JP2009072712A - Method for producing adsorbent for removing microingredient in hydrocarbon oil and adsorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent which is made of hard active carbon having a high specific surface area and a high bulk density and efficiently adsorbs/removes microingredients in hydrocarbon oil, a method for producing the adsorbent, a method for removing the microingredients in the hydrocarbon oil using the adsorbent, and a fuel battery system. <P>SOLUTION: The method for producing the adsorbent includes the molding carbonization treatment process in which a binder made of saccharide is added into vegetable biomass or a vegetable biomass preliminary carbonization treatment product, and the mixture, after being kneaded and molded, is carbonized to obtain a molded carbonization treatment product and the activation treatment process in which the obtained molded carbonization treatment product, after being impregnated with the binder, is activated to obtain a molded activation treatment product. The adsorbent for removing the microingredients in the hydrocarbon oil containing an activation treatment product which is obtained by the above method and has a specific surface area of at least 600 m<SP>2</SP>/g and a mean micropore width of at least 1.0 nm, the method for removing the mictoingredients in the hydrocarbon oil using the adsorbent, or the fuel battery system provided with the adsorbent are disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an adsorbent that adsorbs and removes trace components in hydrocarbon oil, such as sulfur compounds and polycyclic aromatic compounds, an adsorbent obtained by the production method, and a hydrocarbon using the adsorbent. The present invention relates to a method for removing trace components in oil and a fuel cell system equipped with the adsorbent.

And CO ₂ gas as a greenhouse gas, from the viewpoint of reducing the emissions of automotive exhaust gases, such as NO _X, further reduction of sulfur content in the fuel, it is strongly desired by society. In Japan, it is said that in the near future, the sulfur content in gasoline and light oil will be regulated to 10 mass ppm or less. On the other hand, recent technological innovations in fuel cells are remarkable. When the hydrogen source is determined for petroleum-based fuel, if the sulfur content in the fuel oil is not reduced to the ppb level, the fuel cell reformer and the electrode catalyst are poisoned by the sulfur content, and the fuel cell system Thus, the desired life is not obtained. Against this background, desulfurization technology for obtaining ultra-low sulfur petroleum fuel oil has been actively researched.

  Most of the difficult desulfurization compounds that are difficult to remove by conventional hydrodesulfurization methods are benzothiophenes and dibenzothiophenes. In the case of kerosene, the ratio of benzothiophenes is particularly large, and the ratio of benzothiophenes to the total sulfur compounds is often 70% or more as the sulfur content. However, dibenzothiophenes with a low content are more difficult to remove, and in particular, alkyl dibenzothiophenes having a large number of alkyl groups are very difficult to remove. On the other hand, there is a demand for a method that can be easily and efficiently desulfurized by a simple operation. For example, no reduction treatment or hydrogen is required, no pressure is required, and room temperature to about 150 ° C. Therefore, a desulfurization agent that can efficiently remove dibenzothiophenes at a relatively low temperature is desired. In order to use a large amount of a desulfurizing agent in a refinery or the like, not only the removal performance but also the cost and economy must be excellent.

  Activated carbon having a specific pore structure, particularly fibrous activated carbon, has been reported to have high removal performance with respect to dibenzothiophenes contained in light oil and kerosene (Patent Document 1). However, since the fibrous activated carbon is cotton-like, the packing density cannot be increased. Therefore, there are problems that the adsorption performance per unit volume is not high, the manufacturing process is complicated, the manufacturing cost is extremely high, and it is not economical.

The present inventors perform further activation treatment after carbonizing plant biomass at 300 to 900 ° C. under reduced pressure, or after carbonizing at 200 to 900 ° C. under reduced pressure and / or inert atmosphere. The carbonized product or activated product having a specific surface area of 200 m ² / g or more and an average pore width of 2.0 nm or more obtained by the above can be suitably used for removing trace components in hydrocarbon oil, It has been found that the activated carbon obtained as described above as a raw material has an excellent ability to adsorb dibenzothiophenes, which are hardly desulfurized compounds in fuel oil (Patent Document 2). However, rice husk activated carbon that has undergone carbonization and activation treatment is very brittle, and when used in a flow-type sulfur content adsorption removal device, it is easily pulverized by fluid pressure, so that it does not adversely affect subsequent equipment. It is necessary to install extra equipment, such as removing the activated carbon that has been crushed with a filter or other equipment. In order to prevent this, an improvement such as increasing the strength of the activated carbon to such an extent that it is not pulverized during desulfurization or forming it into a hard granule is desired.
International Publication No. WO2003 / 097771 Pamphlet Japanese Patent Application No. 2007-66492

  The present invention has been made under such circumstances, and a method for producing an adsorbent that can increase the specific surface area, is composed of hard and high bulk density activated carbon, and efficiently adsorbs and removes trace components in hydrocarbon oil. The issue is to provide. Another object of the present invention is to provide an adsorbent obtained by such a production method, a method for removing trace components in hydrocarbon oil using the adsorbent, and a fuel cell system.

  In order to achieve the above object, the present inventors have selected a carbon source and an appropriate binder of activated carbon, which is the main material of the adsorbent for removing trace components in hydrocarbon oil, and their addition amount, As a result of earnest examination of manufacturing conditions such as activation temperature, it is representative of molded rice husk activated carbon that realizes high moldability, excellent shape retention, and excellent adsorption capacity per unit volume, especially adsorption capacity for dibenzothiophenes The present inventors have found a method for producing an adsorbent comprising a molded activation treatment product, and have completed the present invention.

That is, the present invention includes the following inventions.
(1) In a method for producing an adsorbent containing activated carbon, a molding carbonization step of obtaining a molded carbonized product by carbonizing after adding a molding binder made of saccharides to a plant biomass and kneading and molding, and obtaining A hydrocarbon oil comprising an activation treatment step of adding a binder for impregnation made of saccharides to the obtained molded carbonized product and impregnating it, followed by activation treatment to obtain a molded activation processed product having a specific surface area of 600 m ² / g or more which is activated carbon A method for producing an adsorbent that removes trace components therein.

(2) Furthermore, the second activation treatment is performed by impregnating the molded activation treatment product again with a binder for impregnation made of saccharides to obtain a second molding activation treatment product having a specific surface area of 600 m ² / g or more. The manufacturing method of the adsorption agent as described in said (1) including a process.
(3) The adsorbent according to (1) or (2), further including an impregnation carbonization step of impregnating a plant biomass with an impregnation binder composed of a saccharide and performing carbonization before the shaping carbonization step. Production method.
(4) The method for producing an adsorbent according to any one of (1) to (3), further comprising a preliminary carbonization treatment step of pre-carbonizing plant biomass to obtain a pre-carbonized product.
(5) The preliminary carbonization treatment is performed at 200 to 600 ° C. in an inert atmosphere for 0.01 to 2 hours, and the impregnation carbonization treatment and the forming carbonization treatment are performed at 0 to 200 ° C. in an inert atmosphere, respectively. The above (1) to (4) are carried out for 0.01 to 2 hours, and the activation treatment and the second activation treatment are each carried out at 800 to 900 ° C. for 0.1 to 4 hours in a carbon dioxide atmosphere. The manufacturing method of the adsorption agent in any one.
(6) The method for producing an adsorbent according to any one of (1) to (5), wherein the plant biomass is rice husk.
(7) The method for producing an adsorbent according to any one of the above (1) to (6), wherein the saccharide is at least one selected from sugar beet sugar, brown sugar and sugar sucrose.

(8) Activation treatment product obtained by the method for producing an adsorbent according to any one of (1) to (7), having a specific surface area of 600 m ² / g or more and an average pore width of 1.0 nm or more. And / or an adsorbent that removes trace components in the hydrocarbon oil containing the second molding activation treatment product.

(9) Removal of trace components in hydrocarbon oil, characterized by adsorbing and removing sulfur compounds and / or polycyclic aromatic compounds contained in hydrocarbon oil using the adsorbent according to (8) above Method.
(10) The removal method according to (9), wherein the hydrocarbon oil is kerosene or light oil.
(11) The removal method according to (9) or (10), wherein the sulfur compound is adsorbed and removed at a temperature of 150 ° C. or lower.

(12) A fuel cell system equipped with the adsorbent according to (8).

  According to the production method of the present invention, a charcoal of rice husk obtained from plant biomass, particularly rice, and a binder made of saccharide are kneaded and molded, and then carbonized to obtain a molded carbonized product. Since it is an adsorbent made of activated carbon obtained by impregnating a treated substance with a binder made of saccharide and activated, it provides an adsorbent with a high specific surface area, excellent shape retention, and a relatively high bulk density. be able to. For this reason, the adsorbent of the present invention has high adsorption performance per unit volume (volume), and includes hydrocarbon oils, particularly kerosene and light oil containing dibenzothiophenes as sulfur compounds or containing polycyclic aromatic compounds. Adsorption and removal can be efficiently carried out by contacting the hydrocarbon oil with liquid oil at a temperature from room temperature to about 150 ° C. without performing reduction treatment or hydrogenation. In addition, when adsorbing and removing a trace amount of sulfur compounds and / or polycyclic aromatic compounds, it is excellent in shape maintenance, so that there is a possibility that clogging or clogging of the apparatus may occur due to pulverization of the adsorbent. Reduced. For this reason, extra equipment such as a filter can be omitted, and the equipment can be removed with equipment that is more compact and less expensive than the conventional one. Furthermore, when applied to desulfurization of kerosene or the like, which is the raw fuel of the fuel cell, startup and maintenance are relatively easy, and the fuel cell system can be simplified.

[Plant biomass]
Plant biomass used in the present invention, which is subjected to a carbonization treatment step and an activation treatment step and becomes a molded activation treatment product, includes wood, coconut husk, rice straw, rice husk, pulp waste liquor, etc., but particularly obtained from rice. Rice husk is preferably used. The molded activation treatment product obtained from rice husk is one kind of so-called activated carbon, and the adsorbent comprising this exhibits excellent performance in removing sulfur compounds and / or polycyclic aromatic compounds contained in hydrocarbon oil. . In the case of plant biomass, particularly rice husks, it is presumed that the inorganic components such as silica contained develop mesopores and macropores. Furthermore, rice husks have the advantage that they are produced in a stable amount each year and can be supplied stably, and most of them are incinerated, which contributes to the effective use of resources.

[Binder made of sugar]
As the binder used in the present invention, a binder composed of saccharides is used.
Sugars include sugar beet juice, sugar cane juice, sugar beet sugar, sugar cane sugar, molasses, molasses, molasses, molasses sugar, brown sugar, sugar, sucrose, starch, oligosaccharide, etc. It is done. These are mainly composed of carbohydrate-based components such as cellulose, saccharides and starch, and are familiar (affinity, structural similarity) because the main component is the same carbohydrate as the plant-based biomass that is the raw material of activated carbon. The mixing property between the two is good, the strength of the obtained activated carbon is increased, and the specific surface area is also improved. Among these, sugar beet juice, sweet squeezed juice, sugar beet sugar, sugar cane sugar, brown sugar and starch, which are relatively easily available, are preferred, and sugar beet juice and sugar beet sugar are particularly preferred.

  Since the above saccharides are not sticky in the dry state, they can be used as they are when they are in liquid form, such as juice, for use as a binder. Are preferably used. In addition, the saccharide is often handled in a solid or powder form with a reduced water content. When the saccharide is in such a solid state or dry state, it may be used after being dissolved in water, or may be boiled and concentrated as necessary, like juice.

  Here, the binder is mixed with a plant-based biomass or carbonized product that is difficult to be molded and hardened by using the adhesive force of the binder to obtain a molded carbonized product, and a carbonized product or molded product. In order to improve the specific surface area and strength of the carbonized product, there is an impregnation binder used by impregnating plant biomass or carbonized product before carbonization treatment or before activation treatment.

  The molding binder is prepared by adding approximately the same mass of water to a powdered or solid saccharide and stirring it to prepare a uniform saccharide aqueous solution. At this time, when heated, the solubility becomes high, and it can be dissolved quickly. In addition, when the mixture is boiled, a strong stirring effect is added, and a uniform aqueous sugar solution can be obtained efficiently. When the water is evaporated by continuing gentle boiling, a viscous syrupy liquid (aqueous sugar solution) that can be suitably used as a molding binder can be obtained. The molding binder is used for strongly bonding components such as a carbon material in a shape suitable for use as an adsorbent and for facilitating the molding process. If the moisture content is too high, molding may not be possible and processing efficiency may be impaired. If the amount is too small, it can be adjusted by adding water during mixing or kneading. Therefore, it is preferable to use a syrup-like sugar aqueous solution having moderate viscosity, for example, having a viscosity of about loose honey. The viscosity can be adjusted by the amount of moisture. To increase the viscosity, add a large amount of water once to prepare a sugar solution with a sufficiently uniform composition, and then evaporate the water by heating to prepare a syrup-like sugar solution with the desired viscosity. Is preferred.

  The amount of the binder used for molding is not particularly limited as long as the amount that the plant-based biomass or carbonized product can be molded into a desired shape is not particularly limited, but the dried plant-based biomass or carbonized product to be molded is processed. It is preferable to use about 5 to 200 parts by mass with respect to 100 parts by mass. In addition, the usage-amount of said binder is based on the residual amount except a water | moisture content (dry standard).

As the impregnation binder, an aqueous sugar solution having a viscosity much lower than that of the molding binder, in which powdered saccharides are uniformly dissolved in water having a mass of 1 to 20 times at about 60 ° C. can be used.
Although the usage-amount of these binders with respect to carbonized material and activation processed material or dried plant biomass or pre-carbonized material is not specifically limited, 5-200 mass with respect to 100 mass parts of these processed materials. It is preferable to use about part (dry basis), more preferably 20 to 100 parts by mass. When the amount is less than 5 parts by mass, the strength of the obtained activated carbon is lowered. On the other hand, when the amount is more than 200 parts by mass, the pore structure which is a feature of activated carbon such as rice husk cannot be obtained sufficiently.

[Pre-carbonization process]
The plant-based biomass is preferably first heated and carbonized in an inert atmosphere. The carbonization temperature is preferably a relatively low temperature such as 200 to 600 ° C. Therefore, here, carbonization performed at a relatively low temperature is referred to as preliminary carbonization. By performing this preliminary carbonization treatment, moisture and volatile components that volatilize at the above-mentioned temperature are removed. In the subsequent carbonization treatment process and activation treatment process, problems such as cracks in the processed products due to these volatile components, and the carbonization furnace In addition, unnecessary fouling of the activation furnace can be prevented, and the handleability is greatly improved.

Examples of the inert atmosphere include an inert gas atmosphere such as nitrogen and argon, and a vacuum atmosphere. From the viewpoint of economy and the like, it is preferable to perform a preliminary carbonization treatment in a nitrogen atmosphere. In addition, it is preferable to perform the carbonization time of the preliminary carbonization treatment for about 0.01 to 2 hours.
In performing the preliminary carbonization treatment, the plant-based biomass is preferably arranged in a size that is easy to handle. For example, the rice husk may be left as it is, but wood, coconut husk, rice straw etc. are preferably arranged in the form of a so-called wood chip or toothpick of about 5 cm.
The preliminary carbonization treatment is not particularly limited as long as the carbonization treatment can be performed in an inert atmosphere, but can be performed using a furnace such as an atmospheric furnace or a rotary kiln.

[Molding carbonization process (process to obtain a molded carbonized product)]
When plant-based biomass is used as it is for the forming carbonization process, it is dried before use. For example, it is dried at 50 to 150 ° C., preferably 80 to 130 ° C. for about 1 to 24 hours.
The dried plant biomass (sometimes referred to as dried plant biomass) or a pre-carbonized product is pulverized to about 1 to 500 μm, preferably 5 to 50 μm, and the above-mentioned molding comprising saccharides Add binder and mix thoroughly. The blending amount of the molding binder is not particularly limited, but 5 to 200 parts by mass of the molding binder (as a dry basis sugar content) is uniformly mixed with 100 parts by mass of the dried plant biomass or the pre-carbonized product. It is preferable to make it. The molding binder can be sufficiently uniformly mixed using a pulverized product of dried plant biomass or a pre-carbonized product and various commercially available mixing machines such as a stirrer, a mixer, a kneader, and a kneader. The mixture is formed into a molded product using an appropriate molding machine. When the state of the mixture is crumbly or a loose paste, it may not be pressure molded. In the case of papasa, it can be adjusted without changing the mixing ratio of the impregnated carbonized product and the saccharide in the molding binder by adding water. In the case of a loose paste, the mixing ratio changes when the amount of the impregnated carbonized product is increased. Therefore, it is preferable to prepare a syrup-like sugar aqueous solution having a high sugar content to such an extent that the molding binder does not cause this.

  The shape of the molded product is not particularly limited, and examples thereof include a spherical shape, a granular shape, a columnar shape (the cross section has a deformed shape such as a circle, a corner, or a four-leaf shape), a cylindrical shape, a pellet shape, and a honeycomb shape. When used as a desulfurization agent, in order to increase the concentration gradient of the sulfur compound, in the case of a flow type, a small shape, particularly a spherical shape, is preferable so long as the differential pressure before and after the vessel filled with the desulfurization adsorbent does not increase. In the case of a spherical shape, the diameter is preferably 0.5 to 5 mm, particularly preferably 1 to 3 mm. In the case of a cylindrical shape, the diameter is preferably 0.1 to 4 mm, particularly preferably 0.2 to 2 mm, and the length is preferably 0.5 to 5 times the diameter, particularly preferably 1 to 4 times. The molding method of the molded product having such a shape is not particularly limited, and can be performed using various commercially available extrusion molding machines, press molding machines, tableting machines, tablet machines, and the like. Further, a pellet or columnar molded product can be obtained by combining a kneader and an extruder.

  Prior to carbonization, the molded mixture of the dried plant biomass or pre-carbonized product thus obtained and the molding binder thus obtained is, for example, 100 to 150 ° C, preferably 105 to 130 ° C. Dry for about 2 hours.

  Next, carbonization is preferably performed at 200 to 900 ° C. for 0.01 to 2 hours in an inert atmosphere to obtain a molded carbonized product. As in the case of the preliminary carbonization treatment, the inert atmosphere includes an inert gas atmosphere such as nitrogen and argon, a vacuum atmosphere, and the like, but it is preferably performed in a nitrogen stream from the viewpoint of economy and the like. By flowing an appropriate amount of nitrogen gas, moisture and volatile components generated from the molded product can be removed and the atmosphere in the carbonization furnace can be made uniform. The carbonization temperature is more preferably 400 to 900 ° C, still more preferably 500 to 900 ° C, and particularly preferably 700 to 900 ° C. It is preferable to carry out at a temperature equal to or higher than the temperature of carbonization treatment (impregnation carbonization treatment) after impregnation described below, and it is particularly preferable to carry out at the same temperature as the temperature of activation treatment described later. The carbonization time is more preferably 0.03 to 1 hour, and further preferably 0.05 to 0.2 hour.

  In addition, before carrying out shaping | molding carbonization, it is impregnating the carbonization process (impregnation carbonization process) by impregnating the binder for impregnation which consists of saccharides into dry plant biomass or a preliminary carbonization processed material. This is preferable because it can reduce general unevenness and increase the specific surface area. In this case, the carbonization treatment is performed by impregnating a dry plant biomass or a pre-carbonized product with a binder for impregnation, not a dry plant biomass or a pre-carbonized product, as a raw material (carbonization treatment). Except for using the obtained impregnated carbonized product, the same method as in the case of using the dried plant biomass or the pre-carbonized product can be used.

  As the impregnation method, a known method such as a spray method, a dipping method, or an evaporation to dryness method can be used. From the viewpoint of ease of operation, the spray method and the dipping method are preferable. For example, in the case of the spray method, the impregnation binder is uniformly sprayed on the dried plant biomass or the pre-carbonized product so as to be impregnated as uniformly as possible. The impregnation amount of the binder is preferably about 5 to 200 parts by mass (dry basis) with respect to 100 parts by mass of the dried plant biomass or the pre-carbonized product. If the desired amount cannot be impregnated by a single spray, the desired amount of binder can be impregnated by once drying and spraying the impregnating binder again, and by repeating this operation as necessary. In the case of dipping and impregnation, a desired amount can be impregnated by repeating the dipping and drying operations. The amount of impregnation of the binder can be grasped by adding up the respective impregnation amounts obtained each time impregnation from the mass after impregnation and the saccharide concentration of the binder, since the dry basis mass of the saccharide does not change even when dried. .

  After impregnation with the binder, drying is performed at 100 to 150 ° C., preferably 105 to 130 ° C. for about 1 to 2 hours, and carbonization treatment (impregnation carbonization treatment) is performed in an inert atmosphere to obtain an impregnated carbonized product. The impregnation of the dried plant biomass or the pre-carbonized product and the carbonization treatment after the drying (impregnation carbonization treatment) are performed at 200 to 900 ° C. for 0.01 to 2 hours. The carbonization temperature is more preferably 400 to 900 ° C, still more preferably 500 to 900 ° C, and particularly preferably 700 to 900 ° C. The carbonization time is more preferably 0.03 to 1 hour, and further preferably 0.05 to 0.2 hour.

From the above, the plant biomass can be treated in the following form in the combination of the preliminary carbonization treatment step, the impregnation carbonization treatment step and the shaping carbonization treatment step before the activation treatment in the activation treatment step described later. it can.
(1) Adding a molding binder to plant biomass and carbonizing to obtain a molded carbonized product (molded carbonization process only)
(2) After impregnating the plant biomass with a binder for impregnation and carbonizing, the molding carbonized product is added to the resulting impregnated carbonized product to obtain a molded carbonized product (impregnated carbonized process + molding) Carbonization process)
(3) A molding binder is added to a pre-carbonized product obtained by pre-carbonizing plant-based biomass and carbonized to obtain a molded carbon-treated product (pre-carbonized process + molded carbonized process)
(4) A pre-carbonized product obtained by pre-carbonizing plant biomass is impregnated with a binder for impregnation and carbonized. Then, a molding binder is added to the obtained carbonized product for impregnation, and carbonization is performed by molding carbonization. Obtain processed material (pre-carbonization process + impregnation carbonization process + molding carbonization process)

[Activation treatment step (step of obtaining a molded activation treatment product)]
The molded carbonized product obtained as described above is impregnated with a saccharide binder (impregnation binder), dried, and then subjected to activation treatment to obtain a molded activated product as activated carbon used for the adsorbent.

  As the impregnation method, a known method such as a spray method, a dipping method, an evaporation to dryness method or the like can be used which is impregnated with the above-mentioned dried plant biomass or pre-carbonized product. Among these, the spray method and the dipping method are preferable from the viewpoint of ease of operation. When a desired amount of the binder for impregnation cannot be impregnated by one impregnation operation, the impregnation operation can be performed again after drying once to increase the impregnation amount of the binder. By repeating this, a desired amount of the molding binder can be impregnated.

The molded carbonized product impregnated with the binder is dried at 100 to 150 ° C., preferably 105 to 130 ° C. for about 1 to 2 hours, and subjected to activation treatment. Examples of the activation treatment include gas activation, water vapor activation, and drug activation. In the case of drug activation, after the activation process, a post-treatment that removes the drug (KOH, NaOH, ZnCl ₂ , H ₂ SO _4, etc.) used in the activation process from the activation process is required, which is troublesome and takes time. On the other hand, gas activation or water vapor activation may be performed by heat treatment in a gas atmosphere or water vapor atmosphere, and does not require an extra complicated operation for removing the drug. Therefore, steam activation or gas activation is preferred.

  Examples of the gas used for steam activation and gas activation include water vapor, carbon dioxide gas, air, combustion gas, etc., but it is easy to control activation conditions by performing gas activation using carbon dioxide, This is preferable because post-treatment after activation is easy. Specifically, the molded carbonized product impregnated with the binder and dried is placed in a carbon dioxide atmosphere, preferably at an activation temperature of 800 to 900 ° C., for 0.1 to 4 hours, more preferably 0.5 to 3 The heat treatment is performed for a time, more preferably 0.7 to 2.3 hours. Note that the carbon dioxide atmosphere means that the activation gas in the furnace containing the molded carbonized product is carbon dioxide, and 100% carbon dioxide may be used, but inert gases such as nitrogen gas and argon gas are used. It is preferable to use a gas, a combustion gas, a gas obtained by mixing carbon dioxide with water vapor, or the like.

  After impregnating the binder for impregnation as described above, the activation treatment product obtained by the activation treatment can be impregnated again with the binder for impregnation to carry out the activation treatment (two-stage activation treatment). According to the two-stage activation treatment, the obtained two-stage activation treatment product is preferable because a product having a relatively large specific surface area and total pore volume and a relatively large bulk density can be obtained. The impregnation, drying, and heat treatment in the two-stage activation treatment can be performed under exactly the same conditions as in the activation treatment.

[Adsorbent]
As the adsorbent of the present invention, an activated product and / or a two-stage activated product (hereinafter simply referred to as activated carbon) can be used as an adsorbent as it is, or, as described later, kneaded and molded with zeolite or the like. The active metal can be supported on activated carbon and the performance can be improved. When adsorbing and removing sulfur compounds and / or polycyclic aromatic compounds contained in hydrocarbon oils such as kerosene and light oil, the above-mentioned moldings such as powdered, particulate, or spherical, disc-shaped, cylindrical molded products, etc. It can be used in any form as well as the shape of the molded product in the carbonization process. An adsorbent having a suitable shape may be selected and used in accordance with the processing amount of hydrocarbon oil and the situation of equipment.

  When used in powder or particulate form, the activated carbon is pulverized with a known appropriate pulverizer and then classified with a known appropriate classifier to obtain a powder or average particle having an average particle diameter of about 0.5 μm to 0.1 mm. The activated carbon can be appropriately used according to use conditions by sieving it into particulate activated carbon having a diameter of about 0.1 to 5 mm.

  When the hydrocarbon oil is continuously supplied and passed through the adsorbent and used, and when the deteriorated adsorbent is regenerated and used repeatedly, it is preferable to use activated carbon as a molded article. Since the activated carbon of the present invention activates the molded carbonized product, it can be suitably used as it is. Therefore, in the molding process of the molding carbonization process to obtain a molded carbonized product, it is pre-molded into a shape suitable for the application conditions such as the hydrocarbon oil to be processed and its processing conditions, and after activation treatment and after metal loading It is preferable to maintain the shape. After the activation treatment, the activated carbon may be pulverized and mixed with an inorganic substance such as zeolite or a supported metal, and then shaped into an appropriate shape.

  As the shape of the molded product, in order to increase the concentration gradient of trace components to be removed, such as sulfur compounds, in the case of flow-through type, the shape is small, especially spherical, so long as the differential pressure before and after the container filled with the adsorbent does not increase. Is preferred. In the case of a spherical shape, the size is preferably 0.1 to 5 mm, particularly 0.3 to 3 mm. In the case of a cylindrical shape, the diameter is preferably 0.1 to 4 mm, particularly 0.12 to 2 mm, and the length is preferably 0.5 to 5 times, particularly 1 to 4 times the diameter. The molded article preferably has a breaking strength of 0.5 kg / pellet or more, particularly 1.0 kg / pellet or more so as not to crack during use as an adsorbent. The breaking strength is measured, for example, by a compressive strength measuring device such as a Kiya tablet breaking strength measuring device (manufactured by Toyama Sangyo Co., Ltd., TH-203MP).

  The activated carbon used in the adsorbent of the present invention improves the diffusion rate of sulfur compounds and the like in order to improve the adsorption performance of sulfur compounds and the like that are difficult for activated carbon to adsorb and / or increase the abundance of mesopores and macropores. In order to do so, inorganic substances such as silica, alumina and zeolite may be mixed during or after the carbonization treatment, molding and activation treatment.

  Also, by combining with metals and / or metal oxides such as silver, mercury, copper, cadmium, lead, molybdenum, zinc, cobalt, manganese, nickel, platinum, palladium, iron, etc., that is, by supporting these metals The adsorption performance can also be improved. From the viewpoint of safety and economy, the oxides of copper, silver, manganese, zinc, and nickel are preferable. Among these, copper is inexpensive and has excellent performance for adsorption of sulfur compounds in a wide temperature range from near room temperature to about 300 ° C., in the state of copper oxide without reduction treatment, and in the absence of hydrogen. This is particularly preferable.

  The preferred amount of metal supported is not particularly limited, and varies depending on the type of metal, but is 0.1 to 20% by mass, particularly 0.5 to 5% by mass in the case of noble metal, based on the metal based on the finished adsorbent. % Loading is preferred. If it is less than 0.1% by mass, the supporting effect is small, and if it is more than 20% by mass, it is not economical. In the case of copper and other metals, it is preferable to carry 0.1 to 60 mass%, particularly 3 to 20 mass%. If the amount is less than 0.1% by mass, the supporting effect is small. If the amount is more than 60% by mass, the amount of the metal having a weak bond with the activated carbon that is the carrier increases, so that the metal component may be detached. When the amount of metal supported is large, the adsorption performance of sulfur compounds such as thiophenes and benzothiophenes that are difficult to adsorb activated carbon can be further improved.

  The method for supporting these metals is not particularly limited, and any method that supports a desired amount of metal and exhibits desired performance may be used. For example, a molded activation treatment product (activated carbon) is impregnated with an aqueous solution of metal hydroxide or nitrate by spraying or dipping, or the activated carbon is crushed and an aqueous solution of metal hydroxide or nitrate is kneaded. After forming and drying, the adsorbent of the present invention can be obtained by further heating and removing moisture or nitric acid so as not to lose the carbon component.

The pore characteristics such as the specific surface area, average pore width and pore volume of the adsorbent of the present invention greatly affect the adsorption performance such as desulfurization. The specific surface area of the adsorbent of the present invention is preferably from 600 to 4,000 m ² / g, more preferably from 700 to 3,000 m ² / g, particularly preferably from 800 to 2,000 m ² / g. The average pore width is proportional to the pore volume and inversely proportional to the specific surface area. If the average pore width is too large, the pore volume is too large to obtain a sufficient density, and the adsorption capacity per unit volume becomes low. On the other hand, if the average pore width is too large, the specific surface area is too small to obtain sufficient adsorption sites, and the adsorption capacity is also lowered. The average pore width of the adsorbent of the present invention is preferably 1.0 to 4.0 nm, more preferably 1.0 to 2.0 nm, and particularly preferably 1.0 to 1.5 nm. Pore volume, is also relevant specific surface area is preferably 0.30 cm ³ / g or more, further 0.40 cm ³ / g or more, and particularly 0.50 cm ³ / g or more. Moreover, since the molding activation treatment product or the second molding activation treatment product may be used as it is, the specific surface area and average pores of the molding activation treatment product and the second molding activation treatment product may be used as the adsorbent of the present invention. For the pore characteristics such as the width and the pore volume, the same pore characteristics as those in the above-mentioned range for the adsorbent can be applied.

  Pore characteristics can be analyzed using a gas adsorption analyzer (Autosorb-3B, Cantachrome, Florida, USA). For example, first, at −196 ° C., an adsorption amount of nitrogen gas (referred to as a nitrogen adsorption isotherm) as a function of the relative pressure of nitrogen gas is obtained. From this nitrogen adsorption isotherm, the total pore volume, BET specific surface area, and average pore width are calculated. The total pore volume can be determined by the nitrogen adsorption volume at a relative pressure of 0.995. The BET specific surface area is determined by the nitrogen adsorption volume at a relative pressure of 0.05-0.10. The average pore width can be determined by 2 × total pore volume / BET specific surface area assuming that the pores are slit-like. The adsorption capacity of the porous body cannot be explained entirely by the specific surface area and pore volume, but generally a high specific surface area or a large total pore volume is desirable. The pores are classified into micropores having a width of 2.0 nm or less, mesopores of 2.0 to 50 nm, and macropores of more than that, and the micropores are further divided into ultramicropores of less than 0.7 nm and 0.7-2. Classified as 0 nm super micropores.

  The pore distribution of pore volume as a function of pore width can be analyzed using the Density Functional Theory (DFT) method. The DFT method is a method for obtaining a pore distribution through numerical analysis from the obtained nitrogen adsorption isotherm, and can be analyzed using DFT software (Cantachrome, Version 1.62). A large ultra-micro pore volume is preferable because the specific surface area is large and the number of adsorption sites is large. Further, when the mesopore volume is large, the pore width is increased, and the sulfur compound is easily moved to the adsorption site. Therefore, activated carbon having a large ultramicro pore volume and mesopore volume is preferred. Since rice husk activated carbon contains silica, the mesopore volume is inherently large. Therefore, a production method for increasing the ultramicropore volume without reducing the mesopore volume is effective. The method of impregnating the binder for impregnation of the present invention, carbonizing treatment and activation treatment has a remarkable effect of suppressing the decrease in the mesopore volume and increasing the ultramicropore volume.

[Adsorption and removal of trace components]
Examples of the hydrocarbon oil to which the adsorbent of the present invention is applied include hydrocarbon oils containing 5 to 20 carbon atoms containing dibenzothiophenes as sulfur compounds or polycyclic aromatic compounds. Specific examples include kerosene and light oil, and particularly kerosene for fuel cells that needs to be highly desulfurized (deep).

  These hydrocarbon oils may contain any kind of sulfur compounds such as thiophenes, mercaptans (thiols), sulfides, disulfides, carbon disulfide, etc. In particular, it exhibits a remarkable effect on hydrocarbon oils containing sulfur compounds such as dibenzothiophenes that are extremely difficult to desulfurize. For example, the ratio of dibenzothiophenes to the total sulfur compounds is about 30% for kerosene and almost 100% for light oil. Hydrocarbon oils such as kerosene and light oil are preferred hydrocarbon oils for application of the adsorbent of the present invention. is there. Of course, the application target of the adsorbent of the present invention is not limited to kerosene or light oil.

  For qualitative and quantitative analysis of these sulfur compounds, Gas Chromatograph (GC) -Flame Photometric Detector (FPD), GC-Atomic Emission Detector (AED), GC- Sulfur Chemiluminescence Detector (SCD), GC-Inductively Coupled Plasma Mass Spectrometer (ICP-MS), etc. can be used, but GC-ICP is used for mass ppb level analysis. -MS is most preferable (see JP 2006-145219 A).

  A polycyclic aromatic compound is a compound having two or more benzene rings and may contain heteroatoms other than carbon and hydrogen, but all the carbons forming the two benzene rings are in the same plane. The one located above has a stronger π-electron interaction with the adsorbent of the present invention, and the effects of the present invention can be remarkably obtained.

  When removing impurities such as sulfur and polycyclic aromatic compounds from hydrocarbon oil with the adsorbent of the present invention, if the content of these impurities is too large, a large amount of adsorbent is required, which is uneconomical. is there. In such a case, since other purification methods such as hydrorefining methods are more efficient, the sulfur content in the hydrocarbon oil to be handled in the present invention is 20 mass ppm or less, preferably 10 mass ppm or less. More preferably, it is 1 mass ppm or less, and the content of the polycyclic aromatic compound is 5 mass% or less, preferably 2 mass% or less, more preferably 0.5 mass% or less.

  It is preferable to remove a small amount of moisture adsorbed on the adsorbent as a pretreatment before use. Moisture removal may be performed at about 100 to 200 ° C. in an oxidizing atmosphere such as air. However, when the temperature exceeds 200 ° C., oxygen in the air reacts with the carbon component of the adsorbent to reduce the mass of the adsorbent, which is not preferable. On the other hand, the adsorbent can be dried at about 100 to 800 ° C. in a non-oxidizing atmosphere such as nitrogen. In particular, it is more preferable to heat-treat the adsorbent at 400 to 800 ° C. in a non-oxidizing atmosphere because organic substances and oxygen-containing functional groups are removed and the adsorption performance is improved.

The method of bringing the adsorbent of the present invention into contact with the hydrocarbon oil may be a batch type (batch type) or a continuous type, but a continuous type in which hydrocarbon oil is circulated in a container filled with the adsorbent of the molded product is efficient. It is preferable.
In the case of a continuous type, the pressure for contact is preferably normal pressure to 1.0 MPaG, more preferably normal pressure to 0.1 MPaG, and particularly preferably 0.001 to 0.3 MPaG. Flow rate is preferably 0.001～100Hr ^-1 at a liquid hourly space velocity (LHSV), 0.01~10hr ^-1 are more preferred. The apparent linear velocity (value obtained by dividing the flow rate of hydrocarbon oil by the cross-sectional area of the desulfurizing agent layer) is 0.001 to 100 cm / min, further 0.005 to 10 cm / min, and particularly 0.01 to 1 cm / min. Minutes are preferred. If the apparent linear velocity is high, the moving speed of the liquid phase itself passing through the packed bed of adsorbent is faster than the adsorption speed (moving speed from the liquid phase to the solid phase), and the liquid phase reaches the outlet of the adsorbing layer. Until then, the sulfur content cannot be removed, and the hydrocarbon oil tends to flow out from the outlet while containing the sulfur content that is not removed. Conversely, when the apparent linear velocity is low, the cross-sectional area of the adsorbent layer becomes relatively large, so that the liquid dispersion state becomes poor, and the hydrocarbon oil passing through the cross section perpendicular to the flow direction of the adsorbent layer. Since unevenness occurs in the flow rate (flow rate) and distribution (unevenness) occurs in the sulfur content adsorbed in the cross section of the adsorbent layer, the load on the desulfurizing agent becomes non-uniform, and desulfurization cannot be performed sufficiently efficiently.
10-150 degreeC is preferable and the temperature which performs a desulfurization process has especially preferable 30-100 degreeC.

When the adsorbent of the present invention is used in a fuel cell system, the adsorbent of the present invention may be used in combination with another adsorbent.
Since the adsorbent of the present invention is particularly excellent in removal performance of dibenzothiophenes, other adsorbents excellent in removal performance of other types of sulfur compounds such as benzothiophenes, mercaptans, or sulfides, For example, for the removal of benzothiophenes, the present invention has previously proposed the removal of desulfurization agents such as activated carbon on which a solid acid catalyst and / or transition metal oxide is supported, and mercaptans, which the present inventor previously proposed. A combination with zeolite or the like is preferable for removing copper oxide-supported alumina and sulfides.

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

[Production of activated carbon 1-5]
Put 10g rice husks from Koshihikari (Toyokamura, Shizuoka Prefecture) from a stainless steel wire mesh into a vessel made of stainless steel wire mesh and place it in a stainless steel tube with an inner diameter of 44mm and an outer diameter of 50mm. While flowing at about 600 ml / min, the heater was energized and subjected to a heat treatment at 250 ° C. for 1 hour to carry out a preliminary carbonization treatment to obtain 8.3 g of a preliminary carbonized product.
1 part by mass (dry basis) of dried beet sugar powder was added to 2.5 parts by mass of distilled water, and the mixture was stirred and dissolved while heating on a hot stirrer. When the aqueous solution reached 60 ° C., it was kept at that temperature for 10 minutes to obtain a beet sugar aqueous solution (impregnation binder).
For 1 part by mass of the pre-carbonized product obtained by pre-carbonization treatment while retaining the original rice husk, 1 part by mass of the impregnation binder prepared as described above (as dry-based sugar beet sugar) Spraying was done so that it was evenly impregnated. The binder was impregnated with the pre-carbonized product evenly in the atmosphere overnight and dried.
The pre-carbonized product impregnated with the impregnating binder and dried was placed in the same stainless steel container as described above, and carbonized at 600 ° C. for 1 hour in a nitrogen stream using a tubular furnace to obtain an impregnated carbonized product.

Separately, 10 parts by mass of distilled water was added to 6 parts by mass (dry basis) of dried beet sugar powder, and the mixture was heated and gently boiled on a hot stirrer. When the thickening was caused by evaporating the water, heating and stirring were stopped, and the mixture was left to cool to obtain a sugar beet sugar syrup (molding binder) having a thickening.
1 part by mass of the above-mentioned impregnated carbonized product was pulverized in a mortar, and 0.43 part by mass (dry basis) of a binder for molding was added thereto and mixed thoroughly. The obtained mixture was pressed into a disk shape having a diameter of 30 mm and a thickness of 2 mm by pressing for 1 minute at a pressure of 3 ton (42 MPa) using a pressure molding machine (manufactured by ENERPAC, model number CPF10-1).
The obtained press-molded product is stood on a stainless steel holder and dried at 105 ° C. for 1 hour, and then the same tubular furnace as above is used so that the diameter direction of the press-molded product is substantially coincident with the diameter direction of the stainless steel container. It was installed and carbonized in a nitrogen stream at 875 ° C. for 5 minutes so that a nitrogen stream hits perpendicularly to the diameter direction of the pressure molded product to obtain a molded carbonized product.

  The molded carbonized product thus obtained was immersed in the above impregnation binder overnight, and the impregnated binder was uniformly impregnated into the molded carbonized product, and then dried at 105 ° C. for 2 hours. By this immersion and drying, the molded carbonized product took in 0.1 part by mass (dry basis) of binder per part by mass. Five lots of carbonized carbonized material impregnated with a binder for impregnation and dried were prepared, respectively, using the same tubular furnace as described above, and heated while flowing nitrogen gas at about 600 ml / min. When the temperature reached 875 ° C., nitrogen gas was supplied. Switch to carbon dioxide gas and hold for 0.5 hours, 1.0 hour, 1.5 hours, 2 hours and 2.5 hours at the same temperature (875 ° C.) in a carbon dioxide gas stream (about 600 ml / min). Activated. Then, it stood to cool naturally to room temperature, and obtained activated carbon 1-5 (Examples 1-3, Comparative Examples 1-2) which is five types of shaping | molding activation treatment products from which activation time differs. Properties such as the shape maintaining properties and pore characteristics of the activated carbons 1 to 5 were measured, and the results are shown in Table 1.

In addition, the shape maintainability is determined by visually observing whether or not the shape has changed before and after the activation treatment, and no change is observed. Those that showed a change or were deformed were considered “bad”. The bulk density [g / cm ³ ] was calculated by the following equation (1) from the value of the volume V [cm ³ ] and the mass W _a [g] obtained from the diameter and thickness of the molded activated product.
Bulk density [g / cm ³ ] = W _a / V (1)
The activation mass yield [%] was calculated by the following equation (2) from the mass before and after the activation treatment.
Activation mass yield [%] = 100 × W _a / W _b (2)
In the formula, W _a and W _b represent mass [g] after activation and before activation (after drying), respectively.

[Manufacture of activated carbon 6]
A molding activation treatment product (activated carbon 2) having an activation time of 1.0 hour was immersed in an impregnation binder overnight. After the molded activation product (activated carbon 2) was pulled up from the impregnation binder, it was dried at 105 ° C. for 2 hours. By this impregnation and drying, the molded activated product (activated carbon 2) took in 0.1 parts by mass (dry basis) of binder per part by mass. Then, similarly to said activation process, the activation process was again performed at 875 degreeC for 1.0 hour. Thus, activated carbon 6 (Example 4), which is a two-stage activation treatment product, was obtained. The properties of the activated carbon 6 are shown in Table 1 as with the activated carbons 1-5. In addition, an activation mass yield shows the value of a 2nd step.

[Desulfurization performance evaluation test]
Activated carbons 1 to 6 were used as adsorbents as they were and immersed in kerosene (made by Japan Energy Co., Ltd.) having the properties shown in Table 2 to conduct an adsorption desulfurization test, and the performance as adsorbents was evaluated. Specifically, the disc-shaped activated carbons 1 to 6 were lightly pulverized using a mortar and then dried at 150 ° C. for 3 hours, and then subjected to an adsorption desulfurization test. The ratio (mass) of kerosene to adsorbent was set to 30 (30 parts by mass of kerosene to 1 part by mass of adsorbent), and the adsorbent was immersed in kerosene and allowed to stand at 10 ° C. for 4 days. After standing for 4 days, the sulfur content in kerosene was analyzed. From the sulfur content of kerosene before and after the immersion, the sulfur amount adsorbed on the activated carbon was calculated as the sulfur adsorption amount [mg-S / g-activated carbon] by the following formula (3), and is shown in the lower part of Table 1.
Sulfur adsorption amount = (S ₁ −S ₂ ) × 30 ÷ 10 ³ (3)
In the formula, S ₁ and S ₂ indicate the sulfur content [mass ppm] of kerosene before and after immersion, respectively.

  Moreover, as a reference example, a commercial activated carbon (manufactured by Kuraray Chemical Co., Ltd., FR-25) was similarly subjected to an immersion adsorption desulfurization test, and the desulfurization performance of the fibrous activated carbon was evaluated. The results of the desulfurization performance evaluation test are shown in Table 1 together with the properties of the activated carbon 6 and the fibrous activated carbon of the reference example.

[Measurement of packing density]
The packing densities of the activated carbon 6 and the commercially available fibrous activated carbon were measured as follows. Activated carbon 6 is pulverized into particles having a width of 5 mm or less, filled into a measuring cylinder having an inner diameter of 10.6 mm and a capacity of 10 ml, compressed from above with a glass rod and filled, and then filled from the volume occupied by activated carbon 6 and the filling mass. Was calculated. On the other hand, in the case of fibrous activated carbon, fibrous activated carbon was packed into the same graduated cylinder as described above and sufficiently packed from above using a glass rod as in the case of activated carbon 6, and the packing density was calculated. Each packing density is shown in Table 1.

[Manufacture of activated carbon 7]
Rice husks of Koshihikari (Toyokamura, Shizuoka Prefecture) used as raw materials for activated carbons 1 to 6 were pre-carbonized at 600 ° C. for 1 hour. The obtained pre-carbonized product was not impregnated and carbonized, and 0.5 parts by mass of a molding binder (based on sugar beet sugar) was added to 1 part by mass of the pre-carbonized product, and the same as in the case of activated carbon 2. Then, after press-molding into a disk shape, a pre-carbonized product kneaded into a disk shape by kneading a molding binder, in the same manner as the activation process described above, without carbonizing the molding, Then, activation treatment was performed at 875 ° C. for 1 hour to prepare activated carbon 7 (Comparative Example 3) which is a molded activation treatment product. The properties of the activated carbon 7 are shown in Table 1.

  From Table 1 showing the results of physical properties measurement such as shape maintenance, specific surface area, pore volume, and immersion adsorption desulfurization test, the activated carbons 2 to 4 and 6 (Examples 1 to 3 and 4) of the present invention are shapes. Excellent maintainability, large specific surface area, large total pore volume, and good pore characteristics. Among them, the activated carbon 6 which is a two-stage activation treatment product has substantially the same specific surface area and total pore volume as the activated carbon 4 having the same total activation treatment time of 2 hours, but the bulk density is considerable. You can see that it is getting bigger. As a result, the specific surface area per volume and the total pore volume are increased. In particular, the desulfurization performances of the activated carbons 2, 3, 4, and 6 having a relatively large specific surface area, total pore volume, and super micro pore volume are 0.118, 0.124, 0.111, and 0.132 mg, respectively. -Desulfurization performance comparable to 0.126 mg-S / g-activated carbon, which is high in S / g-activated carbon, and has a very large specific surface area and total pore volume.

Moreover, paying attention to the packing density of the activated carbon 6 and the fibrous activated carbon, the packing density of the activated carbon 6 is 0.41 g / cm ³ and the fibrous activated carbon is 0.16 g / cm ³ . The adsorbent is usually packed in a packed column and used in a continuous manner. When the container is filled and used, the higher the packing density, the more desulfurizing agent can be filled, and the deflow rate per volume can be increased accordingly. Therefore, the adsorbent made of activated carbon of this example is not inferior to expensive fibrous activated carbon in desulfurization performance per unit volume, and activated carbon 6 is expected to have desulfurization performance nearly three times that of fibrous activated carbon. .
It can be seen that the activated carbon 7 of the comparative example manufactured without using the impregnating binder has a small specific surface area, and the specific surface area does not increase unless the impregnating binder is added.

About the physical-property measurement and composition analysis of Table 1 and Table 2, except having already demonstrated, it performed by the following method.
(1) Density (15 ° C.): Measured according to JIS K2249.
(2) Distillation property: Measured according to JIS K2254.
(3) Aromatic content, saturated content, polycyclic aromatic content: British Institute of Petroleum standard IP standard method 391/95 (high-performance liquid chromatograph using refractive index detector of middle distillate Aromatic hydrocarbon analysis).
(4) Sulfur content (total sulfur content): analyzed by combustion oxidation-ultraviolet fluorescence method.
(5) Sulfur compound type analysis: Analyzed by GC-ICP-MS.
(6) Nitrogen content: Measured according to the microcoulometric titration method described in JIS K2609.

Claims (12)

In a method for producing an adsorbent containing activated carbon, a molding carbonization step for obtaining a molded carbonized product by carbonizing after adding a molding binder made of sugar to a plant biomass and kneading and molding, and the obtained molding Carbonization characterized by including an activation treatment step of adding a binder for impregnation consisting of saccharides to the carbonized product and impregnating the carbonized product to obtain a molded activation treatment product having a specific surface area of 600 m ² / g or more which is activated carbon. The manufacturing method of the adsorption agent which removes the trace component in hydrogen oil. Furthermore, the molding activation treatment product includes a second activation treatment step of impregnating a binder for impregnation made of saccharide again and performing a second activation treatment to obtain a second molding activation treatment product having a specific surface area of 600 m ² / g or more. The method for producing an adsorbent according to claim 1.   Furthermore, the manufacturing method of the adsorption agent of Claim 1 or 2 including the carbonization process of impregnation which impregnates the plant-type biomass with the binder for impregnation which consists of saccharides before a shaping | molding carbonization process process.   Furthermore, the manufacturing method of the adsorption agent in any one of Claims 1-3 including the pre-carbonization process process which pre-carbonizes plant biomass and obtains a pre-carbonization processed material.   The preliminary carbonization treatment is performed at 200 to 600 ° C. for 0.01 to 2 hours under an inert atmosphere, and the impregnation carbonization treatment and the molding carbonization treatment are performed at 0.01 to 200 ° C. under an inert atmosphere at 200 to 900 ° C., respectively. The adsorption according to any one of claims 1 to 4, wherein the adsorption treatment is carried out for 2 hours, and the activation treatment and the second activation treatment are each carried out at 800 to 900 ° C in a carbon dioxide atmosphere for 0.1 to 4 hours. Manufacturing method.   The method for producing an adsorbent according to any one of claims 1 to 5, wherein the plant biomass is rice husk.   The method for producing an adsorbent according to any one of claims 1 to 6, wherein the saccharide is at least one selected from sugar beet sugar, brown sugar and sugar sucrose. A molded activation treatment product obtained by the method for producing an adsorbent according to claim 1 and having a specific surface area of 600 m ² / g or more and an average pore width of 1.0 nm or more and / or second An adsorbent that removes trace components in hydrocarbon oils that contain the molded activation product.   A method for removing trace components in hydrocarbon oil, wherein the adsorbent according to claim 8 is used to adsorb and remove sulfur compounds and / or polycyclic aromatic compounds contained in hydrocarbon oil.   The removal method according to claim 9, wherein the hydrocarbon oil is kerosene or light oil.   The removal method according to claim 9 or 10, wherein the sulfur compound is adsorbed and removed at a temperature of 150 ° C or lower.   A fuel cell system equipped with the adsorbent according to claim 8.