desulfurizes liquid fuel, a reformer that reforms the fuel desulfurized by the desulfurization device to be rich in hydrogen, and the reformer that is reformed. In the fuel cell power generation system having a fuel cell main body to which fuel is supplied, the desulfurization device is disposed on the upstream side of the desulfurization unit and a desulfurization unit that stores a desulfurization agent that desulfurizes sulfur contained in the liquid fuel. A preheating part integrally formed with the desulfurization part, a desulfurization container that collectively accommodates the desulfurization part and the preheating part, and at least the desulfurization part of the desulfurization container And a heating container for circulating a heating medium for heating the desulfurization part.

  According to the present invention, the temperature distribution in the desulfurization section is made uniform, and the production of by-products that cause flow rate fluctuations can be suppressed, so that operation with more stable flow control of liquid fuel becomes possible.

  In addition, since the amount of heat released to the outside of the desulfurization vessel is reduced by circulating the heating medium through the heating vessel disposed so as to surround the desulfurization vessel, it is possible to provide a liquid fuel processing apparatus with excellent energy efficiency. .

  Hereinafter, although an embodiment is described about the present invention using a drawing, the present invention is not limited by this. In addition, the same code | symbol is attached | subjected to the same part or a similar part, and duplication description is abbreviate | omitted.

[First Embodiment]
FIG. 1 is a system diagram showing a first embodiment of a liquid fuel processing apparatus according to the present invention, and is a configuration diagram of the liquid fuel processing apparatus including a desulfurization apparatus.

  The liquid fuel processing apparatus of this embodiment includes a desulfurization apparatus 1 that desulfurizes a liquid fuel 16 containing sulfur such as kerosene, a reformer 7 that reforms the desulfurized liquid fuel 16 to be rich in hydrogen, and carbon monoxide. The carbon monoxide transformer 8, the carbon monoxide remover 9, and the heat exchanger 10 are the main components.

  The flow path of the liquid fuel 16 of this embodiment will be described below.

  The liquid fuel 16 is first supplied from the liquid fuel tank 12 and is not vaporized even when heated by the liquid fuel pump 11 to a temperature range suitable for desulfurization. The desulfurization vessel 2 is pressurized while being pressurized at 0.3 MPa to 0.6 MPa. The preheating part 3 is entered.

  After being heated to a temperature range suitable for desulfurization by an electric heater 14 attached to the preheating unit 3, the desulfurization unit 4 is entered. In addition, since the preheating part 3 and the desulfurization part 4 are integrated, there is almost no heat dissipation loss in the meantime.

  The liquid fuel 16 desulfurized in the desulfurization unit 4 exits the pressure regulating valve 13, is depressurized to normal pressure, is mixed with the water vapor 20, and is supplied to the reformer 7. Quality. The reformed gas 19 is reduced in carbon monoxide contained in the gas to several percent by a shift reaction in the carbon monoxide converter 8, further added with air, and cooled by the reforming water 18 in the heat exchanger 10. It is sent to the carbon monoxide remover 9. The reformed gas 19 is reduced in carbon monoxide to several ppm or less by a selective oxidation reaction in the carbon monoxide remover 9 and then supplied to the fuel cell 30.

  The reforming water 18 is heated by the heat exchanger 10 and further heated by an evaporation section (not shown) of the reformer 7 to be mixed with the liquid fuel 16 as water vapor 20 to be reformed catalyst of the reformer 7. Sent to a layer (not shown).

  The heating vessel 5 arranged so as to surround the desulfurization part 4 of the desulfurization vessel 2 keeps the operating temperature of the desulfurizing agent 6 in a temperature range suitable for desulfurization by circulating the heating medium, and the outside of the desulfurization apparatus 1. Suppresses heat dissipation.

  In the present embodiment, the burner combustion exhaust gas 17 coming out from the combustion chamber (not shown) of the reformer 7 is used as the heating medium flowing through the heating container 5.

  FIG. 2 is a schematic longitudinal sectional view showing in more detail the structure of the desulfurization apparatus 1 shown in FIG. The liquid fuel 16 enters the preheating unit 3 from the liquid fuel inlet 16 a and is heated by the electric heater 14 attached to the preheating unit 3 and enters the desulfurization unit 4. The liquid fuel 16 desulfurized in the desulfurization unit 4 flows from the liquid fuel outlet 16b to the outside of the desulfurization apparatus 1.

  The desulfurization apparatus 1 is attached so as to surround at least the desulfurization part 4 of the desulfurization container 2 and the desulfurization container 2 in which the desulfurization part 4 and the preheating part 3 are integrated, and a heating container serving as a flow path for the heating medium 5 is the main component. The shape of the desulfurization vessel 2 of the desulfurization apparatus 1 may be cylindrical or rectangular. In this embodiment, a cylindrical shape is adopted. The flow path of the heating medium is formed so as to enter from the heating medium inlet 5a of the heating container 5 and to be exhausted from the heating medium outlet 5b.

  An electric heater 14 is attached to the preheating unit 3 as preheating means, and the liquid fuel 16 sent from the liquid fuel pump 11 is a thermocouple 15 for temperature measurement attached to the preheating unit 3 of the desulfurization vessel 2. Is heated by the electric heater 14 until it becomes 200 ° C. or higher and 260 ° C. or lower which is a temperature range appropriate for desulfurization.

[Second Embodiment]
FIG. 3 is a system diagram showing a second embodiment of the liquid fuel processing apparatus according to the present invention, and is a configuration diagram of the liquid fuel processing apparatus.

  The liquid fuel processing apparatus of this embodiment includes a desulfurization apparatus 1 that desulfurizes the liquid fuel 16, a reformer 7, a carbon monoxide converter 8, and a carbon monoxide removal that reform the desulfurized liquid fuel 16 to be rich in hydrogen. The vessel 9 is the main component. As the desulfurization apparatus 1, the desulfurization apparatus 1 shown in FIG. 2 of the first embodiment is applied.

  The flow path of the liquid fuel 16 of this embodiment will be described below.

  The liquid fuel 16 is first supplied from the liquid fuel tank 12 and is not vaporized even when heated by the liquid fuel pump 11 to a temperature range suitable for desulfurization. The desulfurization vessel 2 is pressurized while being pressurized at 0.3 MPa to 0.6 MPa. The preheating part 3 is entered. After being heated to a temperature range suitable for desulfurization by an electric heater 14 attached to the preheating unit 3, the desulfurization unit 4 is entered. The liquid fuel 16 desulfurized in the desulfurization unit 4 exits the pressure regulating valve 13, is depressurized to normal pressure, is mixed with the water vapor 20, and is supplied to the reformer 7. Quality. The reformed gas 19 is reduced to several percent of carbon monoxide by the carbon monoxide transformer 8 and supplied to the heating vessel 5 of the desulfurization apparatus 1. Further, air is added and carbon monoxide is reduced to several ppm or less by a selective oxidation reaction in the carbon monoxide remover 9 and then supplied to the fuel cell 30.

  In the present embodiment, a reformed gas 19 at, for example, about 200 ° C. at the outlet of the carbon monoxide converter 8 is used as a heating medium that circulates in the heating vessel 5 attached to the desulfurization apparatus 1.

  In this case, since the reformed gas 19 does not flow when the operation is started, the liquid fuel 16 needs to be heated only by the electric heater 14 attached to the preheating unit 3. However, during the operation of the liquid fuel processing apparatus, desulfurization is performed. It is possible to flow in the reformed gas 19 at a temperature that can maintain a temperature range suitable for the above.

  In addition, after the reformed gas 19 has passed through the heating container 5, the temperature is lower than the reformed gas 19 when not applied as a heating medium due to heat recovery in the heating container 5. Since it is sent to the carbon monoxide remover 9, the heat exchanger 10 (FIG. 1) installed between the carbon monoxide transformer 8 and the carbon monoxide remover 9 can be eliminated, and space saving is possible.

[Third Embodiment]
FIG. 4 is a system diagram showing a third embodiment of the liquid fuel processing apparatus according to the present invention, and is a configuration diagram of the liquid fuel processing apparatus. The main components of this embodiment are the same as those of the first embodiment, and the desulfurization apparatus 1 employs the desulfurization apparatus 1 shown in FIG.

  The flow path of the liquid fuel 16 of this embodiment is the same as that of the first embodiment.

  In the present embodiment, the steam 20 necessary for reforming that has come out from the reformer 7 is used as a heating medium that circulates in the heating vessel 5 attached to the desulfurization apparatus 1. The water vapor 20 is superheated steam of about 200 ° C., for example.

[Fourth Embodiment]
FIG. 5 is a schematic longitudinal sectional view showing a desulfurization apparatus 1 in a fourth embodiment of the liquid fuel processing apparatus according to the present invention. The desulfurization apparatus 1 shown in the present embodiment is incorporated in the system diagram shown in FIG. 1 of the first embodiment.

  By attaching the heating container 5 so as to surround the preheating unit 3, the heating medium is configured to preheat the liquid fuel 16. In the present embodiment, the heating medium flow path is formed so as to enter from the heating medium inlet 5a of the heating container 5 and exhaust from the heating medium outlet 5b, and after heating the desulfurization unit 4, the preheating unit 3 is heated. It is configured.

  Furthermore, it is possible to enhance the preheating effect of the liquid fuel 16 by heating with the electric heater 14 attached to the preheating unit 3. In this case, it is possible to reduce the output of the electric heater 14 as compared to heating the electric heater 14 alone.

[Fifth Embodiment]
FIG. 6 is a schematic longitudinal sectional view showing a desulfurization apparatus 1 in a fifth embodiment of the liquid fuel processing apparatus according to the present invention. 7 is a plan view taken along line VII-VII in FIG. 6, and FIG. 8 is a cross-sectional view taken along line VIII-VIII in FIG. The desulfurization apparatus 1 shown in the present embodiment is incorporated in the system diagram shown in FIG. 1 of the first embodiment.

  In the desulfurization apparatus 1 in the present embodiment, the desulfurization part 4 is formed in an annular shape having a hollow part 22 in the heating vessel 5. A liquid fuel preheating pipe 21 is arranged in the preheating unit 3 so as to pass through the hollow portion 22 of the desulfurization unit 4 and reach the desulfurization unit 4.

  The liquid fuel 16 enters from the liquid fuel inlet 16a, passes through the liquid fuel preheating pipe 21, is supplied to the desulfurization unit 4, and flows from the liquid fuel outlet 16b to the outside.

  The flow path of the heating medium enters from the heating medium inlet 5a, passes through the hollow portion 22 of the desulfurization section 4, passes through the heating container 5 outside the desulfurization section 4, and is exhausted from the heating medium outlet 5b. Yes.

  In the present embodiment, when the liquid fuel 16 is heated by the electric heater 14 attached to the preheating unit 3, a part of the heat is recovered to the heating medium side, but again for maintaining the temperature of the desulfurization unit 4. Therefore, the heating medium is not discharged outside the desulfurization apparatus 1 while being heated. Therefore, it is possible to efficiently maintain the temperature of the desulfurization unit 4.

[Other Embodiments]
The description of the above embodiment is an example for explaining the present invention, and does not limit the invention described in the claims or reduce the scope. Moreover, each part structure of this invention is not restricted to the said embodiment, A various deformation | transformation is possible within the technical scope as described in a claim.

  For example, the desulfurization apparatus 1 (FIG. 5) shown in 4th Embodiment can be utilized for any system | strain of FIG. 3, FIG. Moreover, the desulfurization apparatus 1 (FIGS. 6 to 8) shown in the fifth embodiment can also be used in any of the systems shown in FIGS.

  Further, the liquid fuel treatment apparatus can be applied to other than the fuel cell power generation system.

1 is a system diagram showing a first embodiment of a liquid fuel processing apparatus according to the present invention. It is a schematic longitudinal cross-sectional view which shows 1st Embodiment of the desulfurization apparatus in FIG. It is a systematic diagram which shows 2nd Embodiment of the liquid fuel processing apparatus which concerns on this invention. It is a systematic diagram which shows 3rd Embodiment of the liquid fuel processing apparatus which concerns on this invention. It is a schematic longitudinal cross-sectional view which shows the desulfurization apparatus in 4th Embodiment of the liquid fuel processing apparatus which concerns on this invention. It is a schematic longitudinal cross-sectional view which shows the desulfurization apparatus in 5th Embodiment of the liquid fuel processing apparatus which concerns on this invention. It is a VII-VII line arrow plan view in FIG. It is a VIII-VIII arrow flat cross-sectional view in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Desulfurization apparatus, 2 ... Desulfurization container, 3 ... Preheating part, 4 ... Desulfurization part, 5 ... Heating container, 5a ... Heating medium inlet, 5b ... Heating medium outlet, 6 ... Desulfurizing agent, 7 ... Reformer, 8 ... Carbon monoxide transformer, 9 ... carbon monoxide remover, 10 ... heat exchanger, 11 ... liquid fuel pump, 12 ... liquid fuel tank, 13 ... pressure regulating valve, 14 ... electric heater, 15 ... thermocouple, 16 ... Liquid fuel, 16a ... Liquid fuel inlet, 16b ... Liquid fuel outlet, 17 ... Burner combustion exhaust gas, 18 ... Reformed water, 19 ... Reformed gas, 20 ... Steam, 21 ... Liquid fuel preheating piping, 22 ... Hollow part, 30 …Fuel cell

Claims (8)

In a liquid fuel processing apparatus having a desulfurization apparatus for desulfurizing liquid fuel and a reformer for reforming the fuel desulfurized by the desulfurization apparatus to be rich in hydrogen,
The desulfurization apparatus includes:
A desulfurization section containing a desulfurization agent for desulfurizing sulfur contained in the liquid fuel;
An electric heater disposed on the upstream side of the desulfurization unit to preheat the liquid fuel, and a preheating unit integrally formed with the desulfurization unit ;
A desulfurization container that collectively accommodates the desulfurization part and the preheating part;
A heating container that is disposed so as to surround at least the desulfurization part of the desulfurization container and distributes a heating medium for heating the desulfurization part;
A liquid fuel processing apparatus characterized by comprising: The liquid fuel processing apparatus according to claim 1, wherein the heating container surrounds the preheating portion, and the heating medium is configured to preheat the liquid fuel. The liquid fuel processing apparatus according to claim 2 , wherein the desulfurization unit is disposed so as to surround the preheating unit . In a liquid fuel processing apparatus having a desulfurization apparatus for desulfurizing liquid fuel and a reformer for reforming the fuel desulfurized by the desulfurization apparatus to be rich in hydrogen,
The desulfurization apparatus includes:
A desulfurization section containing a desulfurization agent for desulfurizing sulfur contained in the liquid fuel;
A preheating unit that is disposed upstream of the desulfurization unit and includes an electric heater that preheats the liquid fuel;
A desulfurization container that collectively accommodates the desulfurization part and the preheating part;
A heating container that is disposed so as to surround at least the desulfurization part of the desulfurization container and distributes a heating medium for heating the desulfurization part;
Have
The heating vessel surrounds the preheating section, and the heating medium is configured to preheat the liquid fuel;
The desulfurization part is arranged so as to surround the preheating part,
A liquid fuel processing apparatus. 5. The liquid fuel according to claim 1, wherein the reformer discharges burner combustion exhaust gas using burner combustion, and the heating medium is the burner combustion exhaust gas. 6. Processing equipment. The fuel cell further includes a carbon monoxide converter for reducing carbon monoxide reformed by the reformer, and the heating medium is a fuel that has exited the carbon monoxide converter. The liquid fuel processing apparatus according to claim 1 or 4 . The liquid according to claim 1 or 4, wherein the reformer discharges using superheated steam, and the heating medium is superheated steam discharged from the reformer. Fuel processor. A desulfurization device for desulfurizing liquid fuel, a reformer for reforming the fuel desulfurized by the desulfurization device to be rich in hydrogen, and a fuel cell main body to which the fuel reformed by the reformer is supplied In the fuel cell power generation system,
The desulfurization apparatus includes:
A desulfurization section containing a desulfurization agent for desulfurizing sulfur contained in the liquid fuel;
An electric heater disposed on the upstream side of the desulfurization unit to preheat the liquid fuel, and a preheating unit integrally formed with the desulfurization unit ;
A desulfurization container that collectively accommodates the desulfurization part and the preheating part;
A heating container that is disposed so as to surround at least the desulfurization part of the desulfurization container and distributes a heating medium for heating the desulfurization part;
A fuel cell power generation system characterized by comprising:

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