JP5117014B2 - Kerosene desulfurization agent, desulfurization method, and fuel cell system using the same - Google Patents

Description

  The present invention relates to a desulfurization agent for kerosene. The present invention also relates to a method for desulfurizing kerosene containing sulfur using the desulfurizing agent. Furthermore, the present invention relates to a fuel cell system provided with a desulfurization device filled with the desulfurization agent.

A fuel cell has a feature that high efficiency can be obtained because a free energy change caused by a combustion reaction of fuel can be directly taken out as electric energy. In addition to the fact that it does not emit harmful substances, it is being developed for various uses. In particular, solid polymer fuel cells are characterized by high power density, compactness, and operation at low temperatures.
As a fuel gas for a fuel cell, a gas containing hydrogen as a main component is generally used. The raw material is a hydrocarbon such as natural gas, LPG, naphtha or kerosene, alcohol such as methanol or ethanol, or dimethyl ether. Etc. are used. These raw materials containing carbon and hydrogen are reformed by treating them with steam at a high temperature on a catalyst, partially oxidized with an oxygen-containing gas, or a self-heat recovery type reforming reaction in a system in which steam and an oxygen-containing gas coexist. The hydrogen obtained by performing is basically used as fuel hydrogen for fuel cells.

However, since elements other than hydrogen exist in these raw materials, it is inevitable that impurities derived from carbon are mixed in the fuel gas to the fuel cell. For example, carbon monoxide poisons platinum-based noble metals used as electrode catalysts for fuel cells. Therefore, if carbon monoxide is present in the fuel gas, sufficient power generation characteristics cannot be obtained. In particular, a fuel cell operated at a low temperature has a stronger carbon monoxide adsorption and is more susceptible to poisoning. Therefore, in a system using a polymer electrolyte fuel cell, it is indispensable that the concentration of carbon monoxide in the fuel gas is reduced.
For this reason, a method is adopted in which carbon monoxide in the reformed gas obtained by reforming the raw material is reacted with water vapor, converted into hydrogen and carbon dioxide, and a small amount of remaining carbon monoxide is removed by selective oxidation. .
Finally, the fuel hydrogen removed until the carbon monoxide concentration is sufficiently low is introduced into the cathode of the fuel cell where it is converted into protons and electrons on the electrocatalyst. The produced protons move to the anode side in the electrolyte, react with oxygen together with the electrons that have passed through the external circuit, and produce water. Electrons generate electricity by passing through an external circuit.

The catalyst used for the raw material reforming and carbon monoxide removal steps for producing fuel hydrogen for fuel cells and the cathode electrode is often used in a reduced state such as noble metal or copper. Then, sulfur acts as a catalyst poison, and there is a problem that the catalytic activity of the hydrogen production process or the battery itself is lowered and the efficiency is lowered.
Therefore, it is considered that it is indispensable to sufficiently remove the sulfur content contained in the raw material in order to use the catalyst used in the hydrogen production process and further the electrode catalyst in its original performance.
The so-called desulfurization step, which basically removes sulfur, takes place at the beginning of the hydrogen production step. This is because it is necessary to reduce the sulfur concentration to a level at which the catalyst used in the reforming process immediately after that sufficiently functions. Conventionally, it has been said that the sulfur concentration is 0.1 mass ppm or less or 0.05 mass ppm (50 mass ppb) or less. However, in recent years, the required performance of desulfurization has become severe, and 0.02 mass ppm (20 The mass ppb) or less has been demanded.

Until now, the sulfur content of fuel cell raw materials has been removed by hydrodesulfurizing difficult-to-desulfurize organic sulfur compounds with a desulfurization catalyst, once converted to hydrogen sulfide that can be easily adsorbed and removed, and treated with an appropriate adsorbent. It seemed that the method to do was suitable. However, a general hydrodesulfurization catalyst is used at a high hydrogen pressure. However, when it is used in a fuel cell system, since the technological development is limited to atmospheric pressure or at most 1 MPa, an ordinary desulfurization catalyst is used. The current situation is that the system cannot handle it.
For this reason, studies have been made on catalyst systems that can sufficiently exhibit a desulfurization function even in a low-pressure system. For example, a method for producing hydrogen by steam reforming kerosene desulfurized with a nickel-based desulfurizing agent has been proposed (see, for example, Patent Document 1 and Patent Document 2). However, this method has a process limitation that the temperature range in which desulfurization is possible is 150 to 300 ° C. Moreover, the proposal about the copper-zinc type desulfurization agent is made | formed (for example, refer patent document 3 and patent document 4). However, even though this desulfurization agent is used at a relatively high temperature, carbon precipitation is small, but its desulfurization activity is lower than that of nickel, so light hydrocarbons such as natural gas, LPG, and naphtha can be desulfurized. There is a problem that it is insufficient. In addition, a method using activated carbon or a chemical solution for desulfurization is proposed (see Patent Document 5). However, this desulfurizing agent has been shown to have a desulfurization effect at normal temperature at start-up, but the raw material is limited to a gas body at normal temperature. Although a nickel-zinc system has also been proposed (see Patent Document 6), it is premised on coexistence with hydrogen and use under pressure, and under non-coexistence conditions with hydrogen, the desulfurization performance decreases because of the low nickel content. In Patent Documents 7 to 10, nickel-copper desulfurization agents have been proposed, but a desulfurization agent excellent in further improving durability and suppressing carbon deposition has been demanded.

JP-A-1-188404 Japanese Patent Laid-Open No. 1-188405 JP-A-2-302302 JP-A-2-302303 Japanese Patent Laid-Open No. 1-143155 JP 2001-62297 A JP-A-6-315628 JP 2003-290659 A JP 2004-290660 A JP 2004-75778 A

  As described above, the reforming of raw materials until the production of fuel hydrogen for fuel cells, the removal of carbon monoxide, and the catalyst used for the cathode electrode are often used in the reduced state of noble metals or copper, In such a state, sulfur acts as a catalyst poison, reducing the catalytic activity of the hydrogen production process or the battery itself, and reducing the efficiency. Therefore, it is indispensable to sufficiently remove the sulfur contained in the raw material in order to use the catalyst used in the hydrogen production process and further the electrode catalyst with its original performance. In addition, it is necessary to effectively desulfurize hardly desulfurization substances under low pressure conditions. Furthermore, in the case of liquid hydrocarbons such as kerosene, not only has about 12 carbon atoms, but also contains aromatic components, so desulfurization without hydrogen coexistence requires only the accumulation of sulfur on the desulfurizing agent. In addition, since the loss of active sites due to carbon deposition is a major cause of deterioration, a desulfurization agent that can suppress carbon deposition as much as possible is desired.

  As a result of diligent research on the problem, the present inventor has found that in order to efficiently remove sulfur contained in kerosene, it is very important to suppress deterioration due to carbon deposition of the desulfurizing agent. The present inventors have found a desulfurizing agent that can suppress the production and have completed the present invention. The present invention also provides a desulfurization method using this specific desulfurization agent and a fuel cell system having a desulfurization apparatus using this desulfurization agent.

That is, the first of the present invention contains 50 to 75% by mass of nickel oxide, 3 to 30% by mass of copper oxide and 10 to 30% by mass of silica, and contains 1% by mass or less of alumina and contains sodium. A desulfurization agent having an amount of 0.1% by mass or less and a BET specific surface area of 250 m ² / g or more, in the absence of hydrogen, reaction temperature: 180 to 250 ° C., reaction pressure: normal pressure to 0. When kerosene containing 0.1 to 30 mass ppm of sulfur is passed for 1500 h or more under the conditions of 6 MPa, LHSV: 0.5 to 2.0 h ⁻¹ , it accumulates on the extracted desulfurizing agent after oil passing. The amount of carbon produced is 5 mass% or less, the sulfur concentration of kerosene after desulfurization is 20 mass ppb or less, and the increase in bicyclic aromatics contained in desulfurized kerosene is within 0.5 points. The present invention relates to a desulfurizing agent for kerosene.

A second aspect of the present invention is a kerosene characterized in that the desulfurizing agent for kerosene according to the first aspect of the present invention is used in a temperature range of -50 ° C to 400 ° C and a pressure range of normal pressure to 0.9 MPa. The present invention relates to a desulfurization method.

Furthermore, a third aspect of the present invention relates to a fuel cell system including a desulfurization device filled with the desulfurization agent for kerosene according to the first aspect of the present invention.

  Since the desulfurization agent of the present invention can suppress deterioration due to carbon deposition, sulfur contained in kerosene can be efficiently removed under low pressure conditions in the absence of hydrogen. Therefore, the desulfurizing agent of the present invention is suitable as a desulfurizing agent used in a fuel cell system.

The present invention is described in detail below.
The desulfurizing agent of the present invention is basically composed of nickel oxide, copper oxide and silica, and can be obtained by firing a precursor formed by coprecipitation with a component containing nickel, copper and silica. it can.

  The content of nickel is required to be 50 to 75% by mass as nickel oxide, and preferably 55 to 70% by mass. When the content of nickel oxide is less than 50% by mass, the performance as a desulfurizing agent is lowered.

  The content of copper is required to be 3 to 30% by mass, preferably 5 to 25% by mass as copper oxide. If the copper oxide content is less than 3% by mass, the effect of copper, which suppresses the formation of bicyclic aromatics in kerosene and suppresses carbon deposition on the desulfurizing agent, is reduced, so that the desulfurizing agent deteriorates due to carbon deposition. End up. On the other hand, when the amount is more than 30% by mass, the proportions of nickel and silica are relatively low, and the performance is also lowered.

As the silica, at least one selected from silica powder, silica sol, and silica gel is used.
The content of silica needs to be 10 to 30% by mass, and preferably 15 to 25% by mass. If the content of silica is less than 10% by mass, the surface area of the desulfurizing agent is small, which is not preferable.
It is preferable that the BET specific surface area of the silica to be used is 250 m < ² > / g or more, More preferably, it is 300 m < ² > / g or more. Although there is no restriction | limiting in particular about the upper limit of the BET specific surface area of a silica, Usually, it is 1000 m < ² > / g or less.

  The alumina content in the desulfurizing agent of the present invention is required to be 1% by mass or less, preferably 0.5% by mass or less. Since the presence of alumina promotes carbon deposition on the desulfurizing agent, its content must be 1% by mass or less. The smaller the amount of alumina, the better.

The desulfurization agent of the present invention needs to have a BET specific surface area of 250 m ² / g or more, and preferably 300 m ² / g or more. Although there is no restriction | limiting in particular about an upper limit, It is preferable that it is 1000 m < ² > / g or less. A BET specific surface area of less than 250 m ² / g is not preferable because sufficient performance cannot be obtained.

  When kerosene is desulfurized with a desulfurizing agent, if the amount of carbon deposited on the desulfurizing agent increases, the desulfurization performance deteriorates rapidly, and the sulfur concentration of kerosene after desulfurization cannot be reduced to 20 mass ppb or less. When the amount of carbon on the desulfurizing agent exceeds 5% by mass, the desulfurizing agent is greatly deteriorated. Therefore, it is necessary to desulfurize under the condition that the amount of carbon deposition does not exceed 5% by mass.

The desulfurization agent of the present invention has a sulfur content of 0 under the conditions of reaction temperature: 180 to 250 ° C., reaction pressure: normal pressure to 0.6 MPa, LHSV: 0.5 to 2.0 h ^{−1 in} the absence of hydrogen. When 1 to 30 mass ppm of kerosene is passed through for 1500 h or more, the amount of carbon accumulated on the extracted desulfurization agent after passing through is 5 mass% or less, and the sulfur concentration of kerosene after desulfurization is 20 mass It is not more than ppb, and the increase in bicyclic aromatics contained in the desulfurized kerosene is within 0.5 point.

In general, kerosene contains about 20% by volume of bicyclic and tricyclic aromatics, which promote carbon deposition and degrade the desulfurization agent and reforming catalyst. In particular, it is considered that the influence on deterioration increases as the number of aromatic rings increases. Since the amount of aromatics in one part decreases during desulfurization and the amount of bicyclic aromatics increases, one-part naphthenobenzenes represented by tetralin are dehydrogenated during desulfurization to form bicyclic naphthalenes. The amount of aromatics is thought to increase. The hydrogen desorbed at this time is used for the desulfurization reaction and promotes desulfurization, but it is considered that the deterioration due to carbon deposition is also promoted. Since the reduced nickel desulfurizing agent has a high dehydrogenating ability and deteriorates due to carbon deposition, development of a desulfurizing agent capable of suppressing carbon deposition has been demanded.
Since the desulfurization agent of the present invention can also increase the amount of bicyclic aromatics contained after desulfurization within 0.5 points, not only can the deterioration of the desulfurization agent due to carbon deposition be suppressed, but it is installed after the desulfurizer. Degradation of the reforming catalyst can also be suppressed. Hydrogen can also be used in the coexistence, in which case the durability of the desulfurizing agent is improved.

Specifically, the coprecipitation method for forming a component containing nickel, copper and silica is prepared by mixing silica in an aqueous solution of a nickel compound and a copper compound and dropping a base into the mixed solution, or by adding silica into an aqueous solution of the base. Are mixed, and an aqueous solution of a nickel compound and a copper compound is dropped into the mixed solution to produce a precipitate formed from the nickel compound, the copper compound and silica, thereby preparing a desulfurization agent precursor.
As the nickel compound and the copper compound, respective chlorides, nitrates, sulfates, organic acid salts, hydroxides and the like can be used. Specifically, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, nickel hydroxide, copper chloride, copper nitrate, copper sulfate, copper acetate, copper hydroxide and the like are preferable.
As the base, an aqueous solution of ammonia, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or the like can be used.

After the nickel compound, the copper compound and silica are precipitated, the generated precipitate (desulfurizing agent precursor) is filtered and washed with ion-exchanged water or the like. Insufficient cleaning leaves chlorine, nitric acid traces, sulfuric acid traces, acetic acid traces, sodium, potassium, etc. on the catalyst, which adversely affects desulfurization agent performance. When ion-exchanged water cannot be sufficiently washed, an aqueous solution of a base such as ammonia, sodium carbonate, sodium hydrogen carbonate, or potassium carbonate may be used as the washing liquid. In this case, it is preferable to first wash the precipitated product with an aqueous base solution, and then wash with ion-exchanged water. Since sodium adversely affects the performance of the desulfurizing agent, it is preferable to perform washing until the amount of residual sodium is 0.1% by mass or less.
After washing the precipitated product, the precipitated product is pulverized and then dried. After drying, baking is subsequently performed. If washing after precipitation is insufficient, washing may be performed again after firing. Also in this case, ion-exchanged water or an aqueous solution of the base described above can be used.

  The drying method is not particularly limited, and examples thereof include natural drying in air and deaeration drying under reduced pressure. Usually, drying is performed at 100 to 150 ° C. for 5 to 15 hours in an air atmosphere. The firing method is not particularly limited, and the firing is usually performed in an air atmosphere at 200 to 600 ° C., preferably 250 to 450 ° C. for 0.1 to 10 hours, preferably 1 to 5 hours. desirable.

  When the desulfurizing agent prepared by the above method is used, it can be used for the reaction as it is, but reduction treatment with hydrogen or the like may be performed as a pretreatment. As the conditions, the temperature is 150 to 500 ° C, preferably 250 to 400 ° C, and the time is 0.1 to 15 hours, preferably 2 to 10 hours.

  The shape of the desulfurization agent of the present invention is not particularly limited, and the desulfurization agent obtained as a powder may be used as it is, or may be formed into a molded product by tableting and molding. It is good also as a desulfurization agent which sized the product to an appropriate range after pulverization. Further, it can be an extruded product. In molding, an appropriate binder may be added. Although it does not specifically limit as a binder, The alumina binder used normally is not used in order to accelerate | stimulate carbon production | generation. Carbon black excluding alumina, silica, silica magnesia, titania, zirconia or a composite oxide thereof, or a molding agent made of an organic material can be used. As for the addition amount of a binder, an upper limit is 30 mass% or less normally, Preferably it is 10 mass% or less. The lower limit is not particularly limited as long as it can function as a binder, and is usually 0.5% by mass or more, preferably 1% by mass or more.

  The kerosene used as a raw material in the present invention is a kerosene containing a sulfur content, and the sulfur content contained in the raw material kerosene is 0.1 to 30 mass ppm, preferably 1 to 25 mass ppm, more preferably 5 -20 mass ppm. The sulfur content in the present invention is a generic term for various sulfur, inorganic sulfur compounds, and organic sulfur compounds that are usually contained in hydrocarbons.

The pressure in the desulfurization reaction is preferably a low pressure in the range of normal pressure to 0.9 MPa, and more preferably normal pressure to 0.7 MPa in consideration of economics and safety of the fuel cell system. The reaction temperature is not particularly limited as long as it is a temperature that lowers the sulfur concentration, but it is preferable to work effectively from a low temperature in consideration of the start of the equipment, and in consideration of the steady state, −50 ° C. to 400 ° C. is preferable. More preferably, 0 ° C to 300 ° C, particularly preferably 100 ° C to 260 ° C is employed. If the SV is too high, the desulfurization reaction does not proceed easily. On the other hand, if the SV is too low, the apparatus becomes large. When using a liquid raw material, the range of 0.01-15h- ¹ is preferable, the range of 0.05-5h- ¹ is more preferable, and the range of 0.1-3h- ¹ is especially preferable. The desulfurization method of the present invention is characterized in that it can be desulfurized under non-hydrogen coexistence conditions, but a small amount of hydrogen may be introduced. The flow rate of hydrogen at that time is, for example, 0.05 to 1.0 NL per 1 g of kerosene.

  Although the form of the desulfurization apparatus using the desulfurization method of this invention is not specifically limited, For example, a flow-type fixed bed system can be used. The shape of the desulfurization device can be any known shape depending on the purpose of each process, such as a cylindrical shape or a flat plate shape.

  In the fuel cell system using the desulfurization agent and the desulfurization method of the present invention, the sulfur concentration of the kerosene containing the sulfur content described above can be reduced to 20 mass ppb or less under the hydrogen non-coexistence condition. The sulfur concentration is measured by an ultraviolet fluorescence method. Hydrocarbons desulfurized to a sulfur concentration of 20 mass ppb or less can then be used as a fuel for fuel cells through the reforming step, shift step, carbon monoxide selective oxidation step, etc. .

The reforming process is not particularly limited, but steam reforming in which the raw material is reformed with steam at a high temperature on a catalyst, partial oxidation with an oxygen-containing gas, and steam and an oxygen-containing gas coexist. In such a system, autothermal reforming that performs a self-heat recovery type reforming reaction can be used.
The reaction conditions for the reforming are not limited, but the reaction temperature is preferably 200 to 1000 ° C, particularly preferably 500 to 850 ° C. The reaction pressure is preferably from normal pressure to 1 MPa, and particularly preferably from normal pressure to 0.2 MPa. LHSV is preferably 0.01 to 40 h ⁻¹ , particularly preferably 0.1 to 10 h ⁻¹ .

  The mixed gas containing carbon monoxide and hydrogen obtained at this time can be used as a fuel for a fuel cell as it is in the case of a solid oxide fuel cell. In addition, it can be suitably used as a raw material for hydrogen for a fuel cell, such as a phosphoric acid fuel cell or a polymer electrolyte fuel cell, in which carbon monoxide needs to be removed.

The production of hydrogen for a fuel cell can employ a known method, and can be carried out, for example, by treating in a shift step and a carbon monoxide selective oxidation step.
The shift process is a process in which carbon monoxide and water are reacted to convert to hydrogen and carbon dioxide, and contains, for example, iron-chromium mixed oxide, copper-zinc mixed oxide, platinum, ruthenium, iridium, etc. The carbon monoxide content is reduced to 2 vol% or less, preferably 1 vol% or less, and more preferably 0.5 vol% or less.
Although the reaction conditions for the shift reaction are not necessarily limited by the reformed gas composition or the like as a raw material, the reaction temperature is preferably 120 to 500 ° C, and particularly preferably 150 to 450 ° C. The pressure is preferably normal pressure to 1 MPa, particularly preferably normal pressure to 0.2 MPa. GHSV is preferably 100~50000h ^-1, especially 300～10000H ^-1 are preferred. Usually, in the phosphoric acid fuel cell, the mixed gas in this state can be used as fuel.

On the other hand, in the polymer electrolyte fuel cell, since it is necessary to further reduce the carbon monoxide concentration, it is desirable to provide a step of removing carbon monoxide. This step is not particularly limited, and various methods such as an adsorption separation method, a hydrogen separation membrane method, and a carbon monoxide selective oxidation step can be used. It is particularly preferable to use a carbon monoxide selective oxidation step. In this step, using a catalyst containing iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, etc., 0.5 to 10 times the remaining number of moles of carbon monoxide Mole, preferably 0.7 to 5 times mol, more preferably 1 to 3 times mol of oxygen is added to reduce the carbon monoxide concentration by selectively converting carbon monoxide to carbon dioxide. Although the reaction conditions of this method are not limited, the reaction temperature is preferably 80 to 350 ° C, particularly preferably 100 to 300 ° C. The pressure is preferably normal pressure to 1 MPa, particularly preferably normal pressure to 0.2 MPa. GHSV is preferably 1000~50000h ^-1, especially 3000～30000H ^-1 are preferred. In this case, the carbon monoxide concentration can be reduced by reacting with the coexisting hydrogen simultaneously with the oxidation of carbon monoxide to generate methane.

An example of the fuel cell system will be described below with reference to FIG.
The raw fuel (kerosene) in the fuel tank 3 flows into the desulfurizer 5 through the fuel pump 4. At this time, if necessary, the hydrogen-containing gas from the carbon monoxide selective oxidation reactor 11 or the low temperature shift reactor 10 can be added. The desulfurizer 5 is filled with the desulfurizing agent of the present invention. The fuel desulfurized in the desulfurizer 5 is mixed with water from the water tank 1 through the water pump 2, introduced into the vaporizer 6, and sent into the reformer 7.

The reformer 7 is heated by a heating burner 18. As the fuel for the heating burner 18, the anode off gas of the fuel cell 17 is mainly used, but the fuel discharged from the fuel pump 4 can be supplemented as necessary. As the catalyst filled in the reformer 7, a nickel-based, ruthenium-based, or rhodium-based catalyst can be used.
The gas containing hydrogen and carbon monoxide produced in this way is passed through the high temperature shift reactor 9, the low temperature shift reactor 10, and the carbon monoxide selective oxidation reactor 11 in order, so that the carbon monoxide concentration is adjusted to the fuel cell. It is reduced to the extent that it does not affect the characteristics of Examples of catalysts used in these reactors include an iron-chromium catalyst for the high temperature shift reactor 9, a copper-zinc catalyst for the low temperature shift reactor 10, and a ruthenium catalyst for the carbon monoxide selective oxidation reactor 11. Etc.

  The polymer electrolyte fuel cell 17 comprises an anode 12, a cathode 13, and a solid polymer electrolyte 14, and a fuel gas containing high-purity hydrogen obtained by the above method is provided on the anode side, and an air blower is provided on the cathode side. If necessary, air sent from 8 is introduced after appropriate humidification processing (a humidifier is not shown). At this time, a reaction in which hydrogen gas becomes protons and emits electrons proceeds at the anode, and a reaction in which oxygen gas obtains electrons and protons to become water proceeds at the cathode. In order to promote these reactions, platinum black and Pt catalyst or Pt-Ru alloy catalyst supported on activated carbon are used for the anode, and platinum black and Pt catalyst supported on activated carbon are used for the cathode. Usually, both the anode and cathode catalysts are formed into a porous catalyst layer together with polytetrafluoroethylene, a low molecular weight polymer electrolyte membrane material, activated carbon, and the like as necessary.

Next, the porous catalyst layer is laminated on both sides of a polymer electrolyte membrane known by a trade name such as Nafion (manufactured by DuPont), Gore (manufactured by Gore), Flemion (manufactured by Asahi Glass), Aciplex (manufactured by Asahi Kasei). An MEA (Membrane Electrode Assembly) is formed. Further, the fuel cell is assembled by sandwiching the MEA with a separator having a gas supply function, a current collecting function, particularly an important drainage function in the cathode, and the like made of a metal material, graphite, carbon composite and the like. The electric load 15 is electrically connected to the anode and the cathode.
The anode off gas is consumed in the heating burner 18. The cathode off gas is discharged from the exhaust port 16.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
A solution prepared by dissolving 136.3 g of nickel nitrate hexahydrate (commercial reagent special grade) and 7.6 g of copper nitrate trihydrate (commercial reagent special grade) in ion-exchanged water to make 1400 ml is designated as solution A. 58.3 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 40 g of commercially available silica sol (particle size: about 15 nm) (silica content: 12.5 g), and 600 ml is used as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 70% by mass / 5% by mass / 25% by mass, and the residual Na was 0.05% by mass or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 330 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, sulfur concentration of kerosene after desulfurization after 1500 hours, amount of carbon accumulated on extracted desulfurization agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Example 2)
Nickel acetate tetrahydrate (commercial reagent special grade) 91.6g and copper acetate monohydrate (commercial reagent special grade) 25.1g are melt | dissolved in ion-exchange water, and let the aqueous solution made 1400 ml be A liquid. 57.6 g of sodium carbonate (commercial reagent grade) is dissolved in ion-exchanged water, mixed with 40 g of commercially available silica sol (particle size: about 15 nm) (silica content: 12.5 g), and 600 ml is used as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 55 mass% / 20 mass% / 25 mass%, and the residual Na was 0.05 mass% or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurizing agent (BET specific surface area 310 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, sulfur concentration of kerosene after desulfurization after 1500 hours, amount of carbon accumulated on extracted desulfurization agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Example 3)
Nickel nitrate hexahydrate (commercial reagent special grade) 146.0g and copper nitrate trihydrate (commercial reagent special grade) 22.3g are melt | dissolved in ion-exchange water, and let the aqueous solution made 1400 ml be A liquid. 69.5 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 17 g of commercially available silica sol (particle size: about 15 nm) (silica content: 5.0 g), and a solution made up to 600 ml is designated as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 75% by mass / 15% by mass / 10% by mass, and the residual Na was 0.05% by mass or less.
As a binder, 3% by mass of silica magnesia was added to the obtained fired powder, kneaded, extruded, and desulfurization agent (BET specific surface area 310 m ² / g) 6 cm ³ having a diameter of 1.0 mmφ having a diameter of 1.27 cm. Filled in a flow-type reaction tube and reduced in a hydrogen stream at 350 ° C. for 3 hours, then non-coexistence of hydrogen at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aromatics part: 18.5% by volume, bicyclic: 0.3% by volume) under the conditions, and after desulfurization of kerosene after 1500 hours Table 1 shows the sulfur concentration, the amount of carbon accumulated on the extracted desulfurizing agent, the amount of bicyclic aromatics contained in kerosene after 100 hours of desulfurization, and the increment.

(Comparative Example 1)
Nickel nitrate hexahydrate (commercial reagent special grade) 77.9g and copper nitrate trihydrate (commercial reagent special grade) 60.8g are melt | dissolved in ion-exchange water, and let the aqueous solution made 1400 ml be A liquid. 60.5 g of sodium carbonate (commercial reagent grade) is dissolved in ion-exchanged water, mixed with 33 g of commercially available silica sol (particle size: about 15 nm) (silica content 10.0 g), and a solution made 600 ml is designated as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 40% by mass / 40% by mass / 20% by mass, and the residual Na was 0.05% by mass or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 300 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, and sulfur concentration of kerosene after desulfurization after 1200 hours, amount of carbon accumulated on the extracted desulfurization agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Comparative Example 2)
Nickel acetate tetrahydrate (commercial reagent special grade) 116.6g and copper acetate monohydrate (commercial reagent special grade) 6.3g are melt | dissolved in ion-exchange water, and let the aqueous solution made 1400 ml be A liquid. 58.3 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 12.5 g of commercially available γ-alumina (BET specific surface area 230 m ^{2 /} g), and 600 ml is used as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / Al ₂ O ₃ = 70 mass% / 5 mass% / 25 mass%, and the residual Na was 0.05 mass% or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 180 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, and the sulfur concentration of kerosene after 950 hours elapsed, the amount of carbon accumulated on the extracted desulfurizing agent, 100 h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Comparative Example 3)
136.3 g of nickel nitrate hexahydrate (special grade of commercial reagent) is dissolved in ion-exchanged water, and an aqueous solution made up to 1400 ml is designated as solution A. 54.6 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 50 g (silica content: 15.0 g) of commercially available silica sol (particle size: about 15 nm), and a solution made up to 600 ml is designated as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / SiO ₂ = 70% by mass / 30% by mass, and the residual Na was 0.05% by mass or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 300 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, the sulfur concentration of kerosene after 300 hours of desulfurization, the amount of carbon accumulated on the extracted desulfurizing agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Comparative Example 4)
Nickel nitrate hexahydrate (commercial reagent special grade) 146.0g and copper nitrate trihydrate (commercial reagent special grade) 22.3g are melt | dissolved in ion-exchange water, and let the aqueous solution made 1400 ml be A liquid. 69.5 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 17 g of commercially available silica sol (particle size: about 15 nm) (silica content: 5.0 g), and a solution made up to 600 ml is designated as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 75% by mass / 15% by mass / 10% by mass, and the residual Na was 0.05% by mass or less.
3% by mass of a commercially available γ-alumina powder was added as a binder to the fired powder obtained, kneaded, extruded, and desulfurized with a diameter of 1.0 mmφ (BET specific surface area 320 m ² / g) 6 cm ³ in diameter. After filling a 1.27 cm flow type reaction tube and reducing in a hydrogen stream at 350 ° C. for 3 hours, at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ . , JIS No. 1 kerosene (sulfur concentration: 8 mass ppm, aromatic content part: 18.5% by volume, bicyclic: 0.3% by volume) under non-hydrogen coexisting conditions, and desulfurization after 1500 hours Table 1 shows the sulfur concentration of the later kerosene, the amount of carbon accumulated on the extracted desulfurization agent, the amount of bicyclic aromatics contained in the kerosene after desulfurization after 100 hours and the increment.

(Comparative Example 5)
A solution prepared by dissolving 136.3 g of nickel nitrate hexahydrate (commercial reagent special grade) and 7.6 g of copper nitrate trihydrate (commercial reagent special grade) in ion-exchanged water to make 1400 ml is designated as solution A. 58.3 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 12.5 g of commercially available silica powder (BET specific surface area 300 m ^{2 /} g), and 600 ml is used as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 70% by mass / 5% by mass / 25% by mass, and the residual Na was 0.05% by mass or less.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 230 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, the sulfur concentration of kerosene after desulfurization after 1100 hours, the amount of carbon accumulated on the extracted desulfurization agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

(Comparative Example 6)
A solution prepared by dissolving 136.3 g of nickel nitrate hexahydrate (commercial reagent special grade) and 7.6 g of copper nitrate trihydrate (commercial reagent special grade) in ion-exchanged water to make 1400 ml is designated as solution A. 58.3 g of sodium carbonate (commercial reagent special grade) is dissolved in ion-exchanged water, mixed with 40 g of commercially available silica sol (particle size: about 15 nm) (silica content: 12.5 g), and 600 ml is used as solution B. Liquid A and liquid B were mixed at 40 ° C. with stirring to form a precipitate. After washing the precipitate with ion-exchanged water, the obtained cake was pulverized, dried at 120 ° C. for 10 hours, and then baked at 360 ° C. for 4 hours to obtain 50 g of baked powder. The composition of the calcined powder was NiO / CuO / SiO ₂ = 70% by mass / 5% by mass / 25% by mass, and the residual Na was 0.2% by mass.
The obtained calcined powder was extruded and filled with 6 cm ³ of a desulfurization agent (BET specific surface area 330 m ² / g) having a diameter of 1.0 mmφ in a flow-type reaction tube having a diameter of 1.27 cm, and heated to 350 ° C. in a hydrogen stream. For 3 hours, and at a reaction temperature of 220 ° C., a reaction pressure of 0.3 MPa (gauge pressure), and LHSV = 1.0 h ⁻¹ under conditions of no hydrogen coexistence, JIS No. 1 kerosene (sulfur concentration: 9 mass ppm, aroma (18.5% by volume, bicyclic: 0.3% by volume) desulfurization test was conducted, sulfur concentration of kerosene after desulfurization after 1500 hours, amount of carbon accumulated on extracted desulfurization agent, 100h Table 1 shows the amount of bicyclic aromatics and the amount of increase in kerosene after desulfurization at the time.

In the fuel cell system of FIG. 1, the desulfurizer 5 was filled with the desulfurizing agent obtained in Example 1, and a power generation test was performed using No. 1 kerosene (sulfur concentration: 27 mass ppm) as fuel. During the operation for 200 hours, the desulfurizer operated normally and no decrease in the activity of the desulfurizing agent was observed. The desulfurization conditions were a temperature of 220 ° C., 0.25 MPa (gauge pressure), no hydrogen flow, and LHSV = 0.5 h ⁻¹ .
At this time, a Ru-based catalyst is used for steam reforming, and a copper-zinc based catalyst is used at 200 ° C. in the shift step (reactor 10) under the conditions of S / C = 3, temperature 700 ° C., LHSV = 1h ^−1. In the carbon monoxide selective oxidation step (reactor 11) under the conditions of GHSV = 2000h ⁻¹ , a Ru-based catalyst is used, and the operation is performed under the conditions of O ₂ / CO = 3, temperature 150 ° C., GHSV = 5000h ^−1. It was. The fuel cell also operated normally and the electric load 15 was operated smoothly.

It is the schematic which shows an example of the fuel cell system of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Water tank 2 Water pump 3 Fuel tank 4 Fuel pump 5 Desulfurizer 6 Vaporizer 7 Reformer 8 Air blower 9 High temperature shift reactor 10 Low temperature shift reactor 11 Carbon monoxide selective oxidation reactor 12 Anode 13 Cathode 14 Solid height Molecular electrolyte 15 Electric load 16 Exhaust port 17 Polymer electrolyte fuel cell 18 Heating burner

Claims (3)

50 to 75% by weight of nickel oxide, 3 to 30% by weight of copper oxide and 10 to 30% by weight of silica, an alumina content of 1% by weight or less , and a sodium content of 0.1% by weight or less A desulfurization agent having a BET specific surface area of 250 m ² / g or more, in the absence of hydrogen, reaction temperature: 180 to 250 ° C., reaction pressure: normal pressure to 0.6 MPa, LHSV: 0.5 to 2 When the kerosene containing 0.1 to 30 mass ppm of sulfur is passed for 1500 h or more under the condition of 0.0 h ^−1, the amount of carbon accumulated on the extracted desulfurizing agent after passing is 5 mass% or less in sulfur concentration of kerosene after the desulfurization is not less than 20 mass ppb, and bicyclic aromatic increment of contained in the desulfurized kerosene kerosene desulfurizing agent being in the 0.5 points or less. A method for desulfurizing kerosene, comprising using the desulfurizing agent for kerosene according to claim 1 in a temperature range of -50 ° C to 400 ° C and a pressure range of normal pressure to 0.9 MPa. A fuel cell system comprising a desulfurization device filled with the desulfurization agent for kerosene according to claim 1 .

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