JP2003290659A - Desulfurizing agent and method for producing hydrogen for fuel cell using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially advantageous nickel-copper desulfurizing agent for petroleum hydrocarbons capable of efficiently removing sulfur components from petroleum hydrocarbons to an extremely low concentration and having a long life. I will provide a. SOLUTION: The carrier has a nickel oxide (NiO) amount of 60.
７０70 mass%, copper oxide (CuO) amount 10-20 mass%, total amount of nickel oxide and copper oxide 70-90 mass%
A nickel-copper-based desulfurizing agent characterized by being supported by a nickel-copper-based desulfurizing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a nickel-copper-based desulfurizing agent. More specifically, the present invention is capable of efficiently removing the sulfur content of petroleum hydrocarbons, particularly kerosene, light oil, gasoline, and naphtha to an extremely low concentration, and having a long life nickel for petroleum hydrocarbons. The present invention relates to a copper-based desulfurizing agent.

[0002]

2. Description of the Related Art In recent years, new energy technologies have been in the spotlight due to environmental problems, and fuel cells have been attracting attention as one of these new energy technologies. This fuel cell is one for converting chemical energy into electric energy by electrochemically reacting hydrogen and oxygen, and is characterized by high energy utilization efficiency.
Practical studies are being actively conducted for industrial use or automobile use. For this fuel cell, types such as phosphoric acid type, molten carbonate type, solid oxide type, and solid polymer type are known depending on the type of electrolyte used. on the other hand,
As a hydrogen source, liquefied natural gas mainly composed of methanol and methane, city gas composed mainly of this natural gas, synthetic liquid fuel derived from natural gas, and petroleum-based LP
The use of petroleum hydrocarbons such as G, naphtha and kerosene has been studied.

When the fuel cell is used for consumer use, automobile use, etc., the above-mentioned petroleum hydrocarbons, especially kerosene, light oil, and gasoline are liquid at room temperature and atmospheric pressure, and are easy to store and handle, and at the gas station. It is advantageous as a hydrogen source because it has a well-developed supply system such as stores and stores. When using this petroleum hydrocarbon to produce hydrogen,
Generally, a method of subjecting the hydrocarbon to autothermal reforming, steam reforming or partial oxidation reforming in the presence of a reforming catalyst is used. In such a reforming treatment, since the reforming catalyst is poisoned by the sulfur content in the hydrocarbon, from the viewpoint of catalyst life, the hydrocarbon is desulfurized and the sulfur content is usually It is essential that the content be 0.2 mass ppm or less.

As a method for desulfurizing petroleum hydrocarbons, many studies have been made so far, and for example, a hydrodesulfurization catalyst such as Co-Mo / alumina or Ni-Mo / alumina and a hydrogen sulfide adsorbent such as ZnO are used. A method is known in which hydrodesulfurization is performed at a temperature of 200 to 400 ° C. under normal pressure to 5 MPa. This method is a method of performing hydrodesulfurization under severe conditions to remove sulfur content into hydrogen sulfide, but it is necessary to recycle hydrogen, which complicates equipment for producing petroleum hydrocarbons for fuel cells. There are many problems such as the increase of utility consumption. On the other hand, as a desulfurizing agent capable of adsorbing and removing the sulfur content in petroleum hydrocarbons under mild conditions without performing hydrorefining treatment, nickel-based or nickel-copper is used as a desulfurizing agent. System adsorbents are known [Japanese Patent Publication No. 6-65602 and Dohei 7]
-115842, the same 7-115843,
JP-A-1-188405 and JP-A-2-275701.
Japanese Laid-Open Patent Publication No. 2-204301, Japanese Laid-Open Patent Publication No. 5-707
No. 80, No. 6-80972, No. 6-91
No. 173, No. 6-228570 (above, nickel-based adsorbent), JP-A-6-315628 (nickel-copper-based adsorbent)].

These nickel-based or nickel-copper-based adsorbents are advantageous for being applied as desulfurizing agents to petroleum hydrocarbons for fuel cells, but all of them are long-lived as desulfurizing agents. The reality is that it has not reached a practical level. In particular, the above nickel-copper adsorbent is still insufficient for efficiently desulfurizing the sulfur content in petroleum hydrocarbons.

[0006]

Under the circumstances, the present invention is capable of efficiently removing the sulfur content of petroleum hydrocarbons to an extremely low concentration, and is industrially advantageous with a long life. It is an object of the present invention to provide a nickel-copper desulfurizing agent for petroleum hydrocarbons. In particular, by combining hydrodesulfurization and a nickel-copper-based desulfurizing agent, the desulfurization efficiency can be significantly improved, the system can be downsized and the cost can be reduced, and it can be used more practically. To aim.

[0007]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that by using a nickel-copper desulfurizing agent composed of a specific composition, It has been found that the sulfur content of can be efficiently removed. Furthermore, they have also found that the sulfur content can be removed to an extremely low concentration by using a nickel-copper-based desulfurizing agent having a specific composition in the latter stage of hydrodesulfurization. The present invention has been completed based on such findings. That is, in the present invention, the amount of nickel oxide (NiO) added to the carrier is 60 to 70.
% Nickel, a copper oxide (CuO) amount of 10 to 20% by weight, and a total amount of nickel oxide and copper oxide supported at 70 to 90% by weight. Is. The present invention also provides a method for producing hydrogen for a fuel cell, which comprises subjecting a petroleum-based hydrocarbon to desulfurization using the above nickel-copper-based desulfurizing agent, and then performing a reforming treatment.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The nickel-copper-based desulfurizing agent of the present invention (hereinafter sometimes referred to as the desulfurizing agent of the present invention) contains 60 to 70% by mass of nickel oxide (NiO) in a carrier and copper oxide (CuO). ) The amount is 10 to 20% by mass, and the total amount of nickel oxide and copper oxide is 70 to 90% by mass. In the desulfurizing agent of the present invention, S is used as a carrier.
It is preferable to use silica-alumina having an i / Al molar ratio of 5 to 7. If the molar ratio is outside this range, the surface area of the desulfurizing agent may decrease.

In the desulfurizing agent of the present invention, the amount of nickel supported on the carrier is in the range of 60 to 70 mass% as nickel oxide based on the total amount of desulfurizing agent. If the nickel oxide content is less than 60% by mass, sufficient desulfurization performance may not be exhibited. On the other hand, if it exceeds 70% by mass, the surface area of the desulfurizing agent becomes small and the desulfurizing performance is deteriorated. Also, the amount of copper supported is 1 as copper oxide based on the total amount of desulfurizing agent.
The range is from 0 to 20 mass%. When the content of copper oxide is less than 10% by mass, the adsorption capacity of sulfur becomes low, and 2
When it exceeds 0% by mass, it is difficult to obtain a desulfurizing agent having desired performance such as a slow adsorption rate of sulfur.

Since the desulfurizing agent of the present invention has the above-mentioned specific composition, it has a sulfur content of 0.2 in the petroleum hydrocarbon.
It can be efficiently removed up to ppm or less. Also,
The desulfurizing agent of the present invention has a long life and can remove sulfur content up to 0.2 ppm even after 1000 hours of use. The desulfurizing agent of the present invention can be used as a hydrodesulfurization catalyst. The desulfurization agent of the present invention is preferably placed after the hydrodesulfurization by the hydrodesulfurization catalyst and used to remove the sulfur compound which could not be removed by the hydrodesulfurization. The hydrodesulfurization catalyst used in this case may be the desulfurization agent of the present invention or another hydrodesulfurization catalyst.

The desulfurizing agent of the present invention is suitable for desulfurizing petroleum hydrocarbons containing a large amount of sulfur. The petroleum hydrocarbon is preferably selected from the group consisting of kerosene, light oil, naphtha, gasoline, LPG (liquefied petroleum gas), and natural gas. Those obtained by desulfurizing these hydrocarbons with the desulfurizing agent of the present invention have a very low sulfur content, and therefore, poisoning due to the sulfur content of the reforming catalyst can be suppressed, and thus can be suitably used for producing hydrogen for fuel cells. Then, by using the desulfurizing agent of the present invention, the life of the reforming catalyst can be extended. The desulfurizing agent of the present invention is preferably used in the temperature range of -40 to 400 ° C. If the temperature is lower than -40 ° C, the raw material hydrocarbon may be frozen, and if the temperature is higher than 400 ° C, the deposition rate of carbonaceous matter on the desulfurization agent becomes fast, and the desulfurization agent life tends to be shortened.

Next, the nickel-copper-based desulfurizing agent of the present invention can be manufactured by the following method. First, an acidic aqueous solution containing a nickel source, a copper source and an alumina source, and a basic aqueous solution containing an inorganic base and a silica source are prepared. Examples of the nickel source used in the former acidic aqueous solution include nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, nickel carbonate and hydrates thereof. These may be used alone or in combination of two or more. The amount of these nickel sources used is such that the content of nickel oxide in the obtained desulfurizing agent is 60 to
It is selected to be in the range of 70% by mass. When the nickel oxide content is less than 60% by mass, sufficient desulfurization performance may not be exhibited, and when it exceeds 70% by mass, the surface area of the desulfurizing agent becomes small and the desulfurization performance may be deteriorated. It is difficult to obtain a desulfurizing agent with performance.

Examples of the copper source include copper chloride, copper nitrate, copper sulfate, copper acetate and hydrates thereof. These may be used alone or in combination of two or more. The amount of these copper sources used is selected so that the content of copper oxide in the obtained desulfurizing agent is in the range of 10 to 20% by mass. When the content of copper oxide is less than 10% by mass, the amount of sulfur adsorbed becomes low, and when it exceeds 20% by mass, the desulfurization agent having desired performance is difficult to obtain, such that the adsorption rate of sulfur decreases. As described above, it is preferable to use silica-alumina as the carrier. Silica
The Si / Al molar ratio in alumina is preferably 5-7. It is preferable to use water glass as the silica source and pseudo-boehmite as the alumina source.

It is necessary to adjust the pH of the acidic aqueous solution containing the nickel source, the copper source and the alumina source to 3 or less with an acid such as hydrochloric acid, sulfuric acid or nitric acid. This pH
If it exceeds 3, the dispersibility of nickel and copper will decrease. On the other hand, the inorganic base used in the basic aqueous solution is preferably an alkali metal carbonate or hydroxide, for example,
Examples thereof include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like. These may be used alone or in combination of two or more, but in the present invention, sodium carbonate or sodium hydroxide alone or a combination of sodium carbonate and sodium hydroxide is used as such an inorganic base. Is preferred. The amount of the inorganic base used is advantageously selected so that when the acidic aqueous solution having a pH of 3 or less and the basic aqueous solution are mixed in the next step, the mixed solution becomes substantially neutral to basic.

In the present invention, the thus prepared acidic aqueous solution or the like having a pH of 3 or less and the basic aqueous solution are respectively heated to about 50 to 90 ° C., and then the two are mixed.
This mixing is preferably done as quickly as possible. Further, the obtained mixed liquid is maintained at a temperature of about 50 to 90 ° C.
Stir for about 3 hours to complete the reaction. Next, the produced solid is thoroughly washed and then solid-liquid separated, or the produced solid is solid-liquid separated and thoroughly washed, and then this solid is subjected to a known method at about 80 to 150 ° C. Dry at the temperature of. The desulfurization agent in which nickel and copper are supported on the carrier is obtained by calcining the dried product thus obtained, preferably at a temperature in the range of 200 to 400 ° C, more preferably 300 to 370 ° C. To be If the firing temperature deviates from the above range, it may be difficult to obtain a nickel-copper-based desulfurizing agent having desired properties such as low dispersibility of nickel and copper.

The desulfurizing agent of the present invention produced as described above is a petroleum hydrocarbon containing a large amount of sulfur and having a boiling point not higher than the boiling point of light oil, particularly a petroleum hydrocarbon having a boiling point not higher than the boiling point of kerosene. It is preferably used as a desulfurizing agent for hydrogen. Petroleum-based hydrocarbons having a boiling point of kerosene or lower include hydrogen sulfide, carbonyl sulfide, mercaptans, sulfides, disulfides, thiophenes, benzothiophenes, dibenzothiophenes, but not limited to the present invention. By using a desulfurizing agent, these sulfur compounds can be removed very easily. Also, city gas, L
Odorants such as mercaptans and sulfides are added to PG, but these sulfur compounds can also be easily removed, and hydrocarbons to which odorants are added, desulfurization of dimethyl ether, etc. Desulfurizing agent can be applied.

The desulfurizing agent of the present invention is used for removing sulfur compounds in the latter stage of hydrodesulfurization, and has a sulfur content of 0.
It is possible to desulfurize up to 2 ppm or less. As a method for desulfurizing petroleum hydrocarbons using the desulfurizing agent of the present invention, for example, the following method can be used.
First, the desulfurization tower is filled with the pre-sulfurized hydrodesulfurization catalyst and the nickel-copper-based desulfurizing agent of the present invention. The hydrodesulfurization catalyst used here is preferably a nickel-molybdenum-based catalyst, a cobalt-molybdenum-based catalyst, or the like. Further, the desulfurizing agent of the present invention is filled so that the petroleum hydrocarbon to be desulfurized contacts the hydrodesulfurization catalyst and then contacts the desulfurizing agent of the present invention (that is, in the latter stage). The hydrodesulfurization catalyst and the desulfurizing agent of the present invention may be packed in the same desulfurization tower or different desulfurization towers. A petroleum hydrocarbon, preferably JIS-1 kerosene, is passed through the desulfurization tower in an upward or downward flow at a temperature of 250 to 400 ° C and a pressure of 0 to 1
The hydrodesulfurization treatment is performed at 0 MPa and a hydrogen / oil volume ratio of 20 to 500 Nm ³ / m ³ . At this stage, the hydrogen sulfide produced by the hydrodesulfurization treatment can be removed by an adsorbent such as zinc oxide, and the sulfur compound that cannot be removed by the hydrodesulfurization treatment is the sulfur compound of the present invention packed in the latter stage of the desulfurization tower. It is desulfurized with a nickel-copper-based desulfurizing agent. As a result, petroleum hydrocarbons having a sulfur content of 0.2 ppm or less can be obtained.

Next, in the method for producing hydrogen for a fuel cell of the present invention (hereinafter sometimes referred to as the method of the present invention), the feedstock oil desulfurized as described above is treated with a partial oxidation reforming catalyst and an autothermal method. Hydrogen for a fuel cell is produced by bringing it into contact with a reforming catalyst or a steam reforming catalyst (hereinafter, all may be collectively referred to as simply "reforming catalyst"). There is no particular limitation on the reforming catalyst used in the method of the present invention, and any known catalyst conventionally known as a hydrocarbon reforming catalyst can be appropriately selected and used. As such a reforming catalyst,
For example, a suitable carrier carrying nickel, zirconium, or a noble metal such as ruthenium, rhodium or platinum can be mentioned. The above-mentioned supported metals may be one kind or a combination of two or more kinds. Among these catalysts, nickel-supported catalysts (hereinafter referred to as nickel-based catalysts) and ruthenium-supported catalysts (hereinafter referred to as ruthenium-based catalysts) are preferable. These are partial oxidation reforming treatment and autothermal treatment. The effect of suppressing carbon precipitation during the reforming treatment or steam reforming treatment is great.

In the case of a nickel-based catalyst, the amount of nickel supported is preferably in the range of 3 to 60 mass% based on the carrier. If the supported amount is less than 3% by mass, the activity of the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst may not be sufficiently exhibited, while if it exceeds 60% by mass,
The effect of improving the catalytic activity commensurate with the supported amount is not recognized so much, which is rather economically disadvantageous. Considering the catalyst activity and economic efficiency, the more preferable loading amount of nickel is 5 to 50% by mass, and the range of 10 to 30% by mass is particularly preferable. Further, in the case of a ruthenium-based catalyst, the amount of ruthenium supported is preferably in the range of 0.05 to 20 mass% based on the carrier. If the supported amount of ruthenium is less than 0.05% by mass, the activity of the partial oxidation reforming catalyst, autothermal reforming catalyst or steam reforming catalyst may not be sufficiently exhibited, while if it exceeds 20% by mass, The effect of improving the catalyst activity corresponding to the supported amount is not recognized so much, which is rather economically disadvantageous. Considering the catalytic activity and economical efficiency, the more preferable amount of ruthenium supported is 0.05 to 15.
It is mass%, and the range of 0.1 to 2 mass% is particularly preferable.

As the reaction conditions in the partial oxidation reforming treatment, the pressure is usually atmospheric pressure to 5 MPa, and the temperature is 400 to 11
00 ° C., oxygen (O ₂ ) / carbon (molar ratio) is 0.2 to
0.8, liquid hourly space velocity (LHSV) is 0.1-100h
The condition of r ⁻¹ is adopted. In addition, as the reaction conditions in the autothermal reforming treatment, the pressure is usually from normal pressure to 5M.
Pa, temperature is 400 to 1100 ° C., steam / carbon (molar ratio) is 0.1 to 10, oxygen (O ₂ ) / carbon (molar ratio) is 0.1 to 1, liquid hourly space velocity (LHSV) is 0. 1-2 hr ^-1 , gas hourly space velocity (GHSV) is 10
The conditions of 00 to 100,000 hr ^-1 are adopted.

Further, as a reaction condition in the steam reforming treatment, steam / carbon (molar ratio), which is a ratio of steam and carbon derived from fuel oil, is usually 1.5 to 10,
It is preferably selected in the range of 1.5 to 5, more preferably 2 to 4. If the steam / carbon (molar ratio) is less than 1.5, the amount of hydrogen produced may decrease.
If it exceeds 0, excess steam is required, heat loss is large, and the efficiency of hydrogen production is reduced, which is not preferable. Further, it is preferable to carry out the steam reforming while keeping the inlet temperature of the steam reforming catalyst layer at 630 ° C. or lower, further 600 ° C. or lower. If the inlet temperature exceeds 630 ° C., the thermal decomposition of fuel oil is promoted, and carbon may be deposited on the catalyst or reaction tube wall via the generated radicals, which may make operation difficult. The catalyst layer outlet temperature is not particularly limited, but 650
The range of to 800 ° C. is preferable. If it is less than 650 ° C, the amount of hydrogen produced may not be sufficient, and if it exceeds 800 ° C, it may be necessary to configure the reactor with a heat-resistant material, which is not economically preferable.

The reaction pressure is usually normal pressure to 3 MPa, preferably normal pressure to 1 MPa, and LHSV is
Usually 0.1 to 100 hr ^-1 , preferably 0.2 to 50 hr
It is in the range of r ⁻¹ . In the method of the present invention, CO obtained by the above partial oxidation reforming, autothermal reforming or steam reforming adversely affects hydrogen generation, so it is preferable to remove CO by converting it into CO ₂ by a reaction. Thus, according to the method of the present invention, hydrogen for fuel cells can be efficiently produced.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. [Production of Nickel-Copper Desulfurizing Agent] Nickel-copper desulfurizing agents having various compositions were produced as described below and used in Test Examples and Examples described later.

Production of Desulfurization Agent 1 Nickel sulfate hexahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
730.2 g and 151.3 g of copper sulfate pentahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 8 L of ion-exchanged water heated to 80 ° C., and pseudo-boehmite (trade name: C-
67% by mass of AP and Al ₂ O ₃ , 16.0 g of Catalyst Kasei Kogyo Co., Ltd. were mixed. To this, 1N sulfuric acid 300
The pH was adjusted to 2 by adding mL to obtain a preparation liquid A. Separately prepared, 600.0 g of sodium carbonate was dissolved in ion-exchanged water heated to 80 ° C., and water glass (J-1, Si)
Preparation liquid B was obtained by adding 180.2 g of a concentration of 29 mass%, manufactured by Nippon Kagaku Kogyo Co., Ltd.). While maintaining the temperature of each of the preparation liquid A and the preparation liquid B at 80 ° C.
Stir for hours. Then, the precipitation cake was washed and filtered using 60 L of ion-exchanged water, the product was dried for 12 hours by a 120 ° C. air dryer, and baked at 350 ° C. for 3 hours.
After that, a desulfurizing agent was molded by tableting and crushed again to obtain a nickel-copper-based desulfurizing agent (desulfurizing agent 1) having a particle diameter of 0.8 mm.

Production of Desulfurization Agent 2 Nickel sulfate hexahydrate 898.7 g, copper sulfate pentahydrate 151.3 g, pseudo-boehmite 4.0 g, water glass 4
A nickel-copper desulfurization agent (desulfurization agent 2) was obtained in the same manner as in Production Example 1 except that 5.1 g was used. Production of Desulfurization Agent 3 Nickel sulfate hexahydrate 617.9 g, copper sulfate pentahydrate 151.3 g, pseudo-boehmite 23.9 g, water glass 2
A nickel-copper-based desulfurizing agent (desulfurizing agent 3) was obtained in the same manner as in Production Example 1 except that 70.3 g was used. Production of Desulfurization Agent 4 Nickel sulfate hexahydrate 730.2 g, copper sulfate pentahydrate 252.2 g, pseudo-boehmite 8.0 g, water glass 9
A nickel-copper desulfurization agent (desulfurization agent 4) was obtained in the same manner as in Production Example 1 except that 0.1 g was used. Production of Desulfurization Agent 5 Nickel sulfate hexahydrate 730.2 g, copper sulfate pentahydrate 50.4 g, pseudo-boehmite 24.0 g, water glass 27
A nickel-copper-based desulfurizing agent (desulfurizing agent 5) was obtained in the same manner as in Production Example 1 except that 0.3 g was used. Here, the composition of the nickel-copper-based desulfurizing agent produced as described above is shown in Table 1 below.
Shown in.

[0026]

[Table 1]

[Desulfurization performance test] Desulfurization agents 1 to 5 obtained above
Kerosene was desulfurized under the following conditions to compare the desulfurization performance. In this test example, initial distillation temperature 153 ° C., 10% distillation temperature 176 ° C., 30% distillation temperature 194 ° C., 50% distillation temperature 209 ° C., 70% distillation temperature 224 ° C., 90% distillation temperature 2
It has a distillation property of 49 ℃, end point 267 ℃, sulfur content 48p
JIS-1 kerosene containing pm was used.

As the hydrodesulfurization catalyst used in this test example, one produced as follows was used. In 68 mL of ion-exchanged water, 28.4 g of cobalt nitrate hexahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 31.8 g of 6 ammonium ammonium molybdate tetrahydrate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) A solution in which was dissolved was obtained. This solution was dried in a dryer at 120 ° C. for 12 hours to obtain Al ₂ O ₃ (surface area 200 m ² /
g, pore volume 0.8 ml / g) 100 g
o and Mo were supported. Then, it was dried in a dryer at 120 ° C. for 12 hours and then calcined at 550 ° C. for 3 hours to obtain a hydrodesulfurization catalyst. This was molded by tablet molding and pulverized again to give a hydrodesulfurization catalyst (CoMo / Al ₂ O ₃ , Co loading = 5 mass%, Mo loading = 15 mass%) having a particle size of 0.8 mm. Obtained.

Example 1 and Comparative Examples 1 to 4 (when a hydrodesulfurization catalyst and a nickel-copper desulfurizing agent were filled in separate reaction tubes) A SUS reaction tube having an inner diameter of 9 mm was obtained as described above with hydrogen. 3 mL of a chemical desulfurization catalyst was filled. 40% in 1 hour while flowing a 10% hydrogen sulfide / hydrogen mixed gas through the reaction tube.
The temperature was raised to 0 ° C., and the hydrodesulfurization catalyst was sulfurized for 2 hours. In another SUS reaction tube having an inner diameter of 9 mm, 3 mL of zinc oxide (hydrogen sulfide adsorbent), the nickel-copper-based desulfurization agent (desulfurization agent) obtained in this order on the kerosene introduction part side (upstream) and the outlet side (downstream). 1-5) 2 mL was filled. Under normal pressure, the temperature of this reaction tube was raised to 120 ° C. in a hydrogen stream and kept for 30 minutes,
The temperature was further raised and kept at 300 ° C. for 3 hours to activate the adsorbent and the desulfurizing agent. A reaction tube filled with a hydrodesulfurization catalyst was placed upstream of the kerosene inlet, and zinc oxide and nickel-
A reaction tube filled with a copper-based desulfurizing agent is arranged in series on the downstream side,
While introducing hydrogen, the reaction temperature is 325 ° C. and the pressure is 0.5.
The pressure is set to MPa and the above JIS-1 kerosene is heated to 15 cc under normal pressure.
/ Hr was passed through the reaction tube. The sulfur concentration after 1000 hours was analyzed to compare the desulfurization performance. Table 2 shows the desulfurization performance (sulfur concentration after 1000 hours) at this time.

Example 2 (when a nickel-copper-based desulfurizing agent is used as a hydrodesulfurization catalyst, and the same desiccating agent is filled with the hydrodesulfurizing catalyst) Reaction made of SUS having an inner diameter of 9 mm Kerosene introduction part side (upstream) to the pipe
From the outlet side (downstream) to 3 mL of nickel-copper desulfurization agent (desulfurization agent 1) (as a hydrodesulfurization catalyst), 3 mL of zinc oxide (hydrogen sulfide adsorbent), nickel-copper desulfurization agent (desulfurization agent 1) Filled in 2 mL order. Under normal pressure, the temperature of the reaction tube was raised to 120 ° C. in a hydrogen stream and kept for 30 minutes, further raised, and kept at 300 ° C. for 3 hours to activate the adsorbent and the desulfurizing agent, and hydrogen at 75 cc / min. The reaction temperature was 325 ° C. and the pressure was 0.5 MPa while being introduced. The JIS No. 1 kerosene was passed through the reaction tube at 15 cc / hr under normal pressure. The sulfur concentration after 1000 hours was analyzed to evaluate the desulfurization performance. Desulfurization performance (100
The sulfur concentration after 0 hours) is shown in Table 2.

Comparative Example 5 (when no nickel-copper-based desulfurizing agent is used) An SUS reaction tube having an inner diameter of 9 mm was charged with 5 mL of the hydrodesulfurization catalyst produced as described above, and 10% hydrogen sulfide / hydrogen mixed gas was added. While flowing, the temperature was raised to 400 ° C. in 1 hour, and the hydrodesulfurization catalyst was sulfurized for 2 hours. Another inner diameter 9
Zinc oxide (hydrogen sulfide adsorbent) 3 in mm SUS reaction tube
mL was charged. The reaction tube filled with the hydrodesulfurization catalyst was arranged in series on the upstream side of the kerosene inlet, and the reaction tube filled with zinc oxide was arranged in series on the downstream side. While introducing hydrogen, the reaction temperature was 325 ° C. and the pressure was 0.5 MPa. Then, the above JIS-1 kerosene was passed through the reaction tube at 15 cc / hr under normal pressure.
The sulfur concentration after 1000 hours was analyzed to evaluate the desulfurization performance. Desulfurization performance at this time (sulfur concentration after 1000 hours)
Is shown in Table 2.

[0032]

[Table 2]

From the results shown in Table 2 above, the amount of NiO supported was 60.
In the range of up to 70% by mass, and the amount of CuO supported is 10 to 20% by mass
It can be seen that the nickel-copper-based desulfurizing agent (hereinafter referred to as the desulfurizing agent of the present invention) in the range of 1 can extremely efficiently remove the sulfur compound remaining after the hydrodesulfurization to a low concentration of 0.2 ppm or less. Further, the results of Example 2 in Table 2 show that the desulfurizing agent of the present invention can also be used as a hydrodesulfurization catalyst. Furthermore, the desulfurizing agent of the present invention is 1000
It can be seen that it does not deteriorate over time and has an extremely long life.

Example 3 (Production of Hydrogen for Fuel Cell by Steam Reforming Treatment) A ruthenium-based reforming catalyst (ruthenium carrying amount: 3% by mass, downstream of a desulfurizer having the same structure as that of Example 1 in Table 2 above).
A reformer filled with 20 mL of carrier (standard) was placed, and kerosene desulfurized to 0.2 ppm or less by the desulfurizer was steam-reformed. The reforming treatment conditions were: pressure: atmospheric pressure, steam / carbon (molar ratio) 3, LHSV: 1.0 hr ^-1 , inlet temperature: 550 ° C, outlet temperature: 750 ° C. As a result, the conversion rate to hydrogen at the reforming outlet after 100 hours was 1
It was 00%. Further, the sulfur content of the desulfurization-treated kerosene during this reaction period is 0.2 ppm or less, and it can be seen that by using the desulfurizing agent of the present invention, the poisoning due to the sulfur content of the steam reforming catalyst is greatly reduced.

[0035]

By installing the nickel-copper-based desulfurizing agent of the present invention in the latter stage of hydrodesulfurization, the sulfur content in petroleum hydrocarbons can be removed very efficiently up to 0.2 ppm or less. The nickel-copper desulfurization agent of the present invention can also be used as a hydrodesulfurization catalyst. The nickel-copper-based desulfurizing agent of the present invention has a practical level of life. According to the method for producing hydrogen for a fuel cell of the present invention in which petroleum hydrocarbons desulfurized by using the nickel-copper desulfurization agent of the present invention are reformed, the sulfur content in the hydrocarbon to be reformed is 0. Since it is removed to 0.2 ppm or less, poisoning due to the sulfur content of the reforming catalyst can be suppressed, and the life of the reforming catalyst can be extended.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10G 45/06 C10G 67/06 67/06 H01M 8/06 G C10L 3/10 B01J 23/74 321M H01M 8 / 06 C10L 3/00 B F term (reference) 4G066 AA15B AA20A AA22A AA27B AA47A AA61C CA24 CA25 DA04 DA09 4G069 AA03 AA08 BA03A BA03B BB04A BB04B BC31A BC31B BC68A BC68B CC02 DA05 EA02Y FA01 FB09 FB30 FB64 FC08 4G140 EA03 EA06 EA07 EB01 EC02 EC03 EC07 4H029 CA00 DA00 DA06 DA09 5H027 AA02 BA01 BA16 BA17

Claims (10)

[Claims] 1. A carrier containing nickel oxide (NiO) in an amount of 60.
˜70 mass%, copper oxide (CuO) content 10˜20 mass%, total amount of nickel oxide and copper oxide 70˜90 mass%.
A nickel-copper-based desulfurizing agent characterized by being supported by. 2. The nickel-copper-based desulfurizing agent according to claim 1, which is used as a hydrodesulfurization catalyst. 3. The carrier is silica-alumina, the S of which
The nickel-copper-based desulfurizing agent according to claim 1 or 2, wherein an i / Al molar ratio is 5 to 7. 4. The nickel-copper-based desulfurization according to claim 1, which is used for removing undesulfurized sulfur compounds in the latter stage of hydrodesulfurization of petroleum hydrocarbons. Agent. 5. The nickel-copper system according to claim 1, wherein the petroleum hydrocarbon is selected from the group consisting of kerosene, light oil, naphtha, gasoline, LPG and natural gas. Desulfurization agent. 6. The nickel-copper desulfurizing agent according to claim 1, which is used in a temperature range of −40 to 400 ° C. 7. After desulfurizing petroleum hydrocarbons using the nickel-copper desulfurizing agent according to any one of claims 1 to 6,
A method for producing hydrogen for a fuel cell, which comprises reforming. 8. The method for producing hydrogen for a fuel cell according to claim 7, wherein the reforming treatment is performed by a partial oxidation reforming treatment, an autothermal reforming treatment, or a steam reforming treatment. 9. The method for producing hydrogen for a fuel cell according to claim 8, wherein the partial oxidation reforming catalyst, the autothermal reforming catalyst or the steam reforming catalyst is a ruthenium-based catalyst or a nickel-based catalyst. . 10. The method for producing hydrogen for a fuel cell according to claim 9, wherein the reforming catalyst contains manganese oxide, cerium oxide or zirconia as a carrier component.