JP5755999B2 - Method for producing desulfurizing agent, desulfurizing agent, and method for desulfurizing hydrocarbon - Google Patents

Description

  The present invention relates to a method for producing a hydrocarbon desulfurization agent in a steam reforming process and the like, a desulfurization agent, and a hydrocarbon desulfurization method using the desulfurization agent.

  As raw materials for the steam reforming process, various hydrocarbons such as natural gas, coal gas (COG), liquefied petroleum gas (LPG), naphtha, etc. are used, and these generally contain a sulfur content. . Since this sulfur content poisons the steam reforming catalyst used in the reforming process and the surrounding process catalyst and lowers the catalytic activity, it is necessary to perform a desulfurization treatment of the raw material in advance.

  Conventionally, a typical desulfurization method performed prior to steam reforming of a hydrocarbon is, after hydrocracking organic sulfur in a hydrocarbon raw material using a Co-Mo or Ni-Mo catalyst, This is a hydrodesulfurization method in which produced hydrogen sulfide is adsorbed on zinc oxide and removed.

  However, such a conventional method has a problem. That is, in the hydrodesulfurization process, a certain amount or more of organic sulfur, particularly refractory organic sulfur such as thiophene, slips into the treated hydrocarbon and may pass through without being adsorbed by zinc oxide. .

Further, for adsorption, for example,
ZnO + H ₂ S = ZnS + H ₂ O
ZnO + COS = ZnS + CO ₂
Therefore, the amount of H ₂ S, COS, etc. does not fall below a certain value. This tendency is remarkable especially when H ₂ O and CO ₂ are present. Furthermore, when the desulfurization system is unstable at the time of start-up or shutdown of the apparatus, sulfur may be scattered from the hydrodesulfurization apparatus and the adsorbent desulfurization agent to increase the sulfur concentration in the purified product. Therefore, the desulfurization step in the current steam reforming process is managed at a level at which the sulfur concentration in the refined hydrocarbon is about 0.1 ppm.

  On the other hand, in the steam reforming process, Ni, Ru catalyst or the like is used as a catalyst. These metals are known to form sulfides on the surface even at low concentrations of sulfur below ppm. For example, as clarified in Non-Patent Document 1, since the sulfur adsorption power of Ni and Ru is very strong, even if the sulfur content contained in the raw material is about 0.1 ppm, , Most of the Ni and Ru catalyst surfaces are covered with sulfur (sulfur coverage is 0.8 or more). That is, the steam reforming catalyst is very sensitive to sulfur, and the catalytic activity is lowered even if a slight amount of sulfur is present. Conversely, this means that the current hydrocarbon desulfurization level cannot sufficiently prevent sulfur poisoning of the steam reforming catalyst.

  In particular, since the alternative natural gas production process for producing methane-rich gas is performed at low temperatures, sulfur is easily adsorbed on the catalyst and is more sensitive to low concentrations of sulfur. Even in a steam reforming process carried out at a higher temperature, the effect of low-concentration sulfur becomes serious when downsizing of the reactor is required as in a fuel cell reformer.

  Therefore, in order to prevent sulfur poisoning of the catalyst in the downstream process and improve the economic efficiency of the entire process, it is extremely desirable to reduce the sulfur content in the raw material as much as possible.

  From such a viewpoint, Patent Documents 1 and 2 disclose a method for producing a copper-zinc-based desulfurizing agent and a method for producing a copper-zinc-aluminum-based desulfurizing agent. That is, when these desulfurizing agents are used, the remarkable effect that the sulfur concentration in the raw material can be reduced to 1 ppb or less is achieved. However, even when these desulfurizing agents are used, the amount of the desulfurizing agent used must be increased in order to maintain this high desulfurization level for a long time.

  On the other hand, iron and nickel are conventionally known to have excellent sulfur adsorption capacity and excellent performance as a desulfurizing agent, and are used as a desulfurizing agent in several processes.

However, there is a great obstacle to applying an iron-based desulfurizing agent or a nickel-based desulfurizing agent as it is to the desulfurization of the steam reforming process. That is, the desulfurization in the steam reforming process is normally performed in the presence of hydrogen, and this hydrogen is covered by the recycle gas from the reformer outlet. Since this recycle gas contains CO and CO ₂ in addition to hydrogen, in the presence of an iron-based or nickel-based desulfurizing agent, a reaction between hydrogen, CO, and CO ₂ (methanation reaction) occurs, resulting in large heat generation. There is a problem that accompanies.

  Patent Document 3 discloses a method of using a nickel-based desulfurizing agent in a steam atmosphere after bringing a raw material into contact with a hydrodesulfurization catalyst and a hydrogen sulfide desulfurizing agent in order to suppress this methanation reaction. doing. However, this method requires not only a steam reforming reactor, but also a desulfurizer with a steam introduction line. By introducing steam into the desulfurizer, the original desulfurization of the nickel-based desulfurization agent is required. There is a problem that performance cannot be utilized.

  Furthermore, the use of nickel-based desulfurization agents in the absence of hydrogen has also been reported. However, hydrogen is essential in order to decompose the organic sulfur compound and desorb it as a hydrocarbon containing no sulfur. If the organic sulfur compound is decomposed in the absence of hydrogen, the carbon is likely to break out onto the nickel desulfurization agent, leading to an increase in differential pressure and blockage of the desulfurization layer in the long term.

  In view of this, the main purpose of Patent Document 4 is to provide a new desulfurization agent that can stably desulfurize a hydrocarbon raw material for a long period of time by using a small amount. The resulting mixture is mixed with an aqueous solution of an alkaline substance to form a precipitate, and the resulting precipitate is fired to obtain a molded product of a copper oxide-zinc oxide-aluminum oxide mixture. There has been proposed a method for producing a desulfurizing agent, which is impregnated with at least one selected from the above, further baked, and the obtained oxide fired body is reduced by hydrogen.

JP-A-1-123627 JP-A-1-123628 JP-A-2-204301 Japanese Patent No. 4096128

McCarty et al; Chem. Phys. vol. 72. No. 12, 6332, 1980: J. Am. Chem. Phys. vol. 74, no. 10, 5877, 1981

  However, according to the present inventors, in the above-described method for producing a desulfurizing agent, although the desulfurizing treatment performance of the obtained desulfurizing agent is improved as compared with the conventional method, the desulfurizing agent thus produced has a mechanical strength that has been conventional. It was found that it was lower than those of the products, easily pulverized, and required handling during transportation and application.

  Accordingly, an object of the present invention is to provide a technique capable of providing a new desulfurization agent having high mechanical strength and capable of stably desulfurizing a hydrocarbon raw material for a long period of time.

[Configuration 1]
In order to achieve the above object, the desulfurizing agent production method of the present invention is characterized by mixing a mixture (molded product component) containing a copper compound and a zinc compound and an aqueous solution of an alkaline substance to cause precipitation. After firing the resulting precipitate and obtaining a molded product of the molded product component, an impregnation step of impregnating the molded product with an impregnating liquid containing a target amount of at least one or more catalyst components selected from iron and nickel is performed. Further, a method for producing a desulfurization agent for performing a firing step of firing the molded article impregnated with the impregnating liquid , wherein an impregnating liquid containing a target amount of the catalyst component to be supported on the molded article is prepared, and the impregnating liquid And the impregnation step is performed a plurality of times to impregnate the molded product with the entire amount of the impregnating liquid .

[Operation effect 1]
According to the above configuration, the desulfurizing agent as a whole has a dense structure composed of fine particle aggregates, and very small copper fine particles are dispersed on the surface of the zinc oxide particles. Similar to the above-described conventional technology, since the molded product contains a target amount of at least one selected from iron and nickel, copper and a catalyst component are formed on the surface of the zinc oxide particles as fine particles on the surface of the molded product. Very uniformly mixed and dispersed. Therefore, the molding is in a highly active state due to chemical interaction with zinc oxide. Therefore, side reactions such as methanation and carbon folding, which were conventionally easy to occur with iron or nickel alone, are suppressed, and highly active desulfurization performance can be maintained over a long period of time. High catalytic activity that can be highly desulfurized. In the molded product, aluminum oxide is uniformly distributed throughout, and prevents sintering of copper-nickel fine particles and zinc oxide particles due to heat and maintains a highly active state. In addition, aluminum oxide can greatly improve the heat resistance of the molded product, and can provide a great advantage of significantly reducing the decrease in strength at high temperatures and the decrease in sulfur adsorption power. Therefore, the usable temperature range can be increased.

Here, in the past, the impregnation step of impregnating the impregnation liquid at a time was performed only once, but in the present application, when the firing step is performed, the catalyst component to be supported on the molded product is targeted. An impregnating solution containing an amount is prepared, the impregnating solution is divided into a plurality of parts, and the impregnation step is performed a plurality of times to impregnate the molded product with the entire amount of the impregnating solution . Thereby, the loading amount of the catalyst component can be accurately grasped. Here, the impregnation step refers to the act of bringing the impregnation liquid into contact with the molded product, but when performing the next impregnation step after a certain impregnation step, it is necessary to return the molded product to a state capable of absorbing the impregnation liquid. In the present application, the impregnation step includes a standby state until the next impregnation step.

  Then, the impregnation liquid is expected to be more uniformly impregnated into the molded product, but according to the present inventors, the desulfurizing agent produced in this way is a conventional one. It became clear that it has high mechanical strength compared with the desulfurization agent obtained by the manufacturing method. Although the mechanism for improving the mechanical strength due to the difference in the manufacturing method has not been clarified, the smaller the concentration of the catalyst component in the impregnating liquid, the smaller the cracks on the surface of the molded product that occur during absorption of the impregnating liquid. by. With the above configuration, a desulfurizing agent having improved mechanical strength can be produced, and a high-performance desulfurizing agent that can be easily handled during transportation and application can be provided.

  In addition, from the examples described later, according to the method for producing a desulfurizing agent of the present invention, the nickel particles supported on the molded article have a smaller particle size than those supported by the conventional method and are highly dispersed. The active surface area of the catalyst component is remarkably increased, and the desulfurization performance is improved.

  Since the desulfurizing agent of the present invention can exhibit a high degree of adsorption effect that has been difficult or impossible to implement with conventional desulfurizing agents, after desulfurizing the hydrocarbon raw material as much as possible according to a conventional method, Even when it is used as a secondary desulfurizing agent, it has a remarkable effect.

[Configuration 2, 3]
After performing an impregnation step of impregnating the molded product with an impregnating liquid, a drying step is performed to dry the molded product before performing the next impregnation step, or
After performing the impregnation step of impregnating the molded product with an impregnation liquid, it is preferable to perform a firing step of firing the molded product before performing the next impregnation step.

[Functions 2 and 3]
When the impregnation step is performed in a plurality of times, if the amount of water in the molded article impregnated with the impregnation liquid is large, there is a problem that it is difficult to absorb the impregnation liquid even if the next impregnation step is performed.

  In such a case, if a drying step is performed, moisture is removed by drying, only the catalyst component is fixed to the molded product, and the impregnating liquid further impregnated in the next impregnation step is easily absorbed into the molded product. .

  Further, such an operation can be similarly performed by firing and supporting the catalyst component dried and fixed on the molded product at a higher temperature. When firing, it is common to perform a drying process first, but a firing process can also be performed without performing a special drying process.

[Configuration 4]
It is preferable if the content of at least one selected from iron and nickel in the molded product is 1 to 10% by weight.

[Operation effect 4]
It is preferable that the content (supported amount) of the catalyst component is determined within an appropriate range since sufficient catalytic activity cannot be obtained if the amount is too much, and if the amount is too large, the improvement ratio of the activity with respect to the amount of catalyst used is reduced. . In this respect, if the content of the catalyst component is 1 to 10% by weight, a highly active desulfurizing agent can be obtained. Moreover, if it is such content, by making a catalyst component exist in the molding surface part, the amount of catalyst components in the molding which is not concerned with desulfurization can be reduced, and efficient desulfurization can be performed.

[Configuration 5]
It is preferable to further reduce the molded product with hydrogen.

[Operation effect 5]
The above-mentioned catalyst component is known to exhibit the most activity in the metal state, and can be made into a more active desulfurization agent by further hydrogen reduction of the molded product.
The desulfurization agent of the present invention may be used in a hydrogen reduction atmosphere, but in this case, even if it is a desulfurization agent precursor before hydrogen reduction, it is in a form in which the activity is enhanced in the state of use, It can be used as a desulfurizing agent.

[Configuration 6]
Moreover, the characteristic structure of the desulfurization agent of this invention exists in the point manufactured by the said manufacturing method.

[Operation effect 6]
That is, the desulfurizing agent obtained by the above production method has a high mechanical strength, is easy to handle during transportation and application, and becomes a high-performance desulfurizing agent.

[Configuration 7]
Moreover, the characteristic structure of the hydrocarbon desulfurization method of the present invention is characterized in that the hydrocarbon is desulfurized in the presence of hydrogen using the desulfurization agent produced by the above production method.

[Operation effect 7]
That is, if a desulfurizing agent produced by the above production method is used, desulfurization and purification of high-quality hydrocarbons can be performed over a long period of time because of high desulfurization activity and excellent mechanical strength.

  When using these desulfurization agents according to the present invention, the sulfur content in various gases and oils is guaranteed to be 50 ppb or less, more preferably 5 ppb or less, and even more optimal conditions 0.5 ppb. It can be as follows.

  Examples of the hydrocarbon raw material to be purified by the method of the present invention include various city gases (in this specification, a gas composed of at least one of C1 to C5 hydrocarbons, and a mixed gas thereof as a main component, Natural gas, ethane, propane, butane, LPG, light naphtha, full-range naphtha, COG, and the like.

  Therefore, a high-performance desulfurization agent that has high mechanical strength and is easy to handle during transportation and application can be used. For example, desulfurization and purification of hydrocarbon gas used in fuel cells and the like can be performed with high efficiency.

  Below, the hydrogen production apparatus of this invention is demonstrated. In addition, although suitable examples are described below, these examples are described in order to more specifically illustrate the present invention, and various modifications can be made without departing from the spirit of the present invention. The present invention is not limited to the following description.

(1) Production of molded article First, a copper compound (for example, at least one of copper nitrate, copper acetate, etc.), a zinc compound (for example, at least one of zinc nitrate, zinc acetate, etc.) and an aluminum compound (for example, hydroxylation) A mixture containing at least one of aluminum, aluminum acetate, sodium aluminate, and the like and an aqueous solution containing an alkaline substance (for example, at least one of sodium carbonate, potassium carbonate, etc.) are mixed and stirred to cause precipitation. . In this case, an aluminum compound may be added to the alkaline substance solution, and this mixed solution may be mixed with a mixed solution containing a copper compound and a zinc compound to generate a precipitate. Next, the produced precipitate is sufficiently washed with water, and then filtered and dried. Subsequently, the obtained dried product is fired at about 270 to 400 ° C., and water is added to the slurry to form an aqueous slurry, followed by filtration, molding, and drying, and a molded product of copper oxide-zinc oxide-aluminum oxide. Get.

  The copper concentration in the mixed solution is usually about 0.1 to 1 mol / L. The zinc concentration in the mixed solution is usually about 0.1 to 1 mol / L. The aluminum concentration in the mixed solution is usually about 0.03 to 1 mol / L. The mixing ratio of the copper compound, the zinc compound, and the aluminum compound is not particularly limited, but copper: zinc: aluminum (atomic ratio) = 1: 0.3 to 10: 0. It is set to about 05 to 2, more preferably about 1: 0.6 to 3: 0.3 to 1.

  If necessary, a known molding aid such as graphite may be added to the slurry in advance in an amount of about 1 to 5% by weight.

  The molding can be performed according to a conventional method such as extrusion molding, tablet molding, granule molding, etc., using the above slurry. The shape, dimensions, etc. of the molded product are not particularly limited, but considering the pressure loss in the process, etc., it may be a spherical body, tablet, granule or the like usually having a size of about 2-6 mm. preferable.

  Furthermore, the molded product may contain a metal oxide, for example, chromium oxide or the like up to about 2 to 3% by weight. In this case, a metal compound (for example, chromium nitrate) may be dissolved in advance in a mixture of molding components including a copper compound, a zinc compound, and an aluminum oxide, or in the mixture of molding components, An aqueous solution of a metal compound prepared separately in advance may be mixed.

(2) Impregnation step Next, the molded product obtained as described above contains a target amount of at least one selected from iron and nickel (catalyst component) as a water-soluble salt (for example, nitrate, acetate, etc.). The impregnating solution is impregnated to impregnate and carry the catalyst component.

  The impregnating solution dissolves a predetermined amount of the catalyst component to be impregnated and supported in the molded product in water, and the total amount is absorbed into the molded product in a plurality of times in order to accurately grasp the supported amount of the catalyst component. Although it is desirable to immerse the molded product in the impregnating solution of a predetermined concentration multiple times, the impregnating solution containing the target amount of catalyst components in the total amount is impregnated into the molded product, and the catalyst component contained in the impregnating solution is supported on the molded product You may do as you do.

  Specifically, when it is desired to support an Amol catalyst component in a predetermined amount of the molded product, an impregnating solution (concentration A / 3 Bmol / mL) in which A / 3 mol of the catalyst component is dissolved in BmL of water is used. The impregnation step is divided into three times by repeating the step of impregnating and absorbing the whole amount three times (the molded body absorbs 3 BmL of impregnating liquid) (the amount of impregnated catalyst is (A / 3B) * 3B = A Or the impregnation solution (concentration A / Bmol / mL) in which Amol of the catalyst component is dissolved in BmL of water is impregnated and absorbed by 1/3 of the total amount 3 times (the compact is BmL). The impregnation step can be performed in three steps by absorbing the impregnation liquid (the amount of impregnated catalyst is (A / B) * B = A), and the catalyst component is supported on a predetermined amount of the molded product. Impregnation according to desired target amount A Of it may be adjusted impregnation amount of concentration and the impregnation solution. The amount of the impregnating liquid can also be adjusted by adjusting the contact time between the impregnating liquid and the molded product.

(3) Drying step and firing step The molded product that has been subjected to the impregnation step is dried in the air and then fired at about 270 to 400 ° C in the air. The concentration of the catalyst component as a metal in the aqueous solution is usually preferably about 0.01 to 10 mol / L.

The drying step and the firing step are performed once for each of the impregnation steps performed in a plurality of times, and then the impregnation step is further performed until the amount of the catalyst component supported on the molded product reaches the target amount. Repeat until.
That is, in the above case, between the impregnation step for the molded product and the reduction step described later,
The impregnation step, the drying step, the firing step, the impregnation step, the drying step, the firing step, the impregnation step, the drying step, and the firing step are sequentially performed.

(4) Reduction step Next, the calcined body that has undergone the above-described steps is a desulfurization agent precursor that functions as a desulfurization agent when the catalyst component is supported and exposed to a reducing atmosphere. This desulfurizing agent precursor is prepared in the range of 150 to 350 in the presence of a mixed gas of hydrogen containing 6% by volume or less, more preferably about 0.5 to 4% by volume of hydrogen and an inert gas (for example, nitrogen gas). A desired desulfurizing agent can be obtained by reducing treatment at about ° C.

  In addition, when the molded body that has undergone the firing process is scheduled to be a desulfurization agent used in a reducing atmosphere, the reduction process can be omitted to obtain a desulfurization agent. In this case, the desulfurization agent is subjected to a reducing action in the environment where the desulfurization agent is used, and can exhibit high desulfurization activity.

  The desulfurizing agent according to the present invention is used by, for example, filling an adsorbing desulfurization apparatus having a predetermined shape and allowing the gas or oil to be purified to pass through in the same manner as the known adsorption type desulfurizing agent.

  That is, the sulfur component in the hydrocarbon raw material can be removed by bringing the hydrocarbon raw material into contact with the desulfurizing agent in a temperature range of about 100 to 400 ° C. Preferably, prior to desulfurization, the hydrocarbon raw material is preheated to a predetermined temperature by a method such as using a heater or exchanging heat with desulfurization gas.

  Usually, a desulfurization method is performed by passing a hydrocarbon raw material through the desulfurization pipe filled with the desulfurization agent.

  Hydrogen gas is added to the hydrocarbon raw material. The amount of hydrogen to be added may be determined by the kind and amount of the sulfur compound contained in the raw material, but since the sulfur content is on the order of ppm, the molar ratio with respect to the raw material hydrocarbon is at least 0.00. It is desirable to set it to 0005 or more, preferably 0.001 or more. When desulfurization is performed as a pretreatment for the steam reforming process, hydrogen produced by the steam reforming reaction can be partially recycled.

The amount of the desulfurizing agent to be charged in the desulfurization pipe is appropriately set in consideration of the sulfur content in the hydrocarbon, the use conditions, etc. In the case of a gaseous hydrocarbon, the GHSV is usually from 100 to 5000 (h ^In the case of liquid hydrocarbons, LHSV may be determined to be about ¹ to 10 (h ⁻¹ ).

  In addition, in order to suppress the decrease in the activity of the desulfurizing agent of the present invention and to extend the life, a known zinc oxide-based adsorptive desulfurizing agent is filled on the upstream side of the packed bed of the desulfurizing agent, and adsorbed with zinc oxide or the like. Sulfur compounds that can be removed may be removed beforehand. According to this method, since hydrogen sulfide and the like contained in city gas produced using coal gas or the like as a raw material is removed by zinc oxide or the like, the load of the desulfurizing agent of the present invention is reduced, and as a result. The life of the desulfurizing agent can be extended. Further, even when the raw material gas contains a mercaptan-based sulfur compound, the load of the desulfurizing agent can be reduced and the life of the desulfurizing agent can be extended by similarly removing in advance.

  Further, when the raw material contains a large amount of sulfur, a known Co-Mo catalyst or a Ni-Mo catalyst and a zinc oxide desulfurization agent are filled on the upstream side of the desulfurization agent of the present invention, and a known hydrodesulfurization method is used. The sulfur content may be lowered to about several ppm in advance.

  Since the desulfurizing agent of the present invention can exhibit a high degree of adsorption effect that has been difficult or impossible to implement with conventional desulfurizing agents, after desulfurizing the hydrocarbon raw material as much as possible according to a conventional method, Even when it is used as a secondary desulfurizing agent, it has a remarkable effect.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. It goes without saying that the present invention is not limited by these examples.

[Example 1]
(Desulfurizing agent A)
A mixed aqueous solution (concentration of 0.5 mol / l) containing copper nitrate and zinc nitrate at a ratio of 1: 1 (molar ratio) was converted to an aqueous sodium carbonate solution (concentration of 0.6 mol / l) kept at about 60 ° C. After dropwise addition with stirring to cause precipitation, the precipitate was sufficiently washed with water, filtered and dried. Next, the dried precipitate was calcined at about 280 ° C., added to water to form a slurry, filtered, dried, and added with a molding aid (graphite) to obtain an extruded product having a diameter of 1/8 inch. .
Next, 10 g of the obtained molded product was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration: 0.09 g / ml), dried, and then fired at 300 ° C. twice to obtain a desulfurization agent. . The nickel content of the desulfurizing agent was 6% by weight.

[Example 2]
(Desulfurizing agent B)
10 g of a molded product obtained by the same operation as in Example 1 was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.06 g / ml), dried, and then fired at 300 ° C. three times. A desulfurizing agent was obtained. The nickel content of the desulfurizing agent was 6% by weight.

[Comparative Example 1]
(Desulfurizing agent C)
10 g of the molded product obtained by the same operation as in Example 1 was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.18 g / ml), dried, and then fired at 300 ° C. to obtain a desulfurizing agent. . The nickel content of the desulfurizing agent was 6% by weight.

Example 3
(Desulfurizing agent D)
10 g of a molded product obtained in the same manner as in Example 1 is impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.16 g / ml), dried, and then fired at 300 ° C. twice. A desulfurizing agent was obtained. The nickel content of the desulfurizing agent was 10% by weight.

Example 4
(Desulfurizing agent E)
10 g of the molded product obtained in the same manner as in Example 1 was impregnated with 3.5 ml of a nickel nitrate aqueous solution (Ni concentration 0.11 g / ml) in total, dried, and then fired at 300 ° C. three times. A desulfurizing agent was obtained. The nickel content of the desulfurizing agent was 10% by weight.

[Comparative Example 2]
(Desulfurizing agent F)
10 g of a molded product obtained by the same operation as in Example 1 was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.32 g / ml), dried, and then fired at 300 ° C. to obtain a desulfurizing agent. . The nickel content of the desulfurizing agent was 10% by weight.

Example 5
(Desulfurization agent G)
10 g of a molded product obtained by the same operation as in Example 1 is impregnated with 3.5 ml of a nickel nitrate aqueous solution (Ni concentration: 0.06 g / ml), dried, and then fired at 300 ° C. twice. A desulfurizing agent was obtained. The nickel content of the desulfurizing agent was 4% by weight.

[Comparative Example 3]
(Desulfurizing agent H)
10 g of a molded product obtained by the same operation as in Example 1 was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.12 g / ml), dried, and then fired at 300 ° C. to obtain a desulfurizing agent. . The nickel content of the desulfurizing agent was 4% by weight.

Example 6
(Desulfurization agent I)
10 g of the molded product obtained by the same operation as in Example 1 was impregnated with 3.5 ml of an aqueous nickel nitrate solution (Ni concentration 0.06 g / ml) and dried at 110 ° C. three times, and then 300 ° C. The desulfurization agent was obtained by baking with. The nickel content of the desulfurizing agent was 6% by weight.

[Physical property test]
For the desulfurization agents A to I prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the hydrogen adsorption amount and the compressive strength were measured. Table 1 shows the Ni particle size and the compressive strength obtained from the hydrogen adsorption amount.

  From this table, in the process of impregnating the molded product with Ni, by impregnating the target amount of Ni in multiple steps, the Ni particles that affect desulfurization performance are reduced in diameter, and the desulfurization agent is further pulverized. It is confirmed that the impact strength increases.

[Another embodiment]
In the above embodiment, after the impregnation process, an example in which the drying process and the firing process are repeated once each and an example in which the impregnation process and the drying process are repeated once each are shown, but only the firing process is performed without the drying process. Also good. That is, in the above embodiment,
(1) Impregnation step-drying step-firing step-impregnation step-drying step-firing step-impregnation step-drying step-firing step (2) impregnation step-drying step-impregnation step-drying step-impregnation step-drying step- I went like the firing process,
If firing is possible without a drying step,
(3) It can also carry out like an impregnation process-baking process-impregnation process-baking process-impregnation process-baking process.

  The desulfurizing agent according to the present invention is highly desulfurized by a small amount of use because it is extremely excellent in desulfurizing performance of hydrocarbons and has high mechanical strength, so it is difficult to be pulverized by vibrations, impacts, etc. during transportation and application. Hydrocarbon can be obtained stably and easily over a long period of time. Therefore, even when using a catalyst that is vulnerable to sulfur poisoning, such as when steam reforming hydrocarbons, sulfur poisoning can be completely prevented in practice, and the negative effects of sulfur are eliminated to an extremely high level. Useful for.

Claims (7)

And an aqueous solution of a mixture with an alkali substance containing a copper compound and a zinc compound are mixed to cause precipitation, calcining the resulting precipitate, copper oxide - After obtaining the molded product of the oxide zinc mixed compound, the A desulfurization agent that performs an impregnation step of impregnating a molded product with an impregnating liquid containing a target amount of at least one catalyst component selected from iron and nickel, and further performs a firing step of calcining the molded product impregnated with the impregnating liquid. A manufacturing method comprising:
A desulfurization process is performed in which an impregnation liquid containing a target amount of the catalyst component to be supported on the molded article is prepared, the impregnation liquid is divided into a plurality of parts, and the impregnation liquid is impregnated a plurality of times to impregnate the entire amount of the impregnation liquid. Manufacturing method.   The method for producing a desulfurization agent according to claim 1, wherein after the impregnation step of impregnating the molded product with the impregnating liquid, a drying step of drying the molded product is performed before performing the next impregnation step.   The method for producing a desulfurization agent according to claim 1 or 2, wherein after the impregnation step of impregnating the molded product with the impregnating liquid, a firing step of firing the molded product is performed before the next impregnation step.   The method for producing a desulfurization agent according to any one of claims 1 to 3, wherein the content of at least one selected from iron and nickel in the molded product is 1 to 10% by weight.   The method for producing a desulfurization agent according to any one of claims 1 to 4, wherein the molded product is further subjected to hydrogen reduction. The desulfurization agent manufactured by the manufacturing method of the desulfurization agent of any one of Claims 1-5.   A hydrocarbon desulfurization method comprising desulfurizing a hydrocarbon raw material in the presence of hydrogen using the desulfurization agent produced by the desulfurization agent production method according to any one of claims 1 to 5. .