KR20110032532A - Fuel cell combined power system using waste gasification process - Google Patents

Abstract

PURPOSE: A fuel cell-combined power system is provided to enable efficient use of heat energy and high generation efficiency using a cracking gas obtained through thermal cracking of combustible wastes as a fuel gas. CONSTITUTION: A fuel cell-combined power system applying a waste gasification process comprises: a combustible waste drying devicefor evaporating the moisture of combustible wastes(100); a pyrolysis device(120) for generating cracking gas through thermally decomposing the dried waste; a gas purifier(130) for removing acidic gas from the cracking gas; a fuel cell(150) for producing electricity by receiving the refined cracking gas from an anode(151); and a catalytic combustor(160) for oxidizing carbon monoxide and the unreacted hydrogen exhausted from the anode together with the air using a fuel catalyst.

Description

Fuel cell cogeneration system using pyrolysis / gasification of wastes {FUEL CELL COMBINED POWER SYSTEM USING WASTE GASIFICATION PROCESS}

The present invention relates to a fuel cell cogeneration system using a pyrolysis / gasification method of waste, and more particularly, to a flammable waste by applying a pyrolysis / gasification process, including H ₂ , CO, CH ₄ , CO ₂ , H ₂ O, Fuel that can be used as fuel by producing various pyrolysis gases such as H ₂ S, HCl, and N ₂ , and supplying the pyrolysis gas to fuel cells such as molten carbonate fuel cell (MCFC) or solid oxide fuel cell (SOFC). The present invention relates to a battery cogeneration system.

Generally, various kinds of combustible wastes such as food wastes emitted from homes and restaurants, organic sludges in various industrial sites, livestock sludges and servings from barns, etc. are polluted with soil and rivers when discharged as they are, and various environmental problems and Cause social problems.

Organic sludge such as sewage sludge, wastewater sludge, food waste, and livestock manure are generated in Korea more than 5 million tons, and these organic sludges are currently recycled as feed, compost, and cover materials. Are going through.

Of these, sewage sludge and wastewater sludge generation is expected to increase with capacity expansion. Sewage sludge can be treated by drying and fueling it and treating it with coal and mixed combustion methods, but wastewater sludge contains various heavy metals and sulfur and chlorine, which are harmful gas generating substances during combustion, and burns directly after drying. There are many restrictions. In addition, since food wastes are subjected to anaerobic digestion, a large amount of residues are generated and contain high concentrations of salts. When these foods are dried and burned, they cause salt corrosion in combustion chambers and heat exchangers.

The treatment method using pyrolysis / gasification of such organic waste is widely used, but until now, the pyrolysis gas produced is combusted to use steam or hot water for industrial or heating, or simply burned and discharged to the outside when it is not geographically feasible. The method was mainly used. As a way to utilize organic surplus energy after stable treatment of organic waste due to the recent surge in fossil energy prices, it is strongly considered that the pyrolysis gas generated after pyrolysis treatment is driven to produce steam and gas turbines for power generation. However, the pyrolysis gas obtained by using the pyrolysis process of the waste is 30 ~ 70% of the calorific value compared to LNG or LPG, so when using a steam turbine, the electricity production efficiency is very low, about 20-25%. However, if the steam turbine is driven by burning LNG or LPG exclusively, power generation efficiency is over 40%.

However, the technology of drying, burning or pyrolysis / gasification of food waste containing chlorine (Cl) component or salt (NaCl) or wastewater sludge containing various heavy metals such as chromium (Cr), mercury and aluminum among organic wastes And due to the difficulty of processing chlorine gas has not been commercialized. Since these wastes have a high water concentration of about 80% in general, a large amount of energy is required for the drying process, which causes a great difficulty due to the high treatment cost.

On the other hand, recently, high efficiency and environmentally friendly fuel cells have been spotlighted as a new electric energy source. A fuel cell has a characteristic of continuously generating power by supplying fuel. The fuel cell mainly uses hydrogen as a fuel and generates water by generating water through oxidation of hydrogen and reduction of oxygen using oxygen in the air.

In particular, a fuel cell such as a molten carbonate fuel cell (MCFC) is a system that generates electricity at a high temperature of 600 ° C. or higher because an electrolyte made of carbonate becomes molten at a high temperature to cause an electrode reaction, which is expensive for hydrogen oxidation and oxygen reduction. No noble metal catalyst is needed. Therefore, it is easy to use a toxic gas such as carbon monoxide, and a mixture of hydrogen and carbon monoxide can be used as a fuel, and high-temperature waste heat can be used, which is characterized by high efficiency.

In addition, solid oxide fuel cell (SOFC) uses oxygen ion transfer zirconia as electrolyte, and the electrode uses nickel oxide and conductive ceramic, so it is possible to generate power at high temperature above 700 ℃, and the mixture of hydrogen and carbon monoxide as fuel Can be used.

As a fuel used in such a fuel cell, natural gas whose methane is a main component is steam-modified as shown in Chemical Formula 1 to be converted into hydrogen and carbon monoxide.

[Formula 1]

CH ₄ + H ₂ O = 3H ₂ + CO

However, considering domestic realities that depend on imports of natural gas, economic problems may arise. In addition, it is possible to generate power using coal gasification gas, but domestic coal gasification technology is a situation that has not yet matured, it takes time to use.

Korean Patent Laid-Open Publication No. 2009-0045251 supplies a steam at a low temperature of 200 ° C. or lower to drive a low temperature fuel cell using hydrogen generated together with diesel fuel from the waste. An apparatus for this is described. However, the waste treatment apparatus of Korean Patent Publication No. 2009-0045251 has a problem that an apparatus for separating hydrogen from various generated gases must be included.

An object of the present invention is to use a pyrolysis gas containing a small amount of hydrogen and carbon monoxide generated through the pyrolysis / gasification of the combustible waste, and high power generation efficiency even when using a pyrolysis gas containing a small amount of hydrogen and carbon monoxide as a fuel. The present invention provides a fuel cell cogeneration system that exhibits high efficiency and is environmentally friendly, including a fuel cell.

In order to achieve the above object, the present invention,

A flammable waste drying apparatus for evaporating moisture of the flammable waste;

A pyrolysis device that pyrolyzes the dried waste from the combustible waste drying device to generate a pyrolysis gas;

A gas purifier for removing acid gas contained in the pyrolysis gas generated from the pyrolysis apparatus;

A fuel cell configured to generate electricity by receiving purified pyrolysis gas from an anode through the gas purifier; And

The present invention provides a fuel cell cogeneration system using a pyrolysis / gasification method of waste, comprising a catalytic combustor for oxidizing unreacted hydrogen and carbon monoxide discharged from an anode of the fuel cell together with air using a catalyst.

The present inventors have studied a fuel cell cogeneration system using the pyrolysis / gasification method of waste. As a result, H ₂ , CO is applied by applying the pyrolysis / gasification method to effectively use organic materials, which are energy sources included in flammable waste. After producing the pyrolysis gas including CH ₄ , CO ₂ , H ₂ O, H ₂ S, HCl, N _2, etc., the molten carbonate fuel without having to go through a device for separating hydrogen from the pyrolysis gas It has led to the development of a fuel cell cogeneration system that can be supplied as a fuel to a cell (MCFC) or a solid oxide fuel cell (SOFC).

Hereinafter, a fuel cell cogeneration system using the pyrolysis / gasification method of waste according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a view schematically showing the structure of a fuel cell cogeneration system to which the pyrolysis / gasification of waste of the present invention is applied.

Referring to FIG. 1, the combustible waste drying apparatus 110 among components of the fuel cell cogeneration system 200 to which the pyrolysis / gasification method of waste of the present invention is applied is used to dry the combustible waste 100.

As combustible waste 100 that can be used in the present invention, wastewater sludge containing heavy metals such as nickel, chromium, lead, mercury, as well as municipal waste, waste plastics, and wood-based wastes can be used, and sewage sludge and livestock in sewage treatment plants. Residues generated in the manure, food waste treatment plant may be used, but these are also not particularly limited in kind. The flammable waste 100 used in the present invention usually contains 30 to 90% by weight of water, and may include 0.5 to 2,000 ppm of heavy metals such as nickel, chromium, lead, and mercury.

The flammable waste 100 described above is preferably dried so that the final moisture content is 10% or less using the flammable waste drying apparatus 110.

The combustible waste drying apparatus 110 may be used without limitation as long as it is a device capable of drying combustible waste.

As described above, the combustible waste dried using the combustible waste drying apparatus 110 is input to the pyrolysis apparatus 120 to generate pyrolysis gas.

In one embodiment of the present invention, the pyrolysis device 120 may be a low-temperature pyrolysis device for pyrolyzing volatile matter and organic matter by heating the combustible waste dried by heating at a temperature of 400 ~ 800 ℃ by partial oxidation or indirect heating, It may be a high temperature pyrolysis device for pyrolyzing volatile matter and organic matter using a plasma at a temperature of 1,100 ~ 11,600 ℃.

When pyrolysing the combustible waste dried using the above-described pyrolysis device 120, pyrolysis gas including H ₂ , CO, CH ₄ , CO ₂ , H ₂ O, H ₂ S, HCl, N _2, etc. may be generated. Can be.

The pyrolysis gas may be generated as various synthesis gases according to the type of flammable waste used and the characteristics of the pyrolysis apparatus. In one embodiment of the present invention, the H ₂ concentration in the pyrolysis gas is 13 to 40% by volume, CO concentration is 13 to 35% by volume, CH ₄ concentration is 1 to 3% by volume, CO ₂ concentration is 6 to 16 volumes. %, H ₂ O concentration may be 5 to 40% by volume, H ₂ S is 0.1 to 2% by volume, HCl may be 0.01 to 1% by volume, N ₂ concentration may be 1 to 15% by volume.

The pyrolysis gas generated from the pyrolysis device 120 is introduced into the gas purifier 130.

The pyrolysis gas generated from the pyrolysis device 120 includes sulfur (S), chlorine (Cl) component HCl gas, SO ₂ contained in the flammable waste. Acid gas such as gas, Cl ₂ gas, etc. may be included, such acid gas may be removed via the gas purifier 130.

In one embodiment of the present invention, using the gas purifier 130 to remove the acidic gas contained in the above-mentioned pyrolysis gas, the pyrolysis gas is introduced into the gas purifier 130, and then calcined lime (Ca (OH) ₂ ). The powder, quicklime (CaO) powder, dolomite (CaMg (CO ₃ ) ₂ ) powder and sodium bicarbonate (NaHCO ₃ ) powder can be removed by spraying at least one powder selected from the group consisting of two or more mixed powders. More specifically, the acid gas included in the pyrolysis gas is HCl gas, SO ₂ Gas, Cl ₂ Since the gas is a mixture of slaked lime (Ca (OH) ₂ ), quicklime (CaO), dolomite (CaMg (CO ₃ ) ₂ ) powder and sodium bicarbonate (NaHCO ₃ ) powder to spray the pyrolysis gas, the mixed powder And an acidic gas to form a product such as NH ₄ Cl, CaCl ₂ , CaS, CaSO ₄ , NaCl by a chemical reaction according to the formula 2 to 10 can be removed later to remove the acid gas (Formula 2 below) -10).

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

As described above, the purified pyrolysis gas is supplied as fuel to the anode 152 of the fuel cell 150 and used for power generation.

The fuel cell 150 used in the present invention may be a molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC), and a commonly used molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC). ) Can be used without limitation.

In the molten carbonate fuel cell (MCFC), a porous electrode having a large surface area may be used to smoothly proceed with oxidation of hydrogen and carbon monoxide and reduction of oxygen. The molten carbonate impregnated in the ceramic porous body between the two electrodes prevents direct contact between the fuel mainly composed of hydrogen and the oxidant composed of oxygen. In addition, the carbonate ions (CO ₃ ^{2 −} ) generated in the cathode (cathode) serve as a passage for moving to the anode (anode).

Molten carbonate fuel cell (MCFC) is a fuel cell that operates at high temperature, and the voltage-current and current-power is almost the same as that of ordinary hydrogen fuel, even for the small amount of hydrogen and carbon monoxide mixtures that are expected to be generated from waste due to the fast electrode reaction rate. Can exhibit characteristics.

In addition, the solid oxide fuel cell (SOFC) is made of nickel metal, in which the oxidation of hydrogen and carbon monoxide starts from nickel oxide, and the reduction of oxygen is performed by a conductive ceramic. In addition, an electrolyte such as an oxygen ion conductive zirconia is disposed between the anode, which is the fuel electrode, and the cathode, which is the air electrode, to prevent hydrogen or carbon monoxide from chemically reacting with oxygen.

However, when a molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC) is used as one unit cell, the theoretical electromotive force is about 1V, which is not suitable for practical use. Therefore, such unit cells can be stacked and electrically connected in series through a separator, which is a conductor, to be used as a power generation system having a desired capacity by controlling the number of stacked cells.

That is, a molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC) unit cell is composed of a pair of porous electrode plates (fuel electrode and air electrode) and an electrolyte plate present therebetween. Laminated via the plate. The separator provides electrical connection between the unit cells and provides a flow path of fuel gas to the anode, the anode, and a flow path of oxidant gas to the cathode, the cathode.

As described above, the molten carbonate fuel cell (MCFC) or the solid oxide fuel cell (SOFC) used in the present invention may be a fuel cell having a stacked structure. The molten carbonate fuel cell (MCFC) or the solid oxide fuel cell (SOFC) is provided with a manifold having a distribution and recovery function of the reaction gas, the gas required for the reaction is supplied through the inlet manifold, and the cathode and anode reaction After roughing it can be discharged to the outside through the opposite manifold.

The fuel cell cogeneration system 200 according to the present invention includes a catalytic combustion unit 160 for oxidizing unreacted hydrogen and carbon monoxide discharged from the anode 152 of the fuel cell 150 with air using a catalyst.

The catalytic combustor 160 is a reaction apparatus capable of burning a small amount of hydrogen and carbon monoxide. The catalytic combustion apparatus includes a small amount of unreacted hydrogen and carbon monoxide discharged from the anode 152 of the fuel cell 150 by installing a combustion catalyst inside the combustor. It is a reaction device that generates heat by supplying a gas to be oxidized with air. Therefore, the gas discharged from the catalytic combustor 160 is composed mainly of air, water vapor, and carbon dioxide.

Heat generated by oxidizing a small amount of hydrogen and carbon monoxide together with air in the catalytic combustion unit 160 may be used to preheat the pyrolysis gas supplied to the anode, and may be recovered by the combustible waste drying apparatus 110 to dry the combustible waste. Can be used.

Exhaust gas of the catalytic combustor 160 including air, water vapor, carbon dioxide, etc. is supplied to the cathode 151 of the fuel cell 150 and used for the electrochemical reaction by oxygen components in the air. Can be discharged through. The discharged gas may also be recovered to the combustible waste drying apparatus 110 and used to dry the combustible waste.

The fuel cell cogeneration system 200 according to the present invention is disposed between the gas purifier 130 and the fuel cell 150, so as to maintain a temperature of the pyrolysis gas supplied from the gas purifier 130. ) May be further included.

The heat exchanger 140 serves to supply the fuel cell 150 by maintaining the temperature of the gas supplied from the gas purifier 130 or the catalytic burner 160 at a temperature suitable for the reaction.

In addition, the fuel cell cogeneration system 200 according to the present invention may further include a DC-AC converter 170 for converting the DC generated from the fuel cell 150 into AC.

The fuel cell cogeneration system 200 according to the present invention described above uses a pyrolysis gas containing a small amount of hydrogen and carbon monoxide generated through pyrolysis / gasification of flammable waste, and uses a pyrolysis gas containing a small amount of hydrogen and carbon monoxide. By using a fuel cell that exhibits high power generation efficiency even with fuel, more than 45% power generation efficiency and 65% or more thermal efficiency can be obtained.

In addition, the present invention,

Drying the combustible waste using a combustible waste drying apparatus (step 1);

Pyrolysing the dried combustible waste to produce a pyrolysis gas (step 2);

Purifying by removing the acid gas contained in the pyrolysis gas (step 3); And

Provided is a pyrolysis / gasification method of waste and a cogeneration method using a fuel cell including the step of generating electricity from a fuel cell by receiving the purified pyrolysis gas.

Hereinafter, a thermal decomposition / gasification method of organic waste and a cogeneration method using a fuel cell according to the present invention will be described in more detail.

First, the combustible waste is dried using a combustible waste drying apparatus (step 1).

As described above, the combustible waste used in the present invention may be domestic waste, waste plastic, organic sludge, food waste, livestock manure, wood waste, and the like. In step 1, the combustible waste is preferably dried so that the water content is 10% or less.

Next, the dried combustible waste is pyrolyzed to produce a pyrolysis gas (step 2).

In one embodiment of the present invention, the step of pyrolysing the dried combustible waste to generate a pyrolysis gas is generated by supplying 20-30% of the amount of oxygen required for complete combustion to burn a part of the combustible waste. Heat is available. Alternatively, the waste dried by an indirect heating method using a separate external heat source may be heated to about 400 to 800 ° C. to pyrolyze volatile matter and organic matter.

In another embodiment of the present invention, the step of pyrolyzing the dried combustible waste to generate a pyrolysis gas is a high temperature pyrolysis apparatus for rapidly pyrolyzing waste at a reactor atmosphere temperature of 1,100 ~ 11,600 ℃ using a plasma torch or the like. Can be performed using.

The pyrolysis time of the flammable waste may show a difference depending on the moisture content, organic concentration, carbonization degree, etc., and when using a low-temperature pyrolysis device with an ambient temperature of 400 ~ 800 ℃, it may take about 2 to 6 hours, the reactor atmosphere temperature is When using a high temperature pyrolysis apparatus using a plasma of 1,100 ~ 11,600 ℃ it may take about 20 ~ 80 minutes.

Next, the acid gas is removed and purified from the pyrolysis gas generated in step 2 (step 3).

The pyrolysis gas produced through the pyrolysis process of step 2 is HCl gas, SO ₂ by sulfur (S), chlorine (Cl) component contained in the pyrolysis gas Gas, Cl ₂ The pyrolysis gas requires a purification process because it contains an acidic gas such as gas.

In order to remove the acidic gas from the pyrolysis gas, the pyrolysis gas is introduced into the gas purifier as described above, and when the slaked lime powder, quicklime powder, dolomite powder and sodium bicarbonate powder are mixed and sprayed onto the pyrolysis gas, the mixing is performed. Powders and acidic gas can be removed by forming a product by the chemical reaction represented by Chemical Formulas 2 to 10, and later discharging it.

As such, the final purified pyrolysis gas through the purification process of the pyrolysis gas may have a concentration of HCl, NH ₃ , and SO ₂ of 10 ppm or less.

Finally, the pyrolysis gas purified in step 3 is supplied to the fuel cell to generate electricity (step 4).

The fuel cell used in step 4 may use a fuel cell capable of cogeneration with the use of a mixture gas containing a small amount of hydrogen and carbon monoxide as the fuel for power generation and thermal energy at the same time. The fuel cell may be a molten carbonate fuel cell (MCFC) or a solid oxide fuel cell (SOFC) described in the fuel cell cogeneration system of the present invention.

As described above, after generating the direct current by supplying the pyrolysis gas to the fuel cell in step 4, it may be converted into alternating current through a DC-AC converter converting direct current into alternating current.

The cogeneration method of the present invention may further include a step of pyrolyzing the combustible waste in step 2 to generate a pyrolysis gas and then quenching the molten slug discharged.

In one embodiment of the present invention, the pyrolysis of the combustible waste in step 2 to produce a pyrolysis gas, the molten slug discharged after falling to the conical rotating plate can be scattered and quenched to form a fine aggregate. At this time, the rotational speed of the conical rotating plate is in the range of 300 ~ 20,000 rpm, preferably 1,000 ~ 20,000 rpm.

The fine aggregate obtained by dropping and quenching while falling on the conical rotating plate of the above conditions is that the surface is vitrified, the fine aggregate can be produced in a size of about 1 ~ 5mm in diameter. In addition, since the surface is vitrified, the heavy metal originally contained in the sludge becomes impossible to be eluted from the cooled aggregate and can be used as an environmentally friendly recycling material.

The method may further include generating electricity through the fuel cell in step 4, and then recovering the unreacted pyrolysis gas in the pyrolysis gas supplied as the fuel and oxidizing it with air through the catalytic combustion device. Can be.

The catalytic combustion unit may generate heat by oxidizing the unreacted pyrolysis gas together with air, and the generated heat may be recovered by a flammable waste drying apparatus and used to dry flammable waste. In addition, the exhaust gas generated during the oxidation in the catalytic combustor is recovered and supplied to the cathode of the fuel cell so that it can be used for the electrochemical reaction.

The present invention is a pyrolysis gas obtained by a pyrolysis process after the high-temperature drying of waste water sludge, food waste treatment residues, etc., which is difficult to burn and mixed with coal, including heavy metals and pollutants in the combustible wastes. A fuel cell can be used. Therefore, it is possible to provide a fuel cell cogeneration system with high efficiency and eco-friendliness that can efficiently use heat energy with high power generation efficiency.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

Example  One

Among the combustible wastes, the domestic wastes of the components shown in Tables 1 and 2 were pyrolyzed at atmospheric temperature of 400 to 800 ° C. under a pyrolysis condition in a partial oxidation type pyrolysis apparatus which is a low temperature pyrolysis method, and pyrolysis gas was obtained. As a result of analyzing the composition of the pyrolysis gas, H ₂ 18.3%, CO 5.08%, CO ₂ 15.85%, N ₂ 42.1%, H ₂ O 16.2% and included CH ₄ , H ₂ S, HCl as the remaining content.

Household waste industry analysis result division moisture
(wt.%) Combustible
(wt.%) Ash (Ash)
(wt.%) Low calorific value
(Kcal / kg) 31.94 59.08 8.98  2,200

Flammable Elemental Analysis of Household Waste division Goat
(wt.%) carbon
(wt.%) Hydrogen
(wt.%) Oxygen
(wt.%) nitrogen
(wt.%) brimstone
(wt.%) 0.15 29.51 3.71 25.05 0.49 0.10

The obtained pyrolysis gas was introduced into a gas purifier, and the calcined lime (Ca (OH) ₂ ) powder was Ca / Cl molar ratio 3.0, Ca / S molar ratio 3.5, and the quicklime (CaO) powder was Ca / Cl molar ratio 3.0, Ca / S molar ratio 3.5 Dolomite (CaMg (CO ₃ ) ₂ ) powder was removed at a Ca / Cl molar ratio of 3.5, Ca / S molar ratio of 3.0, and sodium bicarbonate (NaHCO ₃ ) powder at a Ca / Cl molar ratio of 3.2 to remove acidic gas. The molten carbonate fuel cell was supplied to generate electricity by the reactions shown in the following Chemical Formulas 11 and 12.

[Formula 11]

An anode (fuel _{^{electrode) H 2 + CO 3 2 -}} → H 2 O + CO 2 + 2e -

[Chemical Formula 12]

Cathode (air _{electrode) 1 / 2O 2 + CO 2} + 2e - → CO 3 2 -

Example  2

In the pyrolysis of household waste in Example 1, the pyrolysis process was performed in the same manner as in Example 1 except that pyrolysis gas was generated through a high temperature plasma torch used as an oxygen plasma gas. As a result of analyzing the composition of the generated pyrolysis gas, H ₂ 40%, CO 35%, CO ₂ 6.5%, H ₂ O 8% was included and N ₂ was included as the remaining content.

Example  3

The pyrolysis process was performed in the same manner as in Example 1 except that pyrolysis gas was generated through a pyrolysis process using a high-temperature plasma torch used as an air plasma gas in the pyrolysis process of household waste in Example 1. As a result of analyzing the composition of the generated pyrolysis gas, H ₂ 12 to 23%, CO 13 to 20%, CO ₂ 10 to 15%, H ₂ O 30 to 40% and CH ₄ , N ₂ was included as the remaining content.

2 is a hydrogen fuel cell using a conventional hydrogen fuel (H ₂ : CO ₂ : H ₂ O = 69%: 17%: 14%) in a high temperature molten carbonate fuel cell as an example and the household waste according to Example 1 Pyrolysis gas (H ₂ : CO: CO ₂ : N ₂ : H ₂ O = 18.3%: 5.08%: 15.85%; 42.1%: 16.2%) is a graph showing the voltage and power characteristics according to the current in a 100 cm ² unit cell. As can be seen in Figure 2 it can be seen that even in the case of a low concentration of waste pyrolysis gas shows a performance similar to the conventional hydrogen fuel.

1 is a view schematically showing the structure of a fuel cell cogeneration system applying the pyrolysis / gasification of waste according to the present invention.

Figure 2 is a 100 cm ² grade using a hydrogen fuel cell using a conventional hydrogen fuel (H ₂ : CO ₂ : H ₂ O = 69%: 17%: 14%) and the thermal decomposition gas of domestic waste according to Example 1 Is a graph showing voltage and power characteristics according to the current in a unit cell.

Explanation of symbols on the main parts of the drawings

200: fuel cell cogeneration system 100: flammable waste

110: flammable waste drying device 120: pyrolysis device

130: gas purifier 140: heat exchanger

150: fuel cell 160: catalytic combustor

170: DC-to-AC converter

Claims (22)

A flammable waste drying apparatus for evaporating moisture of the flammable waste; A pyrolysis device capable of generating pyrolysis gas by pyrolyzing the dried waste from the combustible waste drying apparatus; A gas purifier for removing acid gas from the pyrolysis gas generated from the pyrolysis device; A fuel cell configured to generate electricity by receiving purified pyrolysis gas from an anode through the gas purifier; And And a catalytic combustor for oxidizing unreacted hydrogen and carbon monoxide discharged from the anode of the fuel cell together with air using a fuel catalyst. The method according to claim 1, The combustible waste is a fuel cell cogeneration system applied to the pyrolysis / gasification of the waste, characterized in that the household waste, waste plastic, organic sludge, food waste, livestock manure and wood-based waste. The method according to claim 1, The combustible waste drying apparatus is a fuel cell cogeneration system using the pyrolysis / gasification of waste, characterized in that the drying so that the water content of the combustible waste is less than 10%. The method according to claim 1, The pyrolysis apparatus is a low-temperature pyrolysis apparatus for thermally decomposing volatile components and organic substances by heating the dried waste by heating at a temperature of 400 to 800 ° C. by partial oxidation or indirect heating. Power generation system. The method according to claim 1, The pyrolysis device is a fuel cell cogeneration system using a pyrolysis / gasification method of waste, characterized in that the high temperature pyrolysis device for pyrolyzing volatile matter and organic matter using a plasma at a temperature of 1,100 ~ 11,600 ℃. The method according to claim 1, The gas purifier is a device for removing acid gas from the pyrolysis gas by using one powder or two or more powders selected from the group consisting of slaked lime powder, quicklime powder, dolomite powder and sodium bicarbonate powder. Fuel cell cogeneration system using Pyrolysis / Gasification method. The method according to claim 1, The fuel cell cogeneration system using the pyrolysis / gasification of the waste, characterized in that the fuel cell is a molten carbonate fuel cell or a solid oxide fuel cell. The method according to claim 1, The catalytic combustor is a fuel cell cogeneration system using the pyrolysis / gasification method of waste, characterized in that the unreacted hydrogen and carbon monoxide discharged from the anode of the fuel cell are oxidized with air using a combustion catalyst to generate heat and exhaust gas. Power generation system. The method according to claim 8, The heat generated from the catalytic combustor is recovered by a flammable waste drying apparatus is used for drying the flammable waste, fuel cell cogeneration system applying the pyrolysis / gasification of waste. The method according to claim 8, A fuel cell cogeneration system using the pyrolysis / gasification method of waste, characterized in that the exhaust gas generated from the catalytic combustor is supplied to the cathode of the fuel cell and used for electrochemical reaction. The method according to claim 1, And a heat exchanger disposed between the gas purifier and the fuel cell to maintain a temperature of the pyrolysis gas supplied from the gas purifier. The method according to claim 1, The fuel cell cogeneration system is a fuel cell cogeneration system using a pyrolysis / gasification method of the waste, characterized in that it further comprises a DC-AC converter for converting the direct current generated from the fuel cell into alternating current. Drying the combustible waste using a combustible waste drying apparatus (step 1); Pyrolysing the dried combustible waste to produce a pyrolysis gas (step 2); Purifying by removing the acid gas contained in the pyrolysis gas (step 3); And Receiving the purified pyrolysis gas to generate electricity from a fuel cell (step 4), waste pyrolysis / gasification method and cogeneration method using a fuel cell. 14. The method of claim 13, The combustible waste in step 1 is characterized in that the water content is dried to less than 10%, pyrolysis / gasification of waste and cogeneration method using a fuel cell. 14. The method of claim 13, Pyrolysis / gasification of the waste, characterized in that pyrolysis of the waste dried in the step 2 by using a partial oxidation or indirect heating pyrolysis apparatus at a temperature of 400 ~ 800 ℃ to generate pyrolysis gas and organic matter, and Cogeneration method using fuel cell. 14. The method of claim 13, A pyrolysis / gasification method of a waste and a cogeneration method using a fuel cell, characterized in that pyrolysis gas is generated by pyrolyzing the waste dried in the step 2 into a volatile component and an organic substance using plasma at a temperature of 1,100 to 11,600 ° C. 14. The method of claim 13, And pyrolyzing the flammable waste in step 2 to generate a pyrolysis gas, and further comprising quenching the molten slug discharged, the pyrolysis / gasification method of the waste and the cogeneration method using a fuel cell. 14. The method of claim 13, In step 3, the pyrolysis gas to remove the acidic gas by spraying at least one powder selected from the group consisting of slaked lime powder, quicklime powder, dolomite powder and sodium bicarbonate powder or two or more mixed powders. Pyrolysis / gasification and cogeneration with fuel cells. 14. The method of claim 13, The fuel cell used in step 4 is a molten carbonate fuel cell or a solid oxide fuel cell, pyrolysis / gasification of waste and cogeneration method using a fuel cell. 14. The method of claim 13, Generating electricity from a fuel cell by receiving the pyrolysis gas purified in step 4, and then oxidizing unreacted hydrogen and carbon monoxide together with air using a catalytic combustor to generate heat and exhaust gas. A pyrolysis / gasification method of waste and a cogeneration method using a fuel cell. The method of claim 20, Heat generated from the catalytic combustion unit is recovered by a flammable waste drying apparatus, characterized in that used for drying the flammable waste, waste pyrolysis / gasification method and cogeneration method using a fuel cell. The method of claim 20, The exhaust gas generated from the catalytic combustor is supplied to the cathode of the fuel cell and used for the electrochemical reaction, waste pyrolysis / gasification method and cogeneration method using a fuel cell.

Images