JPWO2015119269A1 - Activated carbon production method and activated carbon - Google Patents

Abstract

A method for producing activated carbon, comprising an activation step of obtaining activated carbon by activating petroleum coke, wherein the petroleum coke contains petroleum coke having a particle size of 100 μm or less. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of activated carbon which can obtain activated carbon with a large specific surface area can be provided using petroleum coke as an activation process raw material.

Description

The present invention relates to a method for producing activated carbon, and specifically relates to a method for producing activated carbon using petroleum coke as an activation raw material.
In addition, the present invention relates to activated carbon, and specifically relates to activated carbon excellent in metal adsorptivity.

  Conventionally, activated carbon has been produced by using various activation treatment raw materials as raw materials and activating by various activation methods such as steam activation, alkali activation, gas activation by carbon dioxide gas, air, combustion gas, etc. It was.

  And as activation treatment raw materials, sawdust, hard wood chips, charcoal (primary ash), grass charcoal (peat), charcoal, coconut charcoal, coal (lignite, lignite, bituminous coal, anthracite, etc.), oil carbon, phenol resin Rayon, acrylonitrile, coal pitch, petroleum pitch, phenol resin and the like have been used.

  These activation treatment raw materials are converted into activated carbon by being directly activated or directly carbonized and then activated.

  By the way, petroleum coke is coke remaining after pyrolyzed crude oil is pyrolyzed by a pyrolyzer using a pyrolyzed oil produced in a petroleum refining process as a raw material, and the pyrolyzed oil is collected as a light component. At present, petroleum coke is used for fuel as shown in Patent Document 1 and the like.

  And, as described above, the use of petroleum coke is exclusively for fuel, and the added value of petroleum coke is low. Therefore, high added value of petroleum coke is desired.

  Here, since petroleum coke is a substance with a high carbon content, conversion to activated carbon is expected from this point by activation. If activated carbon can be produced from petroleum coke, the added value of petroleum coke can be increased.

  However, the production of activated carbon using petroleum coke as an activation raw material has hardly been performed so far.

  Further, since naphtha and LPG contain mercury, it is desirable to remove it, and the demand for removing this trace amount of mercury is increasing more and more. In addition, recovery of useful metals represented by gold and silver is desired.

  However, since the amount of mercury in naphtha and LPG is very small, it is difficult to remove by distillation, and removal by chemicals is not preferable because a large-scale facility is required. Therefore, removal with an adsorbent is efficient for removing mercury in naphtha and LPG.

  Here, activated carbon is known as an adsorbent material used for adsorbing various substances. Conventionally, activated carbon and a method for producing the same have been studied. For example, JP-A-52-92894 (Patent Document 2), JP-A-8-332375 (Patent Document 3), JP-A-2007-112704. Various activated carbons and methods for producing the same are disclosed in Japanese Patent Publication (Patent Document 4) and Japanese Translation of PCT International Publication No. 2004-532722 (Patent Document 5).

  Among the above-mentioned prior art documents, Patent Documents 2 to 4 are Patent Documents 5 in which activated carbon for metal removal is not disclosed but activated carbon for metal removal is disclosed. Patent Document 5 discloses an adsorbed powder containing carbon-based powder and copper chloride, and the carbon-based powder is activated carbon.

JP 2012-132603 A JP 52-92894 A JP-A-8-332375 JP 2007-112704 A JP-T-2004-532722

  Then, the present inventors tried activation treatment of petroleum coke for the purpose of performing activation treatment using petroleum coke as an activation treatment raw material to produce activated carbon. However, petroleum coke is activated to some extent, but unlike coconut husk charcoal and charcoal, it is difficult to activate and the specific surface area of the obtained activated carbon remains small.

  Accordingly, a first object of the present invention is to provide a method for producing activated carbon that can obtain activated carbon having a large specific surface area using petroleum coke as an activation treatment raw material.

  Moreover, since the adsorbent disclosed in Patent Document 5 has a large content of copper chloride, a new problem of contamination with copper may occur. The adsorbent is based on the idea of adsorbing mercury by copper, and the carbon powder functions as a carrier for immobilizing copper.

  For this reason, there is a need for a new activated carbon that can effectively adsorb and remove trace amounts of metals such as mercury.

  Accordingly, a second object of the present invention is to provide a novel activated carbon that can effectively adsorb and remove metals such as mercury.

The above problems are solved by the present invention described below.
(1) having an activation step of obtaining activated carbon by activating petroleum coke,
The petroleum coke contains petroleum coke having a particle size of 100 μm or less,
A process for producing activated carbon characterized by
(2) The method for producing activated carbon according to (1), wherein the activation in the activation step is steam activation.
(3) The method for producing activated carbon according to (2), wherein the steam activation is performed at 700 to 1000 ° C. in the steam activation.
(4) The method for producing activated carbon according to (1), wherein the activation in the activation step is alkali activation.
(5) Activated carbon obtained by activating the activation treatment raw material,
The activation treatment raw material is petroleum coke having a sulfur content of 5 to 12% by mass in a dry state;
Activated carbon characterized by
(6) The activated carbon according to (5), wherein the activation is steam activation or alkali activation.
(7) The ratio of the pore volume of pores having a pore diameter of 1 to 10 nm to the pore volume of pores having a pore diameter of 1 to 100 nm is 80% or more (5) or (6) Any activated carbon.
(8) The activated carbon according to any one of (5) to (7), wherein the BET specific surface area is 20 to 2000 m ² / g.
(9) The petroleum coke is a dried product obtained by drying coke collected by pyrolyzing an atmospheric distillation residue oil or a vacuum distillation residue oil of crude oil at 100 to 1500 ° C. (5) ~ (8) Any activated carbon.

According to 1st invention of this invention, the manufacturing method of activated carbon which can obtain activated carbon with a large specific surface area can be provided using petroleum coke for an activation process raw material.
In addition, according to the second invention of the present invention, a novel activated carbon capable of effectively adsorbing and removing metals such as mercury can be provided.

It is a measurement result of pore distribution of Experimental Examples 4 and 5.

The method for producing activated carbon which is the first invention of the present invention (hereinafter referred to as the method for producing activated carbon of the first invention) has an activation step of obtaining activated carbon by activating petroleum coke,
The petroleum coke contains petroleum coke having a particle size of 100 μm or less,
A process for producing activated carbon characterized by

  The activation process which concerns on the manufacturing method of the activated carbon of this 1st invention is a process of activating petroleum coke which is an activation processing raw material by activating petroleum coke, and obtaining activated carbon. Hereinafter, the activation treatment raw material used in the activation step according to the method for producing activated carbon of the first invention is referred to as “activation treatment raw material (1)”.

  In the activation step according to the method for producing activated carbon of the first invention, petroleum coke to be activated is produced by thermally decomposing raw material oil produced in the petroleum refining process being pyrolyzed in a pyrolysis apparatus, It is coke remaining after collecting light components produced in the decomposition process.

  The pyrolysis raw oil to be pyrolyzed includes atmospheric distillation residue oil after crude oil distillation, atmospheric distillation residue oil after distillation of atmospheric distillation residue oil, and atmospheric distillation residue oil. A mixed oil of a vacuum distillation residue oil or a mixed oil of at least one of an atmospheric distillation residue oil and a vacuum distillation residue oil and another hydrocarbon oil (1) may be mentioned.

  There is no restriction | limiting in particular in the atmospheric distillation residue oil which concerns on a pyrolysis raw material oil, It is a residue part after carrying out atmospheric pressure distillation and isolate | separating an evaporation fraction. There is no restriction | limiting in particular in the vacuum distillation residue oil which concerns on a pyrolysis raw material oil, It is a residue part after carrying out vacuum distillation of the atmospheric distillation residue oil, and isolate | separating an evaporation fraction. The pyrolysis raw material oil may be a mixed oil of atmospheric distillation residue oil and vacuum distillation residue oil. When the pyrolysis raw oil is a mixture oil of atmospheric distillation residue oil and vacuum distillation residue oil, The mixing ratio of the distillation residue oil and the vacuum distillation residue oil is not particularly limited, and is appropriately adjusted.

  The crude oil used as the distillation raw material for atmospheric distillation residue oil is not particularly limited, and examples of crude oil types include, for example, Arabian Heavy, Arabian Medium, Arabian Light, Arabian Extralite, Kuwait, Basra, Oman, Marban, Mubaras Blend. , Zakum, Upper Zakum, Qatar Land, Qatar Marine, Umshaif, Shiri, Kafuji, Espo, etc., any one or a combination of two or more.

  The pyrolysis raw material oil is a mixed oil of at least one of atmospheric distillation residue oil and vacuum distillation residue oil and other hydrocarbon oil (1), that is, atmospheric distillation residue oil and other hydrocarbon oil. Mixed oil of (1), mixed oil of vacuum distillation residue oil and other hydrocarbon oil (1), or mixed oil of atmospheric distillation residue oil, vacuum distillation residue oil and other hydrocarbon oil (1) It may be. When the pyrolysis raw material oil is a mixed oil of at least one of atmospheric distillation residue oil and vacuum distillation residue oil and other hydrocarbon oil (1), the other hydrocarbon oil (1) is the present invention. For example, a slurry oil in a fluid catalytic cracking process, an ethylene cracker residue oil, or the like may be used.

  The pyrolysis temperature is preferably 490 to 510 ° C., particularly preferably 495 to 505 ° C., and the pressure (gauge pressure) during the pyrolysis treatment is preferably 0.00. 01 to 0.6 MPaG, particularly preferably 0.05 to 0.4 MPaG. Moreover, the atmosphere of a thermal decomposition process is steam. Moreover, when excessive foaming is recognized during a thermal decomposition process, an antifoamer may be thrown in. As the antifoaming agent, generally, a silicon-based antifoaming agent or the like can be used.

  Petroleum coke obtained by pyrolysis is collected from, for example, a pyrolysis apparatus after being pulverized with a water jet or the like. In this way, petroleum coke collected from the inside of the pyrolyzer includes a granular shape generally called shot coke and a large lump shape generally called porous coke, which is porous. Therefore, when petroleum coke is collected from the pyrolyzer, if the oil coke is crushed with a water jet and then collected, the petroleum coke contains water, so the collected petroleum coke is dried at 100-1500 ° C. You may let them. Moreover, when extracting petroleum coke from the inside of a thermal decomposition apparatus, petroleum coke may contain water, and in that case, the collected petroleum coke may be dried at 100 to 1500 ° C.

  Then, after the petroleum coke obtained by pyrolysis as described above is collected from the inside of the pyrolysis apparatus or dried as necessary, it is pulverized and classified to obtain petroleum coke having predetermined particle characteristics. This is used as the petroleum coke of the activation treatment raw material (1) in the activation step according to the method for producing activated carbon of the first invention.

  In the activation step according to the method for producing activated carbon of the first invention, petroleum coke as the activation treatment raw material (1) has a particle diameter of 100 μm or less, preferably 1 to 100 μm, more preferably 1 to 50 μm. Contains particles. Since petroleum coke having a particle diameter in the above range is easily activated, the specific surface area of the activated carbon can be increased by including the petroleum coke in the activated particle size (1) in the range of the above particle diameter.

  In the first aspect of the present invention, the petroleum coke used as the activation treatment raw material (1) preferably contains 100% of particles having a particle size of 100 μm or less, but may contain particles having a particle size of 100 μm or more. When the petroleum coke used as the activation treatment raw material (1) includes particles having a particle diameter exceeding 100 μm, the particle diameter of the particles having a particle diameter exceeding 100 μm is 400 μm or less, preferably 300 μm or less. And in all the particles of petroleum coke used as the activation treatment raw material (1), the content of petroleum coke having a particle size of 100 μm or less, preferably 1 to 100 μm, more preferably 1 to 50 μm is preferably 50% by volume or more More preferably, it is 70 volume% or more, More preferably, it is 100 volume%.

  In the activation step according to the method for producing activated carbon of the first invention, the average particle diameter (D50) of petroleum coke serving as the activation treatment raw material (1) is preferably 1 to 100 μm, more preferably 1 to 80 μm. When the average particle diameter of petroleum coke is in the above range, the specific surface area of the activated carbon can be increased.

In the activation step according to the method for producing activated carbon of the first invention, the following formula (1) of petroleum coke to be the activation raw material (1):
Span = (D90−D10) / D50 (1)
Is preferably 1 to 8, more preferably 2 to 6. When the span of petroleum coke is in the above range, the specific surface area of the activated carbon can be increased.

  In addition, in this 1st invention, D10, D50 (average particle diameter), D90 is 10% of integration calculated | required by the volume frequency particle size distribution measurement measured with the laser diffraction scattering type particle size distribution measuring apparatus based on JISZ8825, The particle size is 50% and 90%. In addition, the particle diameter and content of particles of 100 μm or less and all particles exceeding 100 μm in all the particles of petroleum coke are also determined by volume frequency particle size distribution measurement measured by a laser diffraction / scattering particle size distribution measuring device.

  In the activation step according to the method for producing activated carbon of the first invention, the sulfur content in the dry state of petroleum coke as the activation treatment raw material (1) is 1 to 12% by mass, preferably 2 to 10% by mass. Preferably it is 4-8 mass%. When the sulfur content in the dry state of petroleum coke is in the above range, the activation easily proceeds, and as a result, the metal adsorption performance of the activated carbon increases.

  The petroleum coke obtained by pyrolysis treatment of the pyrolysis raw oil and collected from the pyrolysis apparatus usually contains about 1 to 12% by mass of water, so the mass of the petroleum coke in the wet state is When the sulfur content is calculated as a standard, the calculated value of the sulfur content in the petroleum coke varies depending on the water content of the petroleum coke. Therefore, in the present invention, when calculating the sulfur content in petroleum coke, the oil-containing coke in a water-containing state is dried at 200 ° C. ± 10 ° C. for 4 hours (according to JIS M 8811), and the obtained oil coke in the dry state is obtained. The mass is measured, and the sulfur content in the petroleum coke is calculated based on the mass of the dried petroleum coke. That is, the sulfur content in the dry state of the petroleum coke used as the activation treatment raw material is the mass of sulfur in the petroleum coke relative to the mass of the petroleum coke in the dry state.

  In the activation process according to the method for producing activated carbon of the first invention, petroleum coke as the activation treatment raw material (1) is composed of a substance having a carbon atom content of 70 to 90% by mass, and contains 1 to 10% by mass of hydrogen atoms. Have. Moreover, the nitrogen content of the petroleum coke which is an activation processing raw material (1) is 0.1-2 mass%. Moreover, the aromatic carbon ratio of the petroleum coke which is the activation processing raw material (1) is 75 to 98%, preferably 85 to 95%. Moreover, the fixed carbon content of the petroleum coke which is an activation processing raw material (1) is 70-98 mass%, Preferably it is 85-95 mass%. Moreover, the ratio (H / C molar ratio) of the number of moles of the hydrogen component to the number of moles of the carbon component of the petroleum coke which is the activation treatment raw material (1) is 0.1 to 1, preferably 0. .2 to 0.8. In addition, as above-mentioned, since petroleum coke collected from the inside of a thermal cracking apparatus normally contains about 1-12 mass% of water | moisture content, in the case of calculation of sulfur content, carbon atom content , Hydrogen atom content, aromatic carbon ratio, fixed carbon content, water-containing petroleum coke is dried at 200 ° C. ± 10 ° C. for 4 hours (according to JIS M 8811), and mass of dried petroleum coke obtained And the carbon atom content, the hydrogen atom content, the aromatic carbon ratio, and the fixed carbon content in the petroleum coke are calculated based on the mass of the dried petroleum coke.

  And in the activation process which concerns on the manufacturing method of the activated carbon of this 1st invention, petroleum coke is used for an activation process raw material, activation process is performed, and petroleum coke is activated. The activation treatment is not particularly limited, and examples thereof include water vapor activation, alkali activation, gas activation with carbon dioxide gas, air, combustion gas, and the like.

  In the activation step according to the method for producing activated carbon of the first invention, when petroleum coke is activated by steam, as the steam activation treatment, an inert gas containing nitrogen (such as nitrogen gas) is brought into contact with petroleum coke. The method of performing steam activation of petroleum coke is mentioned. The activation temperature during steam activation is 750 to 1500 ° C., preferably 800 to 1200 ° C., particularly preferably 850 to 1000 ° C., and the activation time is 0.1 to 8 hours, preferably 0.5 to 4 hours. Particularly preferably, it is 0.5 to 2 hours.

  Further, in the activation step according to the method for producing activated carbon of the first invention, when the petroleum coke is alkali-activated, the alkali activation is performed by mixing an alkali compound and petroleum coke, under an inert gas atmosphere (such as under a nitrogen gas atmosphere). ) And a method of activating the alkali of petroleum coke by heating. Examples of the alkali compound used for alkali activation include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like. The activation temperature at the time of alkali activation is 500 to 1000 ° C., preferably 600 to 1000 ° C., particularly preferably 700 to 950 ° C., and the activation time is 0.5 to 4 hours, preferably 0.5 to 3 hours. It is.

  As the activation treatment in the activation step according to the method for producing activated carbon of the first invention, steam activation and alkali activation are preferable. Moreover, when performing steam activation or alkali activation as an activation process, the petroleum coke which is an activation process raw material (1) may be what contained water, or what was dried previously.

BET specific surface area of the activated carbon obtained performed a manufacturing method of the activated carbon of the present first invention is preferably 20~2000m ² / g, more preferably 100~1500m ² / g, more preferably 100~1000m ² / g .

  In activation using petroleum coke as an activation treatment raw material, in the activated carbon production method of the first invention, activation is performed by using petroleum coke having a particle diameter of 100 μm or less and a small particle diameter as a raw material for activation treatment of petroleum coke. The surface area of the petroleum coke used as the processing raw material (1) is increased to facilitate activation. Therefore, in the method for producing activated carbon of the first invention, activated carbon having a large specific surface area can be produced. On the other hand, if the particle size of petroleum coke used as the raw material for the activation treatment is too large, it becomes difficult to activate, so the specific surface area of the activated carbon cannot be increased.

  On the other hand, in the conventional activation using palm husk charcoal or charcoal as the activation treatment raw material, the degree of easiness of activation due to the difference in the particle size of the activation treatment raw material does not change greatly. Even if the particle diameters of the treated raw materials were different, there was no significant difference in the specific surface area of the obtained activated carbon. Therefore, the knowledge in the conventional activation was that the specific surface area of activated carbon did not increase even if the particle diameter of the activation treatment raw material was reduced.

The activated carbon which is the second invention of the present invention (hereinafter referred to as activated carbon of the second invention) is activated carbon obtained by activating the activation treatment raw material,
The activation treatment raw material is petroleum coke having a sulfur content of 5 to 12% by mass in a dry state;
Is an activated carbon characterized by Hereinafter, the activation treatment raw material used in the activation treatment according to the method for producing activated carbon of the second invention is referred to as “activation treatment raw material (2)”.

  The activated carbon of the second invention is activated carbon obtained by activating the activation treatment raw material (2), but the activation treatment raw material (2) to be activated has a sulfur content of 5 to 12 in a dry state. It is petroleum coke which is mass%.

  In the activated carbon of the second invention, the petroleum coke which is the activation treatment raw material (2) is obtained by pyrolyzing the pyrolysis raw material oil produced in the petroleum refining process with a pyrolysis apparatus. Petroleum coke obtained by pyrolysis may contain water during collection from the pyrolysis apparatus. Moreover, when extracting petroleum coke from the inside of a thermal decomposition apparatus, it may extract | collect after pulverizing petroleum coke with a water jet. When petroleum coke which is an activation treatment raw material contains water, the collected petroleum coke may be dried at 100 to 1500 ° C.

  The activation treatment raw material (2) according to the activated carbon of the second invention and the activation treatment raw material (1) according to the activation process of the method for producing activated carbon of the first invention have a partial sulfur content range of petroleum coke. Although different, the pyrolysis raw material oil, the atmospheric distillation residue oil, the vacuum distillation residue oil, the atmospheric distillation residue oil and the vacuum distillation residue oil to be pyrolyzed according to the activation raw material (2) in the activated carbon of the second invention of the present invention Mixed oil, mixed oil of one or more of atmospheric distillation residue oil and vacuum distillation residue oil and other hydrocarbon oil (1), crude oil as distillation raw material for atmospheric distillation residue oil, conditions for thermal decomposition Is a pyrolysis raw material oil, atmospheric distillation residue oil, vacuum distillation residue oil, atmospheric distillation residue oil to be pyrolyzed according to the activation treatment raw material (2) in the activation step of the method for producing activated carbon of the first invention Of the mixed oil of vacuum distillation residue oil, atmospheric distillation residue oil and vacuum distillation residue oil Mixed oil of the seed or other hydrocarbon oil (1), crude oil as the distillation raw material of atmospheric residue, the same as the conditions of the pyrolysis process.

  In the activated carbon of the second invention, the sulfur content in the dry state of the petroleum coke which is the activation treatment raw material (2) is 5 to 12% by mass, preferably 6 to 10% by mass. When the sulfur content in the dry state of petroleum coke is in the above range, the metal adsorption performance is enhanced. On the other hand, if the sulfur content in the dry state of petroleum coke is less than the above range, the metal adsorption performance is not sufficient, and if it exceeds the above range, the strength as activated carbon decreases and crushing caused by wear There is a concern that clogging will occur.

  In the activated carbon of the second invention, the petroleum coke which is the activation treatment raw material (2) is obtained by the thermal decomposition treatment of the pyrolysis raw material oil, but usually contains about 1 to 12% by mass of water. If the mass of the petroleum coke in the state is used as a reference for calculating the sulfur content, the calculated value of the sulfur content in the petroleum coke varies depending on the water content of the petroleum coke. Therefore, in the present invention, when calculating the sulfur content in petroleum coke, the oil-containing coke in a water-containing state is dried at 200 ° C. ± 10 ° C. for 4 hours (according to JIS M 8811), and the obtained oil coke in the dry state is obtained. The mass is measured, and the sulfur content in the petroleum coke is calculated based on the mass of the dried petroleum coke. That is, the sulfur content in the dry state of the petroleum coke according to the activated carbon of the present invention is the mass of sulfur in the petroleum coke relative to the mass of the petroleum coke in the dry state.

  Petroleum coke includes a granular shape generally called shot coke and a large massive porous shape generally called sponge coke. In the activated carbon of the second invention, the activation treatment raw material (2) A certain petroleum coke may be shot coke, sponge coke, a mixture thereof, or a pulverized product thereof.

  The activation treatment according to the activated carbon of the second invention is a treatment for activating petroleum coke to obtain activated carbon. The method for activating petroleum coke is not particularly limited, and examples thereof include steam activation, alkali activation, gas activation with carbon dioxide, air, combustion gas, and the like.

  In the activation treatment according to the activated carbon of the second aspect of the invention, when petroleum coke is activated by steam, the steam activation of petroleum coke is performed by bringing an inert gas containing nitrogen (such as nitrogen gas) into contact with petroleum coke. . The activation temperature during steam activation is 750 to 1500 ° C., preferably 800 to 1200 ° C., particularly preferably 850 to 1000 ° C., and the activation time is 0.1 to 8 hours, preferably 0.5 to 4 hours. Particularly preferably, it is 0.5 to 2 hours.

  In the activation treatment according to the activated carbon of the second invention, when petroleum coke is activated with alkali, an alkali compound and petroleum coke are mixed and heated in an inert gas atmosphere (such as a nitrogen gas atmosphere), thereby heating the petroleum coke. To activate the alkali. Examples of the alkali compound used for alkali activation include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like. The activation temperature at the time of alkali activation is 500 to 1000 ° C., preferably 600 to 1000 ° C., particularly preferably 700 to 950 ° C., and the activation time is 0.5 to 4 hours, preferably 0.5 to 3 hours. It is.

  In addition, the activation treatment according to the activated carbon of the second invention includes a method of activating petroleum coke using an aqueous solution of phosphoric acid, zinc chloride, aluminum chloride, magnesium chloride, potassium hydroxide, sodium hydroxide and the like. .

  As the activation treatment according to the activated carbon of the second invention, steam activation and alkali activation are preferable, and alkali activation is particularly preferable. Moreover, when performing steam activation or alkali activation as activation processing, the petroleum coke which is an activation processing raw material may be what contained water, or what was dried previously.

BET specific surface area of the activated carbon of the present second invention is preferably 20~2000m ² / g, particularly preferably 100~1500m ² / g, most preferably 100~1000m ² / g.

  In the activated carbon of the second invention, the ratio of the pore volume of pores having a pore diameter of 1 to 10 nm to the pore volume of pores having a pore diameter of 1 to 100 nm is preferably 80% or more, particularly preferably 85%. That's it. In the present invention, an adsorption isotherm of activated carbon is obtained by a specific surface area / pore distribution measuring apparatus ASAP2020 (manufactured by micromeritics), and a pore distribution is obtained from the adsorption isotherm by a BJH method (Barrett, Joyner, Hallender). From the relationship between the obtained pore diameter and pore volume, the ratio (percentage) of the pore volume of pores having a pore diameter of 1 to 10 nm to the pore volume of pores having a pore diameter of 1 to 100 nm is calculated.

  The activated carbon of the second invention is obtained by activation treatment using petroleum coke containing 5 to 12% by mass, preferably 6 to 10% by mass, and sulfur-rich petroleum coke as a raw material in a dry state. Therefore, there are many sulfur atoms in the pores. And in the activated carbon of this 2nd invention, since it becomes possible to coordinate a metal to the sulfur atom in this pore, the activated carbon of this 2nd invention does not contain a sulfur atom or contains a sulfur atom. Even if it exists, it is excellent in the adsorptivity of metal, especially mercury compared with activated carbon with a small content. From this, the activated carbon of the second invention is suitably used as an adsorbent used for adsorption removal of metals, particularly mercury.

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

(1) Experimental example relating to the first invention <Petroleum coke>
(Shot coke A)
Using pyrolysis residue oil and slurry oil as pyrolysis raw material oil, pyrolysis treatment under conditions of 500 ° C. and 0.1 MPaG, pyrolysis treatment, pulverization with a water jet, and visually divide shot coke A It was prepared as petroleum coke of the activation treatment raw material (1). Table 1 shows the properties of shot coke A.

<Analysis of petroleum coke>
(moisture)
The sample before drying was performed in accordance with JIS M 8811.
(Measurement of sulfur content in the dry state)
The sample was dried at 300 ° C. for 5 minutes and cooled to obtain a dry sample, and the mass in the dry state was measured. Subsequently, the sulfur content of the dried sample was measured according to JIS M 8819.
(ash)
About the dry sample, it carried out based on JISM8812.
(For CHN)
The dry sample was measured according to JIS M 8813.
(BET specific surface area)
In order to remove molecules adsorbed on the surface of the sample, the BET specific surface area of the dried sample was measured after vacuum heating and drying at 150 ° C. for 10 hours.

(Experimental example 1)
Shot coke A is pulverized with a mill model 911 manufactured by Hamilton Beach Co., Ltd., then sieved with a sieve of 140 mesh (aperture 100 μm) and collected under the sieve to classify petroleum coke with all particles having a particle size of 100 μm or less. A processed product A was obtained. Next, the obtained petroleum coke classification product A was dried at 300 ° C. for 5 minutes and cooled. Next, 1.675 g of the petroleum coke classification processed product A which has been dried is weighed, placed on a quartz boat having a length of 10 cm and a width of 2 cm, and a nitrogen gas attached with a steam supply pipe. The supply pipe was placed in one end side, and the exhaust gas exhaust pipe was placed in a tubular furnace provided on the other end side. Subsequently, nitrogen gas was supplied into the tubular furnace at 50 ml / min, and the inside of the furnace was replaced with nitrogen gas. Subsequently, the flow rate of nitrogen gas was set to 50 ml / min, and the temperature in the furnace was raised to 850 ° C. while supplying nitrogen gas into the furnace. When the temperature in the furnace reaches 850 ° C., the nitrogen gas is supplied to the furnace at 50 ml / min while keeping the temperature in the furnace at 850 ° C., and water vapor is supplied to the nitrogen gas supply pipe at 0.375 g / min. Introduced in minutes, water vapor was supplied into the furnace together with nitrogen gas, and the supply of water vapor was continued for 2 hours, and water vapor activation was performed at 850 ° C. for 2 hours. Next, the supply of water vapor was stopped, only nitrogen gas was supplied, and the mixture was allowed to cool to room temperature to obtain 0.530 g of activated carbon A (yield 31.7%).
Subsequently, the BET specific surface area of the obtained activated carbon A was measured. The results are shown in Table 2.

(BET specific surface area)
It carried out similarly to petroleum coke.

(Experimental example 2)
Weighed 1.675 g of the dried petroleum coke classified processed product A and placed it on a quartz boat having a length of 10 cm and a width of 2 cm, and dried the petroleum coke classified processed product. Except for weighing 0.795 g of A and placing it on a quartz boat having a length of 5 cm and a width of 1 cm, the same procedure as in Experimental Example 1 was performed, and steam activation was performed at 850 ° C. for 2 hours to obtain activated carbon. 0.396 g of B was obtained (yield 49.8%).
Subsequently, the BET specific surface area of the obtained activated carbon B was measured. The results are shown in Table 2.

(Experimental example 3)
Shot coke A was pulverized with a mill model 911 manufactured by Hamilton Beach Co., Ltd., then sieved with a 16 mesh (aperture 1000 μm) sieve, the sieve was collected, and the sieve was further screened with a 36 mesh (aperture 400 μm) sieve. The sieve and what remained on the sieve were collected to obtain a petroleum coke classified product a having a particle diameter of 400 to 1000 μm.
Thereafter, the same procedure as in Experimental Example 1 was performed, and steam activation was performed at 850 ° C. for 2 hours to obtain 0.667 g (yield 64.0%) of activated carbon a.
Subsequently, the BET specific surface area of the obtained activated carbon C was measured. The results are shown in Table 2.

(2) Experimental example relating to the second invention <Petroleum coke>
(Shot coke B and sponge coke B)
Using pyrolysis residue oil and slurry oil as pyrolysis raw material oil, pyrolysis treatment under conditions of 500 ° C. and 0.1 MPaG, pyrolysis treatment, pulverization with water jet, and visually, shot coke B and sponge Coke B was fractionated and prepared as petroleum coke as an activation treatment raw material. Properties of shot coke B and sponge coke B are shown in Table 3.

<Analysis of petroleum coke>
(moisture)
The sample before drying was performed in accordance with JIS M 8811.
(Measurement of sulfur content in the dry state)
The sample was dried at 300 ° C. for 5 minutes and cooled to obtain a dry sample, and the mass in the dry state was measured. Subsequently, the sulfur content of the dried sample was measured according to JIS M 8819.
(ash)
About the dry sample, it carried out based on JISM8812.
(For CHN)
The dry sample was measured according to JIS M 8813.
(BET specific surface area)
In order to remove molecules adsorbed on the surface of the sample, the BET specific surface area of the dried sample was measured after vacuum heating and drying at 150 ° C. for 10 hours.

(Experimental example 4)
Shot coke B was pulverized in a mortar, dried at 300 ° C. for 5 minutes, and cooled. Next, 4.897 g of the dried shot coke B was weighed, placed on an alumina boat, a nitrogen gas supply pipe with a water vapor supply pipe attached to one end, and an exhaust gas exhaust pipe It left still in the tubular furnace installed in the end side. Subsequently, nitrogen gas was supplied into the tubular furnace at 8.0 ml / min, and the inside of the furnace was replaced with nitrogen gas. Next, the flow rate of the nitrogen gas was set to 0.6 ml / min, and the temperature in the furnace was raised to 900 ° C. while supplying the nitrogen gas into the furnace. When the temperature in the furnace reaches 900 ° C., while maintaining the inside of the furnace at 900 ° C., while supplying nitrogen gas into the furnace at 0.6 ml / min, water vapor is supplied to the nitrogen gas supply pipe at 1. Introduced at 56 g / min, water vapor was supplied into the furnace together with nitrogen gas, and the supply of water vapor was continued for 60 minutes, and water vapor activation was performed at 900 ° C. for 60 minutes. Next, the supply of water vapor was stopped, only nitrogen gas was supplied, and the mixture was allowed to cool to room temperature, to obtain 2.976 g of activated carbon D (yield 60.8%).
Subsequently, the BET specific surface area of the obtained activated carbon D was measured. The results are shown in Table 4. Further, the adsorption isotherm of activated carbon D was measured, and the pore distribution was determined by the BJH method. The results are shown in FIG. 1, and the ratio of the pore volume of pores having a pore diameter of 1 to 10 nm to the pore volume of pores having a pore diameter of 1 to 100 nm was calculated from the pore distribution. The results are shown in Table 4.
Next, 50 ml of an aqueous gold chloride (III) acid solution having a gold concentration of 105 ppm was prepared, 0.1 g of activated carbon D was added to the aqueous solution, and the mixture was stirred at room temperature for 16 hours. The activated carbon was then separated and the residual gold concentration in the aqueous solution was measured. The results are shown in Table 4. Also, 50 ml of an aqueous mercury (II) chloride solution having a mercury concentration of 105 ppm was prepared, 0.1 g of activated carbon D was added to the aqueous solution, and the mixture was stirred at room temperature for 16 hours. Subsequently, after separating activated carbon, the residual mercury concentration in the aqueous solution was measured. The results are shown in Table 4.

(BET specific surface area)
It carried out similarly to petroleum coke.
(Adsorption isotherm, BJH method pore distribution)
Specific surface area / pore distribution measuring apparatus ASAP2020 (manufactured by micromeritics) was used to determine the adsorption isotherm of activated carbon, and the pore distribution was determined from the adsorption isotherm by the BJH method.

(Experimental example 5)
Activated carbon E was obtained in the same manner as in Experimental Example 4 except that sponge coke B was used instead of shot coke B. The results are shown in Table 4 and FIG.

(Experimental example 6)
Shot coke A was pulverized in a mortar and sieved to 106 to 250 μm, then placed in a magnetic dish, dried in an electric furnace at 200 ° C. for 4 hours, and cooled. Next, 13.6 g of 50% phosphoric acid aqueous solution and 4 g of shot coke A that had been dried were mixed in a 100 ml Erlenmeyer flask and allowed to stand overnight. Next, the mixture of the phosphoric acid aqueous solution and shot coke A is transferred to a magnetic dish, and kept in an electric furnace at 500 ° C. for 1 hour in a nitrogen atmosphere while supplying nitrogen gas at 1 L / min into the furnace. Activation treatment with phosphoric acid was performed. After cooling, the activated product is washed twice in a 300 ml flask with 100 ml of 5% HCl aqueous solution at 80 ° C. for 1 hour, and then washed with 100 ml of hot water at 80 ° C. for 2 hours. The operation was performed 4 times. Subsequently, it filtered and the filtrate was dried at 150 degreeC for 3 hours within the electric furnace, and the activated carbon F was obtained.
Subsequently, the sulfur content of the activated carbon F was measured. The results are shown in Table 5.

(Experimental example 7)
Shot coke A was pulverized in a mortar and sieved to 106 to 250 μm, then placed in a magnetic dish, dried in an electric furnace at 200 ° C. for 4 hours, and cooled. Next, 12 g of a 64% zinc chloride aqueous solution and 4 g of shot coke A that had been dried were mixed in a 100 ml Erlenmeyer flask and allowed to stand overnight. Next, the mixture of the aqueous zinc chloride solution and shot coke A was transferred to a magnetic dish, dried in an electric furnace at 120 ° C. for 2 hours, and then supplied with nitrogen gas at a rate of 1 L / min. The sample was kept at 500 ° C. for 1 hour and subjected to activation treatment with zinc chloride. After cooling, the activated product is washed twice in a 300 ml flask with 100 ml of 5% HCl aqueous solution at 80 ° C. for 1 hour, and then washed with 100 ml of hot water at 80 ° C. for 2 hours. The operation was performed 4 times. Subsequently, it filtered and the filtrate was dried at 150 degreeC for 3 hours in the electric furnace, and the activated carbon G was obtained.
Next, the specific surface area and sulfur content of the activated carbon G were measured. The results are shown in Table 5.

According to the present invention, activated carbon having a large specific surface area can be produced using petroleum coke as a raw material.
In addition, according to the present invention, an adsorbent effective for removing various metals can be provided.

Claims (9)

Having an activation process to obtain activated carbon by activating petroleum coke,
The petroleum coke contains petroleum coke having a particle size of 100 μm or less,
A process for producing activated carbon characterized by   The method for producing activated carbon according to claim 1, wherein the activation in the activation step is steam activation.   In the said steam activation, steam activation is performed at 700-1000 degreeC, The manufacturing method of the activated carbon of Claim 2 characterized by the above-mentioned.   The method for producing activated carbon according to claim 1, wherein the activation in the activation step is alkali activation. Activated carbon obtained by activating the activation treatment raw material,
The activation treatment raw material is petroleum coke having a sulfur content of 5 to 12% by mass in a dry state;
Activated carbon characterized by   The activated carbon according to claim 5, wherein the activation is steam activation or alkali activation.   The ratio of the pore volume of pores having a pore diameter of 1 to 10 nm to the pore volume of pores having a pore diameter of 1 to 100 nm is 80% or more, or any one of claims 5 or 6. Activated carbon. The activated carbon according to claim 5, wherein the BET specific surface area is 20 to 2000 m ² / g.   The oil coke is a dried product obtained by drying coke obtained by pyrolyzing an atmospheric distillation residue oil or a vacuum distillation residue oil of crude oil at 100 to 1500 ° C. The activated carbon according to claim 1.

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