JP2003290660A - 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 which can efficiently remove sulfur content of petroleum hydrocarbons to a low concentration and has a long life. provide. 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%
And a mean particle size of 0.2 to 2.4 mm.

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 for a petroleum hydrocarbon having a long life and capable of efficiently removing a sulfur content in petroleum hydrocarbons, particularly kerosene, light oil, gasoline, naphtha, and LPG to an extremely low concentration. The present invention relates to a nickel-copper 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. In addition, LPG has a supply system maintained by retailers. When hydrogen is produced using this petroleum hydrocarbon, a method of autothermal reforming, steam reforming or partial oxidation reforming the hydrocarbon is generally used in the presence of a reforming catalyst. In such a reforming process, since the reforming catalyst is poisoned by the sulfur content in the hydrocarbon,
From the viewpoint of catalyst life, it is important to subject the hydrocarbon to a desulfurization treatment so that the sulfur content is usually 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.

[0007]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have used a nickel-copper-based desulfurizing agent having a specific composition and a specific average particle size. As a result, it has been found that the sulfur content in petroleum hydrocarbons can be efficiently removed. The present invention is
It was completed based on this knowledge. That is,
60 to 70% by mass of nickel oxide (NiO) on the carrier,
The amount of copper oxide (CuO) is 10 to 20% by mass, the total amount of nickel oxide and copper oxide is 76 to 87% by mass, and the average particle size is 0.2 to 2.4 mm. A nickel-copper-based desulfurizing agent is provided. 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, the total amount of nickel oxide and copper oxide is 70 to 90% by mass, and the average particle size is 0.2 to 2.4 mm. The average particle size of the desulfurizing agent of the present invention needs to be in the range of 0.2 to 2.4 mm, preferably 0.2 to 1.2 mm.
Is the range. In order to efficiently contact the desulfurizing agent with hydrocarbons such as kerosene to efficiently remove the sulfur content in the hydrocarbons over a long period of time and maintain the sulfur concentration low, the desulfurizing agent should have a small particle size. Preferable, but the average particle size of the desulfurizing agent is 2.4.
If it is larger than mm, the contact efficiency with a hydrocarbon such as kerosene is lowered, and a desired desulfurization life cannot be obtained. If it is less than 0.2 mm, the problem of differential pressure arises. Here, the differential pressure is the pressure difference between the inlet and the outlet of the reactor, and when the differential pressure increases, the design pressure of the reactor increases,
It is necessary to increase the capacity of the gas booster. The nickel-copper-based desulfurizing agent is required to be a molded product because of the above-mentioned problem of differential pressure. By using a desulfurizing agent as a molded product, a simple reactor,
The gas booster is ready for use. There is no limitation on the method for molding the desulfurizing agent, and tableting molding, extrusion molding, spherical molding, crushing molding and the like can be used. The average particle size may be adjusted to the above range by crushing the product once molded by tableting or the like.

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, it becomes difficult to obtain a desulfurizing agent having desired properties such as a cause of deterioration in mechanical strength and desulfurizing performance of the desulfurizing agent. The amount of copper supported is 10 to 2 as copper oxide based on the total amount of the desulfurizing agent.
The range is 0% by mass. When the copper oxide content is less than 10% by mass, the sulfur adsorption capacity becomes low, and when it exceeds 20% by mass, the desulfurization agent having desired performance is difficult to obtain, such as the sulfur adsorption rate is lowered. The total amount of nickel oxide and copper oxide of the desulfurizing agent of the present invention needs to be 70 to 90 mass%. When the total amount is less than 70% by mass,
There is a possibility that sufficient desulfurization performance will not be exhibited. Also, 9
If it exceeds 0% by mass, the surface area of the desulfurizing agent decreases.

The method for producing the desulfurizing agent of the present invention will be described in detail below. 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 for the former acidic aqueous solution include nickel chloride, nickel nitrate,
Examples thereof include 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 selected so that the content of nickel oxide in the obtained desulfurizing agent is in the range of 60 to 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, mechanical strength and desulfurization performance of the desulfurizing agent may be deteriorated. It is difficult to obtain a desulfurizing agent with performance.

Further, 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 the carrier, silica-alumina is preferably used. The Si / Al molar ratio in silica-alumina is preferably 5-7. Outside this range, the surface area of the desulfurizing agent tends to decrease. 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 above nickel source, copper source and alumina source to pH 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 production of the desulfurizing agent of 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 each heated to about 50 to 90 ° C., and then both 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. and stirred for about 0 to 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 dried product thus obtained is preferably 200 to 400.
The desulfurizing agent having nickel and copper supported on the carrier is obtained by calcining at a temperature in the range of 300 ° C, more preferably 300 to 370 ° C. 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-based hydrocarbon having a boiling point not higher than that 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.

When the desulfurization agent of the present invention is used to desulfurize petroleum-based hydrocarbons, the sulfur content in the petroleum-based hydrocarbon is 0.2 pp because the desulfurization agent has the above specific composition.
It can be efficiently removed up to m or less. In particular, when the desulfurizing agent of the present invention is used for desulfurizing LPG, the sulfur content in LPG can be efficiently removed to less than 0.1 ppm over a long period of time. The desulfurizing agent of the present invention is -40
It is preferably used in a temperature range of to 400 ° C. −
If the temperature is lower than 40 ° C, the raw material may be frozen.
When the temperature exceeds 00 ° C, the carbonaceous material deposition rate on the desulfurizing agent is increased, which may shorten the life of the desulfurizing agent. Since the petroleum hydrocarbons desulfurized by the desulfurizing agent of the present invention have an extremely low sulfur content, when used in the production of hydrogen for fuel cells, poisoning due to the sulfur content of the reforming catalyst is suppressed, and the life of the reforming catalyst is reduced. Can be lengthened.

The method for desulfurizing petroleum hydrocarbons using the nickel-copper desulfurizing agent of the present invention will be described below. First, a desulfurization tower is filled with the nickel-copper-based desulfurization agent of the present invention, and hydrogen is supplied to the desulfurization tower in advance to 150 to 40.
The desulfurizing agent is reduced at a temperature of about 0 ° C. Next, petroleum hydrocarbons are passed through the desulfurization tower in an upward or downward flow, and the temperature is about 130 to 230 ° C., the pressure is from normal pressure to about 1 MPa · G, and the gas hourly space velocity (GHSV) when the raw material is gas. 3000 hr ^-1 degree or less, when the raw material is liquid liquid hourly space velocity (LHSV) is desulfurized under the conditions of the degree 2 hr ^-1 or less. At this time, a small amount of hydrogen may coexist if necessary. By appropriately selecting the desulfurization conditions within the above range, petroleum hydrocarbons having a sulfur content of 0.2 ppm or less can be obtained.

Next, the method for producing hydrogen for a fuel cell of the present invention (hereinafter sometimes referred to as the method of the present invention) is a partial oxidation of a feed oil (petroleum hydrocarbon) desulfurized as described above. Hydrogen for fuel cells is produced by contacting with a reforming catalyst, an autothermal 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. Examples of such a reforming catalyst include those in which nickel or zirconium or a noble metal such as ruthenium, rhodium or platinum is supported on a suitable carrier. The above-mentioned supported metals may be one kind or a combination of two or more kinds. Among these catalysts, those supporting nickel (hereinafter,
A nickel-based catalyst) and a catalyst supporting ruthenium (hereinafter referred to as ruthenium-based catalyst) are preferable, and these have an effect of suppressing carbon deposition during partial oxidation reforming treatment, autothermal reforming treatment or steam reforming treatment. Is big. The carrier supporting the reforming catalyst preferably contains manganese oxide, cerium oxide, zirconia, or the like.

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 from atmospheric pressure to 3 MPa, preferably from atmospheric 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.

[0022]

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 an average particle diameter of 0.8 mm.

Production of Desulfurizing Agent 2 In the production of the desulfurizing agent 1, the tableting desulfurizing agent was crushed to obtain a nickel-copper desulfurizing agent (desulfurizing agent 2) having an average particle diameter of 2.0 mm. Production of Desulfurization Agent 3 In the production of the desulfurization agent 1, the tableting-molded desulfurization agent was pulverized to obtain a nickel-copper-based desulfurization agent (desulfurization agent 3) having an average particle diameter of 2.5 mm. Production of Desulfurization Agent 4 Nickel sulfate hexahydrate 898.7 g, copper sulfate pentahydrate 151.3 g, pseudo-boehmite 4.0 g, water glass 4
A nickel-copper-based desulfurizing agent (desulfurizing agent 4) was obtained in the same manner as in Production Example 1 except that 5.1 g was used.

Production of Desulfurization Agent 5 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 5) was obtained in the same manner as in Production Example 1 except that 70.3 g was used. Manufacture of desulfurization agent 6 Nickel sulfate hexahydrate 730.2 g, copper sulfate pentahydrate 252.2 g, pseudo-boehmite 8.0 g, water glass 9
A nickel-copper-based desulfurizing agent (desulfurizing agent 6) was obtained in the same manner as in Production Example 1 except that 0.1 g was used. Production of Desulfurization Agent 7 Nickel sulfate hexahydrate 730.2 g, copper sulfate pentahydrate 50.4 g, pseudo-boehmite 24.0 g, water glass 27
A nickel-copper desulfurization agent (desulfurization agent 7) was obtained in the same manner as in Production Example 1 except that 0.3 g was used. The composition of the nickel-copper desulfurizing agent produced as described above is shown in Table 1 below.

[Examples 1 and 2 and Comparative Examples 1 to 5] -JI
Desulfurization test of No. S-1 kerosene Using the desulfurizing agents 1 to 7 obtained above, the kerosene was desulfurized under the following conditions, and the desulfurization performance was compared. In the desulfurization test, initial distillation temperature 153 ° C, 10% distillation temperature 176 ° C, 30% distillation temperature 1
94 ° C, 50% distillation temperature 209 ° C, 70% distillation temperature 22
JIS-1 kerosene having a distillation property of 4 ° C, a 90% distillation temperature of 249 ° C and an end point of 267 ° C and containing a sulfur content of 48 ppm was used.

Desulfurizing agent 1 was added to a SUS reaction tube having an inner diameter of 17 mm.
Filled with 5 mL. 12 reaction tubes in a hydrogen stream under normal pressure
After raising the temperature to 0 ° C and holding for 30 minutes, further raise the temperature to 3
The desulfurization agent was activated by holding it at 00 ° C. for 3 hours. Then, the temperature of the reaction tube was lowered to 180 ° C. and maintained. The above JIS No. 1 kerosene was used under normal pressure at a liquid space velocity of 1
It was circulated in the reaction tube at ⁰ hr ⁻¹ . The sulfur concentration in kerosene after 16 hours was analyzed to compare the desulfurization performance of the desulfurization agent.
The composition of each desulfurizing agent and the desulfurization performance (sulfur concentration after 16 hours) are shown in Table 1 below.

[0028]

[Table 1]

From the results shown in Table 1 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
Range, the total amount of NiO and CuO is 76 to 87% by mass,
It can be seen that the nickel-copper-based desulfurizing agent having an average particle size of the desulfurizing agent in the range of 0.2 to 2.4 mm can efficiently remove sulfur in kerosene to a low concentration. Further, it can be seen that with the desulfurizing agent 3 having a particle size larger than the above range (2.5 mm), the contact area between the desulfurizing agent and kerosene is small, so that the desulfurizing performance is deteriorated.

Example 3 LPG Desulfurization Test Using the desulfurization agent 1 obtained above, LPG was desulfurized under the following conditions, and the desulfurization performance was evaluated. Here, LP with the following properties
Using G (JIS-1 type 1 No. _{LPG): C 3 H 7 97.9} % C 2 H 6 0.9% i-C 4 H 10 0.9% n-C 4 H 10 0.3% Sulfur concentration 5 ppm The results of the morphological analysis of sulfur are as follows: Carbonyl sulfide 0.3 ppm Mercaptans 2.4 ppm Sulfides 1.3 ppm Disulfide 1.0 ppm Desulfurization agent 1 was added to a SUS reaction tube with an inner diameter of 17 mm. 15 mL was filled. The temperature of the reaction tube was raised to 120 ° C. in a hydrogen stream under normal pressure, held for 30 minutes, and further raised to 3 ° C. at 300 ° C.
The desulfurizing agent was activated by holding for a time. Then, the temperature of the reaction tube was lowered to 180 ° C. and maintained. JIS-1 type 1 above
No. LPG was passed through the reaction tube under atmospheric pressure at a gas space velocity of 4000 hr ^-1 . When the sulfur concentration in LPG after 800 hours was analyzed, it was less than 0.1 ppm.

[Embodiment 4] -Manufacturing hydrogen for fuel cell by steam reforming process The production liquid hourly space velocity (LHSV) was set to 1 hr ^-1 , except that
0.2 pp in the same manner as in Example 1 using the above desulfurizing agent 1.
Kerosene desulfurized to m or less was steam-reformed with a reformer filled with 20 mL of a ruthenium-based reforming catalyst (ruthenium supported amount: 3% by mass, based on carrier). The modification treatment conditions are
Pressure: atmospheric pressure, steam / carbon (molar ratio) 3, LH
SV: 1.0 hr ^-1 , inlet temperature: 550 ° C, outlet temperature:
It was 750 ° C. As a result, the conversion rate to hydrogen at the reforming outlet after 100 hours was 100%.

[0032]

EFFECTS OF THE INVENTION The nickel-copper desulfurizing agent of the present invention has a specific composition, so that the sulfur content in petroleum hydrocarbons can be removed very efficiently. Since the nickel-copper-based desulfurizing agent of the present invention has an average particle diameter of 0.2 to 2.4 mm, the contact efficiency with petroleum hydrocarbons is improved,
And the life is extended. The method for producing hydrogen for fuel cells of the present invention can efficiently produce hydrogen for fuel cells by reforming petroleum hydrocarbons desulfurized using the nickel-copper desulfurization agent of the present invention. In addition, the life of the reforming catalyst can be extended.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10L 3/10 B01J 23/74 321M // H01M 8/06 C10L 3/00 BF term (reference) 4G066 AA15B AA20C AA22C AA27B BA09 BA20 CA25 DA05 DA09 FA12 FA37 4G069 AA03 AA08 BA03A BA03B BB04A BB04B BC31A BC31B BC68A BC68B CC02 DA06 EA02Y EB18X EB18Y16FB01 A02 BA16A07A06 EC06 4H140A27EA01 EC06 4H140AEAEA03

Claims (11)

[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%.
And a mean particle size of 0.2 to 2.4 mm. A nickel-copper desulfurizing agent. 2. The carrier is silica-alumina, the S of which
The nickel-copper desulfurizing agent according to claim 1, wherein the i / Al molar ratio is 5 to 7. 3. The nickel-copper-based desulfurizing agent according to claim 1, wherein the average particle size is 0.2 to 1.2 mm. 4. The nickel-copper desulfurization agent according to claim 1, which is used for desulfurization of petroleum hydrocarbons. 5. The nickel-copper desulfurizing agent according to claim 4, wherein the petroleum hydrocarbon is selected from the group consisting of kerosene, light oil, naphtha, gasoline, LPG and natural gas. 6. The nickel-copper desulfurizing agent according to claim 5, wherein the petroleum hydrocarbon is kerosene or LPG. 7. The nickel-copper desulfurizing agent according to claim 1, which is used in a temperature range of −40 to 400 ° C. 8. After desulfurizing petroleum hydrocarbons using the nickel-copper desulfurizing agent according to any one of claims 1 to 7,
A method for producing hydrogen for a fuel cell, which comprises reforming. 9. The method for producing hydrogen for a fuel cell according to claim 8, wherein the reforming treatment is performed by a partial oxidation reforming treatment, an autothermal reforming treatment, or a steam reforming treatment. 10. The method for producing hydrogen for a fuel cell according to claim 9, 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. . 11. The method for producing hydrogen for a fuel cell according to claim 10, wherein the reforming catalyst contains manganese oxide, cerium oxide or zirconia as a carrier component.