Desulfurization catalyst and method for desulfurizing hydrocarbon gas

Abstract

This desulfurization catalyst comprises a porous carrier and an active metal supported on the porous carrier. The porous carrier contains a zinc oxide, and the active metal contains a platinum group element.　This method for desulfurizing hydrocarbon gas comprises bringing a hydrocarbon gas containing a sulfur-containing compound into contact with said desulfurization catalyst in the presence of hydrogen.

Description

Desulfurization catalyst and method for desulfurizing hydrocarbon gases

[0001] The present invention relates to a desulfurization catalyst and a method for desulfurizing hydrocarbon gases.

[0002] Fuel cells convert chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen. Hydrocarbons such as liquefied natural gas (LPG), city gas, naphtha, and kerosene are used as hydrogen sources. When producing hydrogen using gaseous hydrocarbons such as LPG and city gas (hereinafter also referred to as "hydrocarbon gas"), a reforming catalyst is generally used to carry out partial oxidation reforming, autothermal reforming, or steam reforming.

[0003] Sulfur-containing compounds such as tetrahydrothiophene (THT) and tert-butyl mercaptan (TBM) are added to hydrocarbon gases as odorants. Reforming catalysts used to produce hydrogen are poisoned by sulfur-containing compounds, reducing their catalytic performance; therefore, it is necessary to remove these sulfur-containing compounds from the hydrocarbon gas. One known method for removing sulfur-containing compounds from hydrocarbon gases is to pass the hydrocarbon gas through a desulfurizer containing desulfurizing agents such as iron oxide, zinc oxide, impregnated activated carbon, and silver ion exchange zeolite.

[0004] Furthermore, for example, Patent Document 1 below proposes a method in which the sulfur content in kerosene is converted to hydrogen sulfide using a hydrodesulfurization catalyst such as CoMo / alumina, and then removed with a predetermined desulfurizing agent.

[0005] Japanese Patent Publication No. 2003-290659

[0006] The technology of using a hydrogenation desulfurization catalyst and a desulfurizing agent in series is expected to sufficiently reduce the sulfur content even in hydrocarbon gases containing various sulfur-containing compounds such as odorants. On the other hand, a simple and compact desulfurization apparatus is advantageous in terms of energy efficiency, etc. However, the above technology is not necessarily suitable for simplifying or compacting the apparatus, and such considerations have not been sufficiently made.

[0007] This invention has been made in view of the above circumstances, and aims to provide a desulfurization catalyst and a desulfurization method using the same that have sufficient desulfurization performance while enabling simplification and compactness of desulfurization equipment.

[0008] The inventors investigated a system using both a hydrogenation desulfurization catalyst and a desulfurizing agent, and found that the expected desulfurization performance could not be obtained with a mixture of the two. They hypothesized that this was due to uneven packing caused by the difference in specific gravity between the hydrogenation desulfurization catalyst and the desulfurizing agent. Specifically, in desulfurization performance tests of a desulfurization apparatus packed with a mixture of hydrogenation desulfurization catalyst and desulfurizing agent, the breakthrough time (the time required for the desulfurization rate to fall below a predetermined value) was sometimes shortened. They considered that the reason the desulfurization rate tends to decrease is that the uneven flow of the circulating gas due to the above-mentioned unevenness reduces the area of ​​sites that can be used for sulfur adsorption. Based on this hypothesis, they diligently investigated from the perspective of suppressing uneven flow of the circulating gas and found that a desulfurization catalyst, in which a specific active metal is supported on a porous carrier containing a specific metal oxide, can extend the breakthrough time (the time required for the desulfurization rate to fall below a predetermined value) in desulfurization performance tests of a desulfurization apparatus compared to a mixture of a hydrogenation desulfurization catalyst containing the same active metal and a desulfurizing agent made of the same metal oxide.

[0009] One aspect of the present invention relates to the following desulfurization catalyst and desulfurization method.

[0010] [1] A desulfurization catalyst comprising a porous carrier and an active metal supported on the porous carrier, wherein the porous carrier contains zinc oxide and the active metal contains a platinum group element. [2] The desulfurization catalyst according to [1], wherein the porous carrier contains 60% by mass or more of zinc oxide based on the total amount of the porous carrier, and the active metal contains platinum or palladium. [3] The desulfurization catalyst according to [1] or [2], wherein the porous carrier contains sepiolite. [4] The desulfurization catalyst according to any one of [1] to [3], wherein the active metal is unevenly distributed near the surface of the porous carrier. [5] The desulfurization catalyst according to any one of [1] to [4], wherein the average pore size of the porous carrier is 20 to 60 nm. [6] The specific surface area of ​​the porous carrier is 30 to 70 m². ２[1] to [5] a desulfurization catalyst according to any one of the following: [7] The amount of active metal supported is 0.001 to 0.1% by mass on a basis of the total amount of the desulfurization catalyst according to any one of the following: [8] A method for desulfurizing a hydrocarbon gas, comprising the step of contacting a hydrocarbon gas containing a sulfur-containing compound with a desulfurization catalyst according to any one of the following: [1] to [7] in the presence of hydrogen. [9] A method for desulfurizing a hydrocarbon gas according to [8], wherein the hydrocarbon gas contains one or more hydrocarbons selected from methane, ethane, ethylene, propane, propylene, butane, and butene.

[0011] According to the present invention, it is possible to provide a desulfurization catalyst that has sufficient desulfurization performance while enabling the simplification and compactness of the desulfurization apparatus, and a method for desulfurizing hydrocarbon gas using the same.

[0012] Figure 1 shows the relationship between the reaction time of the catalyst and the desulfurization rate.

[0013] <Desulfurization Catalyst> The desulfurization catalyst of this embodiment comprises a porous carrier and an active metal supported on the porous carrier, wherein the porous carrier contains zinc oxide and the active metal contains a platinum group element.

[0014] According to the desulfurization catalyst of this embodiment, by having the above configuration, a hydrocarbon gas containing a sulfur-containing compound can be brought into contact with it in the presence of hydrogen to obtain a hydrocarbon gas with a sufficiently reduced sulfur content. Furthermore, since the desulfurization catalyst of this embodiment has superior desulfurization performance compared to the case in which a hydrogenation catalyst and a hydrogen sulfide adsorbent are mixed, the desulfurization apparatus (e.g., a hydrogenation desulfurizer) can be made more compact.

[0015] The zinc oxide content in the porous carrier may be 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total amount of the porous carrier.

[0016] The porous carrier may further contain components other than the zinc oxide mentioned above. Such components include binders.

[0017] Examples of binders include alumina, silica, titania, zirconia, and clay.

[0018] Examples of clays include sepiolite, attapulgite, and bentonite. From the viewpoint of further improving the desulfurization performance of the desulfurization catalyst, the porous support can contain sepiolite.

[0019] The binder content in the porous carrier may be 5 to 40% by mass, 10 to 40% by mass, 15 to 40% by mass, or 30 to 40% by mass, based on the total amount of the porous carrier.

[0020] The porous support may have mesopores (2 to 50 nm) from the viewpoint of further improving the desulfurization performance of the desulfurization catalyst.

[0021] The average pore size of the porous support may be 20 to 60 nm. The average pore size can be measured by the mercury intrusion method.

[0022] The specific surface area of ​​the porous support is 30 m², from the viewpoint of the desulfurization performance of the desulfurization catalyst. ２ / g or more, 40m ２ / g or more, or 50m ２ It may be 30 to 70 m / g or more, and from the viewpoint of achieving a high level of both the desulfurization performance and mechanical strength of the desulfurization catalyst, ２ It may also be / g, 40-70m ２ It may also be / g, 50-70m ２ It may also be / g. The specific surface area can be measured by nitrogen adsorption / desorption.

[0023] Porous carriers can be prepared using known methods. For example, a porous carrier may be prepared by molding a mixture of zinc oxide, a binder, and, if necessary, additives such as lubricating and release agents such as methylcellulose, porosizing agents, and aggregates, and then firing it in an air atmosphere.

[0024] The zinc oxide incorporated into the mixture may be in particulate form, and its particle size may be 45 μm or less, or 20 μm or less. The binder incorporated into the mixture may also be in particulate form, and its volume-average particle size (D50) may be 5 to 40 μm, or 10 to 20 μm.

[0025] The platinum group elements may be one or more selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt), and among these, platinum or palladium may be preferred from the viewpoint of their ability to hydrogenate sulfur compounds.

[0026] The amount of active metal supported may be 0.001 to 0.1% by mass, 0.005 to 0.05% by mass, or 0.008 to 0.02% by mass, based on the total amount of desulfurization catalyst. Alternatively, the amount of active metal supported may be within the above ranges based on the total mass of the porous carrier and the active metal.

[0027] The loading of active metals onto porous carriers can be carried out by known methods such as impregnation and vapor deposition. For example, when using the impregnation method, a solution (usually an aqueous solution) of a platinum group element salt is prepared, impregnated into the porous carrier, and then dried and, if necessary, calcined.

[0028] The firing can be carried out under an air or nitrogen atmosphere. The firing temperature may be 400-700°C, 450-650°C, or 500-600°C. The desulfurization catalyst of this embodiment may be subjected to reduction treatment with hydrogen or the like as needed.

[0029] In the desulfurization catalyst of this embodiment, the active metal may be unevenly distributed near the surface of the porous support in order to further improve the desulfurization performance. Such surface support can be carried out, for example, by spray impregnation.

[0030] The shape of the desulfurization catalyst in this embodiment is not particularly limited and can be appropriately selected depending on the form in which the catalyst is used. Examples include pellets, granules, honeycomb, and sponge shapes.

[0031] <Method for desulfurizing hydrocarbon gases> The method for desulfurizing hydrocarbon gases according to this embodiment comprises a desulfurization step in which a hydrocarbon gas containing a sulfur-containing compound is brought into contact with the desulfurization catalyst of this embodiment described above in the presence of hydrogen.

[0032] As the hydrocarbon gas, hydrocarbon gases derived from conventional fossil fuels such as petroleum and coal, hydrocarbon gases derived from synthetic fuels such as synthesis gas, and hydrocarbon gases derived from biomass can be appropriately used.

[0033] Specifically, methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, biogas, etc. can be used.

[0034] In this embodiment, the hydrocarbon gas may contain hydrocarbon compounds having 4 or less carbon atoms, and may contain one or more hydrocarbons of methane, ethane, ethylene, propane, propylene, butane and butene.

[0035] Examples of the sulfur-containing compound include sulfur compounds originally contained in hydrocarbons and the odorants added to detect gas leakage. When the hydrocarbon gas is city gas, for example, hydrogen sulfide (H ２ S), carbonyl sulfide (COS), carbon disulfide (CS ２ ), tetrahydrothiophene (THT), dimethyl sulfide (DMS), tert-butyl mercaptan (TBM), ethyl methyl sulfide (EMS), diethyl sulfide (DES), dimethyl disulfide (DMDS), diethyl disulfide (DEDS), etc. are included.

[0036] As the temperature condition in the desulfurization process according to this embodiment, it may be 200 to 350 °C.

[0037] The GHSV may be 10 to 10,000 h －１ , 10 to 5,000 h －１ , or 10 to 2,000 h －１ .

[0038] The mixing ratio of hydrogen may be set to be 1 to 50% by volume, 5 to 30% by volume, or 10 to 20% by volume with respect to the hydrocarbon gas.

[0039] The hydrocarbon gas may contain moisture, and the moisture content in the hydrocarbon gas may be 10% by volume or less, 8% by volume or less, or 5% by volume or less.

[0040] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples, but the present invention is not limited to the following examples.

[0041] <Preparation of porous carrier> (Carrier A) 80 parts by mass of zinc oxide (particle size: 45 μm or less), 20 parts by mass of pseudo-boehmite (D50: 40 to 50 μm) as alumina, and 3 parts by mass of methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., product name "SM-4000") were mixed to obtain a mixed powder. 38 parts by mass of ion-exchanged water was added to this mixed powder, and the dough was prepared by kneading well using a mixer. Next, the prepared dough was formed into a pellet shape (2 mmφ) using an extrusion molding machine. The obtained molded body was dried at 150°C using a dryer, and then fired at 600°C for 3 hours to obtain Carrier A.

[0042] (Carrier B) 80 parts by mass of zinc oxide (particle size: 45 μm or less), 20 parts by mass of pseudo-boehmite (D50: 40 to 50 μm) as alumina, 3 parts by mass of methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., product name "SM-4000"), and 3 parts by mass of walnut shell (particle size: 200 μm or less) as a pore-forming agent were mixed to obtain a mixed powder. 38 parts by mass of ion-exchanged water was added to this mixed powder, and the dough was prepared by kneading well using a mixer. Next, the prepared dough was formed into a pellet shape (2 mmφ) using an extrusion molding machine. The obtained molded body was dried at 150°C using a dryer, and then fired at 600°C for 3 hours to obtain Carrier B.

[0043] (Carrier C) 80 parts by mass of zinc oxide (particle size: 45 μm or less), 20 parts by mass of sepiolite (D50: 10 to 20 μm), 3 parts by mass of methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., product name "SM-4000"), and 3 parts by mass of walnut shell (particle size: 200 μm or less) as a pore-forming agent were mixed to obtain a mixed powder. 38 parts by mass of ion-exchanged water was added to this mixed powder, and the dough was prepared by kneading well using a mixer. Next, the prepared dough was formed into a pellet shape (2 mmφ) using an extrusion molding machine. The obtained molded body was dried at 150°C using a dryer, and then fired at 600°C for 3 hours to obtain Carrier C.

[0044] (Carrier D) 80 parts by mass of iron oxide (particle size: 1 to 150 μm), 20 parts by mass of sepiolite (D50: 10 to 20 μm), 3 parts by mass of methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., product name "SM-4000"), and 3 parts by mass of walnut shells (particle size: 200 μm or less) as a porosizing agent were mixed to obtain a mixed powder. 30 parts by mass of ion-exchanged water were added to this mixed powder and thoroughly kneaded using a mixer to prepare dough. Next, the prepared dough was molded into pellets (2 mmφ) using an extruder. The resulting molded bodies were dried in a dryer at 150°C and then calcined at 600°C for 3 hours to obtain carrier D.

[0045] (Carrier E) 80 parts by mass of manganese oxide (particle size: 5.04 μm), 20 parts by mass of sepiolite (D50: 10-20 μm), 3 parts by mass of methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., product name "SM-4000"), and 3 parts by mass of walnut shells (particle size: 200 μm or less) as a porosizing agent were mixed to obtain a mixed powder. 46 parts by mass of ion-exchanged water were added to this mixed powder and thoroughly kneaded using a mixer to prepare dough. Next, the prepared dough was molded into pellets (2 mmφ) using an extruder. The resulting molded bodies were dried in a dryer at 150°C and then calcined at 300°C for 3 hours to obtain carrier E.

[0046] <Preparation of Catalyst> (Example 1) 110 g of an aqueous solution of chloroplatinic acid (concentration 84 ppm) was prepared and impregnated and supported on 100 g of support A. Next, the impregnated and supported support was calcined at 540°C for 3 hours under a flow of dry air (flow rate 6.7 L / min), and then subjected to a reduction treatment at 500°C for 1 hour under a flow of pure hydrogen (flow rate 2 L / min) to obtain desulfurization catalyst #1.

[0047] The obtained desulfurization catalyst was analyzed by ICP emission spectrometry. The analysis of the desulfurization catalyst involved measuring the concentration of each component using an ICP emission spectrometer (ICP-OES) (Avio 550 MAX, manufactured by PerkinElmer LLC). For the measurement, the sample was pretreated with acid, and quantitative analysis was performed using the calibration curve method.

[0048] It was confirmed that desulfurization catalyst #1 contains platinum and zinc oxide in amounts of 0.01% by mass and 80% by mass, respectively.

[0049] (Example 2) 110 g of an aqueous solution of chlorplatinic acid (concentration 84 ppm) was prepared, and this aqueous solution of chlorplatinic acid was spray-impregnated into 100 g of carrier A, which was heated and stirred. At this time, the solution delivery rate was set to 5 g / min, and the air flow rate during spray drying was set to 40 L / min. Next, the carrier after spray impregnation was calcined at 540°C for 3 hours under a flow of dry air (flow rate 6.7 L / min), and then subjected to a reduction treatment at 500°C for 1 hour under a flow of pure hydrogen (flow rate 2 L / min) to obtain desulfurization catalyst #2 in which platinum was unevenly distributed near the surface of the carrier.

[0050] When the obtained desulfurization catalyst #2 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and zinc oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0051] (Example 3) Desulfurization catalyst #3 was obtained in the same manner as in Example 1, except that support B was used instead of support A.

[0052] When the obtained desulfurization catalyst #3 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and zinc oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0053] (Example 4) Desulfurization catalyst #4 was obtained in the same manner as in Example 1, except that support C was used instead of support A.

[0054] When the obtained desulfurization catalyst #4 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and zinc oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0055] (Example 5) Desulfurization catalyst #5 was obtained in the same manner as in Example 1, except that support C was used instead of support A and the concentration of the chloroplatinic acid aqueous solution was increased.

[0056] When the obtained desulfurization catalyst #5 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and zinc oxide at concentrations of 0.02% by mass and 80% by mass, respectively.

[0057] (Example 6) Desulfurization catalyst #6 was obtained in the same manner as in Example 1, except that support C was used instead of support A and the concentration of the chloroplatinic acid aqueous solution was reduced.

[0058] When the obtained desulfurization catalyst #6 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and zinc oxide at concentrations of 0.005% by mass and 80% by mass, respectively.

[0059] (Example 7) Desulfurization catalyst #7 was obtained in the same manner as in Example 1, except that 110 g of tetraamminepalladium nitrate solution was prepared instead of chloroplatinic acid aqueous solution and impregnated and supported on 100 g of carrier C with this solution.

[0060] When the obtained desulfurization catalyst #7 was analyzed using the same method as in Example 1, it was confirmed that it contained palladium and zinc oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0061] (Comparative Example 1) As a hydrogenation desulfurization catalyst, 10 parts by mass of an extruded body (platinum concentration: 0.1% by mass) in which platinum is supported on an alumina carrier was crushed and sieved through a 0.85 to 1.40 mm sieve was used, and 90 parts by mass of zinc oxide particles obtained by tumbling granulation (2 mmφ) were crushed and sieved through a 0.85 to 1.40 mm sieve was used as a desulfurization agent. These were mixed to obtain a mixture.

[0062] (Comparative Example 2) Carrier C was prepared.

[0063] (Comparative Example 3) Desulfurization catalyst #C3 was obtained in the same manner as in Example 1, except that support D was used instead of support A.

[0064] When the obtained desulfurization catalyst #C3 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and iron oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0065] (Comparative Example 4) Desulfurization catalyst #C4 was obtained in the same manner as in Example 1, except that support E was used instead of support A.

[0066] When the obtained desulfurization catalyst #C4 was analyzed using the same method as in Example 1, it was confirmed that it contained platinum and manganese oxide at concentrations of 0.01% by mass and 80% by mass, respectively.

[0067] <Evaluation of Catalysts> The specific surface area, average pore diameter, and desulfurization performance of the desulfurization catalysts obtained in the examples and comparative examples were measured by the following methods. In addition, the desulfurization performance of the mixture in Comparative Example 1 and the specific surface area, average pore diameter, and desulfurization performance of support C in Comparative Example 2 were evaluated by the same methods.

[0068] [Measurement of Specific Surface Area] The specific surface area of ​​the desulfurization catalyst was measured using a nitrogen adsorption device (Micromeristics "TriStar II 3020") by the BET multipoint method. Prior to measurement, the sample was pretreated by heating at 250°C.

[0069] [Measurement of Average Pore Diameter] The average pore diameter of the desulfurization catalyst was measured using a mercury intrusion apparatus (AutoPore IV 9500, manufactured by Micromeristics) with a contact angle of 130° and a measurement pressure range of 0.5 to 33,000 psi.

[0070] [Desulfurization Performance] The desulfurization performance of the desulfurization catalyst was evaluated under the following evaluation conditions. (Evaluation Condition A) The pelletized catalyst was crushed and then sized to a range of 850 to 1400 μm using a sieve of 14 to 20 mesh size. 7.8 ml of the sized catalyst was packed into a vertical atmospheric pressure fixed-bed flow reactor, and a reaction gas containing sulfur-containing compounds and hydrocarbon gases, as shown in Table 1, was added at GHSV = 1000 h. －１ The mixture was passed through at atmospheric pressure and a catalyst inlet temperature of 280°C. For Comparative Example 1, 7.8 ml of a mixture of the hydrogenodesulfurization catalyst and desulfurizing agent was packed into the reaction apparatus.

[0071]

[0072] The sulfur concentration at the outlet of the reaction vessel was measured using a chemiluminescent sulfur detector (SCD)-GC to determine the desulfurization rate. The measurement was performed using a GC column (DS-Sulfur (60 m × 320 μm × 4.2 μm)) which was heated to 180°C at a heating rate of 20°C / min and held at 180°C for 5 minutes. The time required for the desulfurization rate to fall below 98.75% was defined as the catalyst breakthrough time (lifetime).

[0073] (Evaluation Condition B) The breakthrough time (lifetime) of the catalyst was evaluated in the same manner as in Evaluation Condition A, except that the pelletized catalyst was used as is without pulverization. If the desulfurization rate was below 98.75% immediately after the start of the reaction, the breakthrough time was set to 0 hours.

[0074] Figure 1 shows the relationship between the reaction time of the catalyst and the desulfurization rate, and displays the results for evaluation condition B of the catalysts in Examples 1 to 7 and Comparative Examples 1 to 4. In Figure 1, a desulfurization rate of 1 represents 100%.

[0075]

[0076] As shown in Table 2, the desulfurization catalyst of Example 1 was found to extend the breakthrough time in methane gas desulfurization by 10 times compared to Comparative Example 1, which used a mixture of a hydrogenation desulfurization catalyst and a desulfurizing agent. Furthermore, as shown in Figure 1, the desulfurization catalyst of Example 2, in which the active metal is unevenly distributed near the surface, was found to have desulfurization performance equal to or better than that of the desulfurization catalyst of Example 1, and to be less prone to degradation. In addition, the desulfurization catalyst of Example 3, in which the average pore diameter of the carrier was increased by a porosizing agent, was found to have superior desulfurization performance compared to the desulfurization catalyst of Example 1. Furthermore, the desulfurization catalyst of Example 4, which used sepiolite as a binder for the porous carrier, was found to have superior desulfurization performance compared to the desulfurization catalyst of Example 3.

[0077] According to the present invention, as described above, it is possible to provide a desulfurization catalyst that can maintain sufficient desulfurization performance over a long period of time. This makes it possible to suppress the increase in the amount of catalyst required to maintain performance, and facilitates the simplification and compactness of the desulfurization apparatus. Furthermore, according to the present invention, it is possible to reduce the frequency of recovery work (e.g., catalyst replacement) required when the desulfurization rate falls below a predetermined value.

Claims

1. A desulfurization catalyst comprising a porous carrier and an active metal supported on the porous carrier, wherein the porous carrier contains zinc oxide and the active metal contains a platinum group element.

2. The desulfurization catalyst according to claim 1, wherein the porous carrier contains 60% by mass or more of zinc oxide based on the total amount of the porous carrier, and the active metal contains platinum or palladium.

3. The desulfurization catalyst according to claim 1, wherein the porous carrier contains sepiolite.

4. The desulfurization catalyst according to claim 1, wherein the active metal is unevenly distributed near the surface of the porous carrier.

5. The desulfurization catalyst according to claim 1, wherein the average pore size of the porous carrier is 20 to 60 nm.

6. The specific surface area of ​​the porous carrier is 30 to 70 m². ２ The desulfurization catalyst according to claim 1, wherein the amount is / g.

7. The desulfurization catalyst according to claim 1, wherein the amount of the active metal supported is 0.001 to 0.1% by mass based on the total amount of the desulfurization catalyst.

8. A method for desulfurizing a hydrocarbon gas, comprising the step of contacting a hydrocarbon gas containing a sulfur-containing compound with a desulfurization catalyst according to any one of claims 1 to 7 in the presence of hydrogen.

9. The method for desulfurizing a hydrocarbon gas according to claim 8, wherein the hydrocarbon gas comprises one or more hydrocarbons selected from methane, ethane, ethylene, propane, propylene, butane, and butene.

Images