CN109923066B - Spherical activated carbon and method for producing same - Google Patents
Spherical activated carbon and method for producing same Download PDFInfo
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- CN109923066B CN109923066B CN201780068885.0A CN201780068885A CN109923066B CN 109923066 B CN109923066 B CN 109923066B CN 201780068885 A CN201780068885 A CN 201780068885A CN 109923066 B CN109923066 B CN 109923066B
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Abstract
The spherical activated carbon of the present invention is an integrally molded spherical activated carbon. The spherical activated carbon has an average particle diameter of 1.5mm to 4.0mm, and has a pore volume in the range of 50nm to 10000nm inclusive in pore diameter of 0.01ml/g to 0.24ml/g inclusive.
Description
Technical Field
The present invention relates to a spherical activated carbon and a method for producing the spherical activated carbon.
Background
In the chemical industry, activated carbon is used in separation processes, purification, catalyst or solvent recovery, and is widely used for wastewater treatment, pollution control, or medical use related to global environmental pollution problems.
For example, non-patent document 1 discloses a powdered activated carbon and a granular activated carbon having an average particle diameter of about several mm.
In addition, activated carbon using a heavy hydrocarbon oil such as petroleum tar or ethylene tar as a raw material (patent document 1) and activated carbon using a resin as a raw material (patent document 2) are known.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2005-119947 "
Patent document 2: japanese laid-open patent publication No. 2000-233916 non-patent publication
Non-patent document 1: zhentaongsan, other 2 new-edition activated carbon foundations and applications, lecture society of Kabushiki Kaisha, 3.1.1992
Disclosure of Invention
Problems to be solved by the invention
Further, in the case of using activated carbon, reduction of pressure loss and suppression of dust are required.
When activated carbon is packed in a device such as a column and used by flowing a fluid containing a target substance at a certain concentration, it is necessary to densely pack activated carbon particles in order to maximize the effect per unit volume of the target substance.
However, when the particle size of the activated carbon is small or when the amount of dust generated by the activated carbon is large, the inter-particle voids of the activated carbon are blocked. In these cases, it is considered that the pressure loss increases due to clogging of the device filter or the like, and as a result, the load on the device increases. In addition, when a large flow of fluid is treated with activated carbon, there is a possibility that the activated carbon having a small particle size or the generated dust may scatter.
In addition, when the activated carbon is brought into contact with a fluid (gas or liquid) containing a target substance and then the activated carbon and the target substance are separated from each other, a treatment such as filtration is required. However, if the particles of the activated carbon are small or the amount of dust generated is large, it takes time and cost to separate them.
In particular, since the particle size of the powdery activated carbon is substantially small, it is considered that the pressure loss is large when the activated carbon is filled in an apparatus and used, and the fluid handling amount is limited.
In addition, when the powdered activated carbon is used in this manner, the powder may be scattered when a fluid having a large flow rate is handled.
On the other hand, it is considered that if the activated carbon is granular with an average particle size of about several mm, the pressure loss during filling can be reduced, and a fluid treatment with a large flow rate can be performed.
However, conventionally, in a method for producing granular activated carbon, a method of mixing powdered carbon with a binder and granulating the mixture has been generally used. That is, the granular activated carbon obtained by the conventional production method is not integrally molded activated carbon. Therefore, it is considered that since conventional granular activated carbon has low strength, when such granular activated carbon is used by being packed in an apparatus, a large amount of dust is generated, and separation from a fluid is difficult.
Further, since conventional granular activated carbon is generally coconut shell carbon or the like, there are problems such as a large amount of impurities and elution of impurities other than dust.
From such a viewpoint, it is required to develop an activated carbon which can suppress pressure loss and dust.
Technical scheme
As a result of intensive studies to solve the above problems, the present inventors have found that the pressure loss and dust can be suppressed by an integrally molded spherical activated carbon having a particle diameter of about several mm.
That is, the present invention provides a spherical activated carbon having an average particle diameter of 1.5mm to 4.0mm, which is integrally molded, and has a pore volume in the range of 0.01ml/g to 0.24ml/g in the range of 50nm to 10000 nm.
Further, the present invention provides a method for producing a spherical activated carbon having the above-described characteristics.
Advantageous effects
According to the present invention, it is possible to provide activated carbon capable of suppressing pressure loss and dust.
Detailed Description
Hereinafter, an embodiment of the spherical activated carbon of the present invention will be specifically described.
[ spherical activated carbon ]
The spherical activated carbon of the present embodiment (hereinafter also simply referred to as "spherical activated carbon") has an average particle diameter of 1.5mm to 4.0mm, and a pore volume in a pore diameter range of 50nm to 10000nm of 0.01ml/g to 0.24 ml/g. The pore diameter and pore volume will be described in detail below.
In the present specification, spherical activated carbon means spherical activated carbon. The degree of sphericity of the spherical activated carbon is not particularly limited, and the aspect ratio is preferably 0.7 or more, more preferably 0.8 or more, and still more preferably 0.9 or more. The aspect ratio is the ratio of the minor axis to the major axis. The major axis and the minor axis are determined by a known method, for example, as an average value of the maximum length and the minimum length in a projected image of the spherical activated carbon. The closer the aspect ratio is to 1, the closer the spherical activated carbon is to a true sphere. When the aspect ratio of the spherical activated carbon is 0.7 or more, abrasion due to collision of the particles of the spherical activated carbon can be further reduced when the spherical activated carbon is used, and therefore generation of dust can be sufficiently suppressed.
The spherical activated carbon of the present embodiment is an integrally molded spherical activated carbon. The "integrally molded spherical activated carbon" means an activated carbon molded as primary particles and having a spherical shape. The spherical activated carbon of the present embodiment is also referred to as activated carbon having porous and spherical primary particles because it has a pore diameter and a pore volume as described below. The spherical activated carbon of the present embodiment is superior in mechanical strength to conventional spherical activated carbon such as a sintered body of aggregated particles. For example, the spherical activated carbon of the present embodiment has a higher crushing strength or a lower underwater vibration wear rate than conventional spherical activated carbons.
(average particle diameter)
From the viewpoint of suppressing an increase in pressure loss in the packed layer of the spherical active carbon, the lower limit value of the average particle diameter of the spherical active carbon in the present embodiment is 1.5mm or more, preferably 1.7mm or more, more preferably 1.8mm, and further preferably 2.0mm or more. From the viewpoint of achieving sufficient contact between the spherical activated carbon and the fluid in the packed layer, the upper limit value is 4.0mm or less, preferably 3.5mm or less, and more preferably 3.0mm or less. When the average particle diameter is within this range, the inter-particle voids of the spherical activated carbon can be sufficiently increased. Therefore, in the case of such a spherical activated carbon, when the spherical activated carbon is packed in an apparatus such as a column or a separation column and brought into contact with a fluid containing a target substance, the pressure loss can be sufficiently reduced.
In the present embodiment, the average particle diameter of the spherical activated carbon can be evaluated according to JIS K1474. That is, a particle size cumulative graph of the spherical activated carbon was prepared based on the results obtained by the procedure of JIS K1474. The mesh (mm) of the sieve indicated by the intersection point was determined by drawing a horizontal line on the vertical axis from the intersection point of the vertical line of the 50% point on the horizontal axis and the particle size integration diagram. The value of the mesh is the average particle diameter of the spherical activated carbon.
(pore size)
In the present specification, the pore diameter means the pore diameter of pores of the spherical activated carbon. In the present embodiment, the pore diameter and pore volume can be measured by, for example, a known mercury intrusion method. The pore diameter and pore volume can be adjusted according to, for example, the properties of the crosslinked and heavy asphalt described later, the type of the additive in the crosslinked and heavy asphalt, or the conditions for extracting the additive with a solvent.
(pore volume)
In the present specification, the pore volume means the volume of pores in a specific pore diameter range of the activated carbon.
The lower limit of the pore volume of the spherical activated carbon in the range of pore diameters of 50nm to 10000nm is 0.01ml/g or more, preferably 0.02ml/g or more, more preferably 0.03ml/g or more, and still more preferably 0.05g/ml or more, from the viewpoint of suppressing a decrease in productivity of the spherical activated carbon in the production method described later. From the viewpoint of preventing the reduction in the crush strength of the spherical activated carbon, the upper limit value is 0.24ml/g or less, preferably 0.22ml/g or less, more preferably 0.20ml/g or less, and still more preferably 0.18ml/g or less.
In addition, the lower limit of the pore volume of the spherical activated carbon in the range of pore diameters of 10nm to 10000nm is 0.01ml/g or more, preferably 0.02ml/g or more, more preferably 0.03ml/g or more, and still more preferably 0.04 ml/or more, from the viewpoint of suppressing a decrease in the productivity of the spherical activated carbon. From the viewpoint of preventing the reduction in the crush strength of the spherical activated carbon, the upper limit is 0.28ml/g or less, preferably 0.27ml/g or less, more preferably 0.26ml/g or less, still more preferably 0.25ml/g, and most preferably 0.24ml/g or less.
According to the present embodiment, by making the spherical activated carbon satisfy the above range, it is possible to form necessary pores sufficiently in the non-melting described later, and therefore, the non-melting can be efficiently performed, and the spherical activated carbon can be produced. In addition, since an increase in pore volume, which is difficult to be associated with the adsorption capacity of the spherical activated carbon, can be suppressed, the density of the spherical activated carbon increases, and the performance per unit volume of the spherical activated carbon improves.
In the present embodiment, the pore volume can be evaluated by, for example, a known mercury intrusion method. (crush Strength)
Since the spherical activated carbon of the present embodiment is a primary particle, it has higher mechanical strength than a conventional spherical activated carbon obtained by sintering aggregated particles. The crushing strength of the spherical activated carbon of the present embodiment is preferably 1.20 kg/piece or more, more preferably 1.25 kg/piece or more, and further preferably 1.30 kg/piece. The crushing strength may be, for example, 10.0 kg/piece or less, as long as the crushing strength is sufficient according to the use of the spherical activated carbon.
The crush strength can be measured by the following method. That is, sample particles (for example, 32 particles) of the spherical activated carbon were arbitrarily extracted, and the hardness at the moment of crushing the sample particles was measured using a simple particle hardness meter (manufactured by chemical and physical instruments of cylindrical well). Then, the maximum value and the minimum value among the measured values of the hardness were excluded, and the average value of the remaining measured values (for example, the measured values of 30 granules) was calculated and used as the crush strength of the spherical activated carbon.
(dust amount)
In the present specification, the dust means fine powder contained in the spherical activated carbon. The dust amount means an amount of the dust, specifically, an amount calculated by measurement of the dust amount described later.
In the present embodiment, the amount of dust contained in 1g of the spherical active carbon is preferably 2000 μ g or less, more preferably 1500 μ g or less, still more preferably 1200 μ g or less, and most preferably 1000 μ g or less, from the viewpoint of suppressing an increase in pressure loss in the packed layer of the spherical active carbon and from the viewpoint of sufficiently exhibiting the separation ability of the spherical active carbon. The lower limit of the amount of the dust is preferably 0. mu.g or more.
The dust amount of the spherical activated carbon of the present embodiment can be measured by a specific method described later. The amount of dust can be reduced by a manufacturing method realized by integral molding, for example.
(rate of abrasion by vibration in Water)
When the spherical activated carbon is put in water and vibrated in the water, the spherical activated carbon collides with each other, and the spherical activated carbon is scraped and peeled off. In the present embodiment, the underwater vibration abrasion rate is calculated from the amount of spherical activated carbon exfoliated at this time. Specifically, the underwater vibration wear rate can be calculated by the following equation.
In-water vibration abrasion ratio (%) - (A-B)/A.times.100 (%). formula 1)
A: mass (g) of spherical activated carbon before vibration in water
B: mass (g) of spherical activated carbon vibrated in water
The spherical activated carbon of the present embodiment preferably has an underwater vibration wear rate of 5% or less, more preferably 4.5% or less. The lower the underwater vibration abrasion rate, the greater the strength of the spherical activated carbon, and therefore the smaller the amount of dust generated by the collision of the spherical activated carbons with each other.
(specific surface area)
The specific surface area is determined by the ratio of the amount of adsorbed gas molecules to the adsorption cross-sectional area of the gas molecules, so that the gas molecules are adsorbed by the substance to be evaluated. Specifically, the nitrogen adsorption amount was calculated by the BET method, and the adsorption cross-sectional area of the nitrogen molecule was set to 0.162nm2The specific surface area was determined. The specific surface area may be referred to as Specific Surface Area (SSA).
The specific surface area in the present embodiment is a specific surface area when nitrogen is used as a gas molecule and adsorbed on the spherical activated carbon at a liquid nitrogen temperature. The specific surface area can be adjusted, for example, according to the degree of activation described later.
The specific surface area of the spherical activated carbon of the present embodiment is preferably 100m from the viewpoint of exhibiting the adsorption function of the spherical activated carbon2A value of at least one of,/g, more preferably 300m2A total of 400m or more2More than g. It is considered that if the specific surface area is 100m2At least g, the adsorption function of the spherical activated carbon can be sufficiently exhibited. From the above-mentioned viewpoint, the larger the specific surface area is, the more preferable, but the range may be within which the desired adsorption function of the spherical activated carbon can be sufficiently obtained, and the specific surface area may be 4000m, for example2The ratio of the carbon atoms to the carbon atoms is less than g.
The spherical activated carbon of the present embodiment may be loaded with other substances. Examples of the other substances include known substances that can be added to activated carbon, such as acids, bases, and metals. Specific examples of the acid include nonvolatile acids such as phosphoric acid and sulfuric acid, and organic acids such as citric acid and malic acid. Specific examples of the base include potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide. Specific examples of the metal include transition elements such as platinum, silver, iron, and cobalt, and compounds thereof.
As described above, the amount of dust contained in the spherical activated carbon of the present embodiment is preferably 2000 μ g or less per 1g of the spherical activated carbon.
Further, the underwater vibration abrasion rate of the spherical activated carbon of the present embodiment is preferably 5% or less.
Further, the aspect ratio of the spherical activated carbon of the present embodiment is preferably 0.7 or more.
Further, the spherical activated carbon of the present embodiment is preferably loaded with an alkali or an acid.
According to the spherical activated carbon of the present embodiment, the pressure loss and the dust amount can be suppressed. Thus, such a spherical activated carbon can be used for various purposes. In addition, the spherical activated carbon of the present embodiment is also superior in crack resistance to conventional activated carbon.
The method for producing a spherical activated carbon according to the present embodiment is not particularly limited as long as it can obtain a spherical activated carbon having the above-described characteristics. An embodiment of the method for producing a spherical activated carbon according to the present embodiment (hereinafter, also simply referred to as "the present production method") will be described below. [ method for producing spherical activated carbon ]
(raw materials)
In the present production method, a heavy hydrocarbon oil is used as a raw material of the spherical activated carbon. Examples of the heavy hydrocarbon oil include one or more selected from the group consisting of petroleum tar, coal tar, ethylene tar, and the like.
Among them, ethylene tar can be obtained by distilling the light components of the residual oil (bottom oil) produced in the production of ethylene under reduced pressure.
In addition, a fossil fuel-derived or plant-derived resin containing a furan resin or a phenol resin may be used as a raw material of the spherical activated carbon.
Specifically, the production method includes six steps of (1) production of a crosslinked and heavy asphalt, (2) addition of an additive to the crosslinked and heavy asphalt, (3) molding of the crosslinked and heavy asphalt, (4) extraction of the additive, (5) non-melting, and (6) firing/activation. Hereinafter, the respective steps will be described in order.
(1) Production of crosslinked and heavy asphalt
In the present production method, first, a crosslinked and heavy asphalt is produced. As will be described later, the process for producing the crosslinked and heavy asphalt comprises: ensuring appropriate incompatibility with the viscosity-adjusting additive containing an aromatic compound, and further, in the step of extracting the additive, a step necessary for making the spherical asphalt porous.
The crosslinked heavy asphalt may be obtained by, for example, crosslinking and heat-treating a liquid heavy hydrocarbon oil at room temperature. Thus, a solid crosslinked and heavy asphalt can be obtained at ordinary temperature. A specific method for producing a crosslinked and heavy asphalt is described in, for example, japanese patent No. 4349627.
(2) Addition of additives to crosslinked, heavy bitumens
Next, the viscosity of the crosslinked and heavy asphalt is adjusted by adding an additive to the obtained crosslinked and heavy asphalt, so that the crosslinked and heavy asphalt has a viscosity suitable for spheroidizing.
Examples of the additive include viscosity adjusting additives such as naphthalene described later.
The spherical asphalt can be obtained by molding the crosslinked heavy asphalt after adding the additive to the crosslinked heavy asphalt and heating and mixing the mixture.
In the present production method, the additive to be added to the crosslinked heavy asphalt derived from the heavy hydrocarbon oil is preferably a bicyclic or tricyclic aromatic compound or a mixture thereof having a boiling point of 200 ℃ or higher, preferably 205 ℃ or higher, and more preferably 210 ℃ or higher.
Specific examples of such a preferable additive include one or more selected from the group consisting of naphthalene, methylnaphthalene, phenylnaphthalene, benzylnaphthalene, methylanthracene, phenanthrene, biphenyl, and the like. Among them, naphthalene is preferable as the additive.
When the total amount of the mixture of the crosslinked and heavy asphalt and the additive is 100% by mass, the lower limit of the amount of the additive to be added to the crosslinked and heavy asphalt is preferably 26% by mass or more, more preferably 27% by mass or more, and still more preferably 28% by mass. When the amount of the additive is not more than the lower limit, pores may not be sufficiently formed in the obtained porous spherical asphalt. The upper limit of the amount of the additive is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. When the amount of the additive is not less than the upper limit, the amount of the crosslinked and heavy asphalt in the mixture of the crosslinked and heavy asphalt and the additive is relatively small, and thus the production efficiency may be lowered. In addition, since the extraction hole is formed in the step described later, the strength of the obtained spherical activated carbon may be insufficient. By setting the amount of the additive to this range, the additive can be efficiently extracted from the spherical asphalt in the step described later, and the porous spherical asphalt obtained can have sufficient pores. When the pores of the porous pitch are sufficient, the crosslinking reaction by the oxidation reaction proceeds to the inside of the porous spherical pitch in the below-described non-melting step, and the spherical shape of the porous spherical pitch is maintained and carbonized. For example, if the naphthalene content is 25 mass%, the pores of the porous asphalt may be insufficiently melted.
The pores formed by the additive are included in a part of the pore volume of the spherical activated carbon having a pore diameter in the range of 50nm to 10000 nm.
(3) Formation of crosslinked, heavy bitumens
Next, the crosslinked and heavy asphalt to which the additive is added is molded. At this time, it is preferable to homogenize the mixture of the crosslinked and heavy asphalt and the additive in advance. The mixture of cross-linked heavy bitumen and additives is preferably made into a molten mixture by heating.
The molding of the crosslinked heavy pitch may be performed in the state of a molten mixture, or may be performed by cooling the molten mixture, pulverizing the same, and stirring the same in hot water. In order to facilitate the subsequent extraction step of the additive, it is preferable to mold the crosslinked and heavy pitch so as to obtain a spherical pitch having a particle diameter of 6.0mm or less.
For example, the spherical asphalt can be obtained by melt-dispersing a homogeneous mixture of the crosslinked and heavy asphalt and the additive under normal pressure or under pressure using water containing a suspending agent as a dispersion medium.
In addition, as a method for obtaining a spherical asphalt, for example, a method disclosed in Japanese patent publication No. 59-10930 can be cited. Specifically, a mixture of a crosslinked and heavy asphalt and a viscosity-adjusting additive is extruded in a molten state to form a rod-shaped asphalt, or an asphalt obtained by stretching the asphalt is cooled and solidified, and the obtained rod-shaped asphalt is crushed to form a rod-shaped asphalt having a length/diameter ratio of 5 or less, and then stirred and mixed in hot water containing a suspending agent at a temperature of not less than the softening point of the rod-shaped asphalt to form a spherical shape.
In the present embodiment, the size of the rod-like pitch determines the average particle diameter of the spherical activated carbon. Therefore, in order to set the average particle diameter of the spherical activated carbon to 1.5mm or more and 4.0mm or less, the dimension of the rod-like pitch in the longitudinal direction is preferably about 1.5mm to 10 mm. The diameter of the die is preferably about 1.5mm to 10mm when the bar-shaped asphalt is extruded.
The rod-shaped asphalt obtained as described above is added to hot water heated to a temperature not lower than the softening point of the mixture of the crosslinked and heavy asphalt and the additive, whereby the rod-shaped asphalt is softened and deformed to produce a spherical asphalt.
The temperature of the hot water at the time of cooling and pulverizing the molten mixture of the crosslinked and heavy asphalt and the additive and stirring the same in the hot water (hereinafter, this temperature is referred to as "spheroidization temperature") may be appropriately set according to the viscosity of the molten mixture of the crosslinked and heavy asphalt and the additive.
In the present embodiment, the lower limit of the spheroidization temperature is preferably 95 ℃ or higher, more preferably 97 ℃ or higher, and still more preferably 98 ℃ or higher. The upper limit of the spheroidization temperature is preferably 120 ℃ or less, more preferably 115 ℃ or less, and still more preferably 110 ℃ or less. By setting the spheroidization temperature in this range, spherical asphalt can be efficiently obtained. When the spheroidization temperature is low, the mixture of the crosslinked and heavy asphalt and the additive is not deformed, and thus the rod-shaped asphalt may not be efficiently spheroidized. On the other hand, if the spheroidization temperature is too high, the molten mixture of the crosslinked and heavy pitch and the additive becomes a bag shape or the molten mixture tears, and therefore, the particle diameter of the finally obtained spherical activated carbon may be reduced.
When the rod-like pitch is spheroidized in hot water, stirring or the like is preferably performed. In this case, if the stirring force is weak, the spherical asphalt is likely to settle, and the spherical asphalt is likely to fuse with each other. On the other hand, if the stirring force is too high, the spherical asphalt may be torn by the shearing force. From such a viewpoint, it is preferable to appropriately select an optimum stirring mechanism and a stirring rotation speed for floating/flowing the spherical asphalt in the hot water. The method of fluidizing the spherical asphalt is not limited to stirring, and other suitable methods may be used.
Further, in the present embodiment, it is more preferable that the mixture of the crosslinked and heavy asphalt and the additive is dispersed in hot water by melting and suspending in the presence of a suspending agent. That is, when the rod-shaped asphalt is to be spheroidized, it is more preferable to add the suspending agent to hot water. The hot water containing the suspending agent has the effect of improving the dispersibility of the spherical asphalt and preventing the spherical asphalt from being welded to each other. From such a viewpoint, in the present embodiment, it is preferable that the mixture of the crosslinked and heavy asphalt and the additive is dispersed in hot water by melt suspension to obtain the spherical asphalt.
In the present embodiment, examples of the suspending agent include: polyvinyl alcohol (hereinafter, also referred to as "PVA"), xanthan gum, partially saponified polyvinyl acetate, methyl cellulose, carboxymethyl cellulose, polyacrylic acid and salts thereof, polyethylene glycol and ether derivatives thereof, ester derivative starch, gelatin, and other water-soluble polymer compounds.
In this case, the concentration of the suspending agent may be appropriately set. The higher the concentration of the suspending agent, the lower the settling rate of the spherical asphalt becomes, and therefore, the spherical asphalt can be dispersed with a smaller stirring force and the spherical asphalt can be prevented from being torn by a shearing force.
In the present embodiment, when PVA is used as a suspension concentrate, the lower limit of the content of PVA with respect to the above-mentioned hot water is 0.1 mass% or more, preferably 0.15 mass% or more, more preferably 0.23 mass% or more, and still more preferably 0.3 mass% or more. The upper limit of the content is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.
The lower limit of the temperature of the hot water is preferably 95 ℃ or higher, more preferably 97 ℃ or higher, and still more preferably 98 ℃ or higher. The upper limit of the temperature of the hot water is preferably 120 ℃ or lower, more preferably 115 ℃ or lower, and still more preferably 110 ℃ or lower.
In the present embodiment, a thickener may be used in combination with the suspending agent, or only a thickener may be used alone.
In the spheroidization, the ratio of the amount of the rod-like pitch to the amount of the hot water containing the suspending agent is preferably high. This reduces the influence of the reduction in particle size and the deformation due to collision of the rod-like pitches with each other.
(4) Extraction of additives
Next, the additives contained in the obtained spherical asphalt are removed, and pores for allowing the oxidizing gas to diffuse into the spherical asphalt are formed in the subsequent non-melting step.
In the present embodiment, since the crosslinked and heavy asphalt has incompatibility with the additive, it is presumed that the inside of the spherical asphalt forms a sea-island structure of the crosslinked and heavy asphalt and the additive. From such a viewpoint, in the present production method, it is preferable that the additive portion contained in the spherical pitch is removed by using a solvent, and pores serving as passages for oxygen to the spherical pitch are formed in the subsequent non-melting step.
The mass ratio of the solvent to the slurry of spherical asphalt is preferably 7 or more, more preferably 9 or more, and still more preferably 13. If the mass ratio of the solvent to the slurry of spherical asphalt is less than 7, the additive in the particles may not be sufficiently extracted, and pores that serve as passages for oxygen to the spherical asphalt may not be formed in the subsequent non-melting step.
The solvent used for extracting and removing the additive from the spherical asphalt is an aliphatic compound. Examples of the aliphatic compound include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, mixtures mainly comprising aliphatic hydrocarbons such as naphtha and kerosene, and aliphatic alcohols such as methanol, ethanol, propanol, and butanol, and n-hexane is preferably used.
In this case, the mass ratio of n-hexane to the slurry of spherical asphalt is preferably 7 or more, more preferably 9 or more, and still more preferably 13 or more. If the mass ratio of n-hexane to spherical pitch slurry is less than 7, the additives in the particles may not be sufficiently extracted, and pores that serve as passages for oxygen to the spherical pitch may not be formed in the subsequent non-melting step.
In the present embodiment, it is preferable that pores for diffusing oxygen to the inside when not melted are sufficiently formed. Thus, it is preferable to sufficiently extract the additive from the spherical asphalt.
By using the solvent in this manner, only the additive can be removed efficiently while maintaining the shape of the spherical asphalt.
In the present production method, when the additive is removed from the spherical asphalt, the spherical asphalt is formed with through holes resulting from extraction of the additive, whereby porous spherical asphalt having uniform porosity can be obtained.
In the present embodiment, the softening point of the crosslinked and heavy asphalt greatly affects the softening point of the porous spherical asphalt. If the softening point is too low, the porous spherical asphalt may be softened or melted when subjected to a heat treatment for non-melting as described later, which is not preferable.
In the present embodiment, the higher the softening point of the porous spherical asphalt is, the more preferable. In order to increase the softening point of the porous spherical asphalt, it is preferable to convert the crosslinked asphalt into a heavy product. If the softening point of the porous spherical asphalt is too high, an anisotropic component is generated in the crosslinked asphalt, and there is a fear that the crosslinked and heavy asphalt is made spherical, extraction of an additive, uniform activation treatment described later, and the like become difficult.
From such a viewpoint, in the present embodiment, the softening point of the porous spherical asphalt is preferably 150 ℃ to 350 ℃, more preferably 200 ℃ to 300 ℃, and still more preferably 220 ℃ to 280 ℃.
Further, the toluene insoluble matter of the porous spherical asphalt has a good correlation with the carbonization yield of asphalt, and the higher the toluene insoluble matter is, the higher the carbonization yield tends to be. Therefore, the toluene insolubles are preferably 40% or more, more preferably 50% or more. The toluene insoluble matter can be measured by a known method, for example, the method described in paragraph 0030 of patent document 1.
(5) Does not melt
Then, porous spherical infusible asphalt, which is infusible to heat, is formed from the porous spherical asphalt. In this production method, the oxidizing gas is uniformly diffused into the porous spherical asphalt by utilizing the pores formed by extracting the additive from the spherical asphalt, and the crosslinking treatment is performed. Thus, porous spherical infusible asphalt can be formed. More specifically, for example, the gas may be flowed against the porous spherical asphalt in the fluidized bed and heated at 100 ℃ to 350 ℃, preferably 120 ℃ to 320 ℃, and more preferably 130 ℃ to 300 ℃.
As the oxidizing gas, O may be used2、O3、SO3、NO2An oxidizing gas such as air, or a mixed gas obtained by diluting the oxidizing gas with an inert gas such as nitrogen, carbon dioxide, or water vapor.
The degree of crosslinking treatment can be determined, for example, from the oxygen content obtained by elemental analysis of the oxidized porous asphalt obtained by elemental analysis. In this case, the oxidation treatment is preferably performed so that the oxygen content is 5 mass% or more, preferably 8 mass% or more and 25 mass% or less, more preferably 10 mass% or more and 23 mass% or less, and further preferably 11 mass% or more and 21 mass% or less.
(6) Firing/activating
Finally, the porous spherical infusible pitch is fired to produce carbon, and pores are formed in the carbon. The pores of the spherical activated carbon formed in the non-melting step are pores for diffusing oxygen when not melted. After the firing/activation step, pores that affect the final adsorption capacity are formed in the spherical activated carbon. For example, the spherical carbon molded body can be obtained by heat-treating the porous spherical infusible asphalt in a non-oxidizing atmosphere at 600 ℃ or higher, preferably 650 ℃ or higher, and more preferably 700 ℃ or higher.
Subsequently, the spherical carbon molded body is fired and activated by a conventional method. In this case, the spherical carbon molded body is activated in an activating gas atmosphere containing a mild oxidizing gas such as carbon dioxide or water vapor as a main component. In this way, the spherical activated carbon of the present embodiment can be obtained.
In the present embodiment, the activated gas is allowed to act on the spherical carbon molded body at preferably 600 ℃ or higher, more preferably 650 ℃ or higher, and still more preferably 700 ℃ or higher. This is preferable from the viewpoint of process economy, because carbonization and activation of the spherical carbon molded body can be performed simultaneously.
In the present embodiment, the spherical activated carbon obtained as described above may be further loaded with other substances such as an acid, an alkali, or a metal. The other substances may be added to the spherical activated carbon by a known method. For example, when a metal is added or supported to a spherical activated carbon, the spherical activated carbon can be used as a catalyst or the like.
Examples
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
[ average particle diameter ]
The average particle size of the activated carbon was evaluated in accordance with JIS K1474. Specifically, a particle size cumulative diagram is prepared in accordance with JIS K1474, a horizontal line is drawn on the vertical axis from the intersection of the particle size cumulative diagram and the vertical line of the 50% point on the horizontal axis, and the mesh (mm) of the sieve indicated by the intersection is obtained, and the value of the mesh is defined as the average particle diameter.
[ pore diameter and pore volume ]
The pore diameter and pore volume of the activated carbon were measured using a pore volume mercury porosimeter (AUTOPORE 9200, manufactured by MICROMERITICS) by mercury intrusion method. Specifically, activated carbon was placed in a sample container, and degassing was performed at a pressure of 2.67Pa or less for 30 minutes. Subsequently, mercury is introduced into the sample container, and the pressure is gradually increased to push the mercury into the pores of the activated carbon. Then, from the relationship between the pressure at this time and the amount of mercury introduced, the pore volume distribution of the activated carbon was calculated by using the following calculation formulas.
The pore diameter was calculated as: when mercury is pressed into a cylindrical pore having a diameter (D) with a pressure (P), the following relationship holds, when the surface tension of mercury is "γ" and the contact angle between mercury and the pore wall is "θ", in terms of the balance between the surface tension and the pressure acting on the cross section of the pore:
-πDγcosθ＝π(D/2)2p.cndot. (formula 2).
Therefore, D (— 4 γ cos θ)/P · (formula 3) is obtained.
In the present specification, the surface tension of mercury is 484dyne/cn, the contact angle of mercury and carbon is 130 degrees, the pressure P is expressed in MPa, and the pore diameter D is expressed in μm, and the relationship between the pressure P and the pore diameter D is obtained by the following equation.
D1.24/P (formula 4)
In the present example, the pore volume in the pore diameter range of 50 to 10000nm corresponds to the volume of mercury to be injected in the range corresponding to the mercury injection pressure.
[ evaluation of dust amount ]
The amount of dust of activated carbon was evaluated by the following procedure.
1) A membrane filter (diameter 47mm, mesh size 1 μm, manufactured by ADVANTEC) was dried at 110 ℃ for 1 hour, cooled in a desiccator, and then weighed to 0.1mg by a precision scientific balance.
2) 5g of the dried sample was taken into a 100ml Erlenmeyer flask and weighed to 0.1mg with a precision scientific balance.
3) 100ml of pure water was added to the Erlenmeyer flask, and an ultrasonic cleaner (Bransonic desktop ultrasonic cleaner 1510J-MT, made by Emerson Japan, Ltd.) was used for 3 minutes.
4) The suspension after the ultrasonic treatment was filtered through a sieve having a mesh size of 106 μm, and the filtrate was filtered through a membrane filter provided in a Millipore filter suction apparatus. The wall surface of the Erlenmeyer flask in the step 3) was rinsed with pure water, and the resultant was also filtered with a membrane filter.
5) The sample remaining on the sieve in the step 4) was returned to the Erlenmeyer flask, and 100ml of pure water was added thereto, and then the operations 3) and 4) were repeated three times in total.
6) After drying the filtered membrane filter at 110 ℃ for 1 hour, it was left to cool in a desiccator for 30 minutes, and then weighed to 0.1mg with a precision scientific balance.
7) The amount of carbon dust was calculated by the following formula.
Carbon dust amount (B-A)/S. cndot. (formula 5)
A: mass (g) of membrane filter before filtration
B: mass (g) of the membrane filter after filtration
S: quality (g) of sample
[ rate of abrasion by vibration in water ]
The underwater vibration abrasion rate of activated carbon was evaluated by the following method.
1) After a membrane filter (mesh 0.3 μm) dried at 110 ℃ for 1 hour in advance was cooled in a desiccator, it was weighed to 0.1mg with a precision scientific balance.
2) A dried sample was weighed at a level of about 10g to 0.1mg, transferred to a 200ml separatory funnel, and after 50ml of pure water was added, it was vibrated for 120 minutes by a vibrator (IWAKI INDUSTRY CO., LTD KM-SHAKER model V-S amplitude 40mm, vibration number 250 cycles/minute).
3) The suspension was filtered through a sieve having a mesh size of 150 μm, and the filtrate was filtered with suction using a membrane filter. The wall surface of the separatory funnel in the step 2) above was washed with pure water, and this was also filtered with a membrane filter.
4) After drying the membrane filter at 110 ℃ for 30 minutes, it was left to cool in a desiccator for 30 minutes, and the mass of the membrane filter was accurately measured to 0.1 mg.
5) The underwater vibration abrasion rate was calculated according to the following formula.
In-water vibration abrasion ratio (%) (b-a)/s × 100 · (formula 6)
a: mass (g) of membrane filter before filtration
b: mass (g) of the membrane filter after filtration
s: quality (g) of sample
[ specific surface area ]
The amount of gas adsorbed by a sample (carbonaceous material) was measured using a specific surface area measuring device ("FLOWSORB III" manufactured by MICROMERITICS) based on a gas adsorption method of a continuous flow-through specific surface area method, and the specific surface area was calculated from the BET equation.
Specifically, a sample tube was filled with a sample, and the following operation was performed while introducing helium gas containing 30 vol% of nitrogen gas into the sample tube, to determine the amount of nitrogen adsorbed to the sample. That is, the sample tube was cooled to-196 ℃ to allow the sample to adsorb nitrogen. Subsequently, the sample tube was returned to room temperature. At this time, the amount of nitrogen desorbed from the porous spherical carbonaceous material sample was measured by a thermal conductivity detector and used as the adsorbed gas amount (v). Then, using an approximation formula derived from the BET equation:
Vm is 1/(v (1-x)) · (formula 7),
vm at the liquid nitrogen temperature was obtained by a one-point method (relative pressure x is 0.3) by nitrogen adsorption, and the specific surface area of the sample was calculated by the following formula:
the specific surface area was 4.35 Xvm (m2/g) · (formula 8).
In each of the above calculation formulas, v is an actually measured adsorption amount (cm)3X is relative pressure.
[ packing Density ]
The packing density was measured according to the method of JIS K1474-1991.
[ aspect ratio ]
The aspect ratio of the sample was calculated using a digital microscope (VHX-700F, manufactured by KEYENCE).
Specifically, in order to achieve even extraction, the sample particles 30 were scattered in a petri dish, and the lengths of the major axis and the minor axis of the 1 particle were measured by a digital microscope. Then, the aspect ratio is calculated from the length ratio of the major axis to the minor axis so as to be at most 1. In the following examples and the like, the average aspect ratio of 30 particles is defined as the aspect ratio.
[ crush strength ]
The crush strength can be determined by the following method. That is, 32 samples of the spherical activated carbon were arbitrarily extracted, and the hardness at the moment of crushing the sample particles was measured using a simple particle hardness meter (manufactured by chemical and physical instruments of cylindrical well). The maximum value and the minimum value were excluded from the measured values of hardness, and the average value of the measured values of hardness of 30 sample grains was calculated as the crushing strength of the sample grains.
[ example 1]
10.0kg of residual oil (ethylene tar) produced in the production of ethylene having a specific gravity (ratio of the mass of the sample at 15 ℃ to the mass of pure water having the same volume at 4 ℃) of 1.08 was charged into a stainless pressure-resistant vessel having an internal volume of 25 liters. Air was blown from the bottom of the reaction vessel at a flow rate of 3.7L/min, and an air blowing reaction (air blowing reaction) was carried out at 230 ℃ to 250 ℃ under a pressure of 0.4MPa for 4 hours and 20 minutes. Thus, 9.5kg of air blowing tar (air blowing tar) was obtained. 3.0kg of the resulting blown tar was thermally reformed at 385 ℃ and then the light components were further distilled off under reduced pressure to obtain 1.4kg of blown asphalt. The resulting asphalt had a softening point of 203 ℃ and a toluene insolubles of 58%.
0.72kg of the blown asphalt and 0.28kg of naphthalene were charged into a pressure vessel having an internal volume of 1.5L and equipped with a stirring blade, and the mixture was melt-mixed at 200 ℃ and then cooled to 140 ℃ to 160 ℃ to extrude the mixture, thereby obtaining a rod-shaped molded article having a diameter of 2 mm. Then, the rod-shaped molded article is crushed to a length of about 2.0mm to 2.8 mm. About 450ml of the above-described fracturing material was put into 1L of an aqueous solution in which 1.2 wt% of polyvinyl alcohol (degree of saponification: 88%) as a suspending agent was dissolved and heated to 100 ℃. The pressed product was spheroidized by stirring and dispersing, then cooled, and the aqueous polyvinyl alcohol solution was replaced with water to obtain a spherical asphalt molded body slurry. After most of the water was removed by filtration, naphthalene in the spherical asphalt slurry was extracted and removed by n-hexane 7 times the weight of the spherical asphalt slurry, and porous spherical asphalt was obtained. The porous spherical asphalt thus obtained was heated from room temperature to 150 ℃ over 1 hour using a fluidized bed while hot air was blown, and then heated from 150 ℃ to 260 ℃ at a heating rate of 20 ℃/h, and then kept at 260 ℃ for 1 hour to oxidize. In this way, porous spherical infusible asphalt which is infusible to heat was obtained. Then, the porous spherical infusible pitch was activated in a fluidized bed at 850 ℃ in a nitrogen atmosphere containing 50 vol% of water vapor to a packing density of 0.79g/ml, thereby obtaining a spherical activated carbon. The average particle diameter, pore diameter distribution, dust amount, underwater vibration abrasion rate, specific surface area, aspect ratio and crushing strength of the obtained spherical activated carbon were evaluated.
[ examples 2 to 8]
Activated carbons of examples 2 to 8 were obtained in the same manner as in example 1 except that the amounts of pitch and naphthalene in melt-mixing blown pitch and naphthalene, the amount of charged rod-shaped molded article in spheroidizing, the spheroidizing temperature, the polyvinyl alcohol concentration, the amount of n-hexane in naphthalene extraction, and the filling density after activation were changed as shown in tables 1 and 2.
[ example 9]
Porous spherical asphalt was obtained in the same manner as in example 1 except that the amount of asphalt, the amount of naphthalene, the size of the rod-shaped molded article, the amount of charge of the rod-shaped molded article during spheroidization, the spheroidization temperature, the polyvinyl alcohol concentration, and the amount of n-hexane during naphthalene extraction were adjusted when blown asphalt and naphthalene were melt-mixed as shown in table 1.
The obtained porous spherical asphalt was heated from room temperature to 150 ℃ for 1 hour while hot air was blown into the layer, and then heated from 150 ℃ to 260 ℃ at a heating rate of 20 ℃/h, and then kept at 260 ℃ for 1 hour to oxidize. In this way, porous spherical infusible asphalt which is infusible to heat is obtained. Then, the porous spherical infusible pitch was activated in a static layer in a nitrogen atmosphere containing 50 vol% of water vapor at 850 ℃ until the packing density became 0.70g/ml, to obtain activated carbon.
[ example 10]
Porous spherical asphalt was obtained in the same manner as in example 1 except that the amount of asphalt, the amount of naphthalene, the size of the rod-shaped molded article, the amount of the rod-shaped molded article charged in spheroidizing, the spheroidizing temperature, the polyvinyl alcohol concentration, and the amount of n-hexane in extracting naphthalene were adjusted in melt-mixing the blown asphalt and naphthalene as shown in table 1.
The obtained porous spherical asphalt was heated from room temperature to 150 ℃ for 1 hour while hot air was blown into the layer, and then heated from 150 ℃ to 300 ℃ at a heating rate of 20 ℃/h, and then kept at 300 ℃ for 1 hour to oxidize. In this way, porous spherical infusible asphalt which is infusible to heat was obtained. Then, the porous spherical infusible pitch was activated in a static layer in a nitrogen atmosphere containing 50 vol% of water vapor at 850 ℃ until the packing density became 0.68g/ml, to obtain activated carbon.
[ example 11]
A porous spherical asphalt was obtained in the same manner as in example 1 except that xanthan gum was used as a suspending agent, and the amount of asphalt, the amount of naphthalene, the size of the rod-shaped molded body, the amount of charge of the rod-shaped molded body in spheroidizing, the spheroidizing temperature, the concentration of xanthan gum, and the amount of n-hexane in extracting naphthalene were adjusted in melt-mixing blown asphalt and naphthalene as shown in table 1.
The obtained porous spherical asphalt was heated from room temperature to 150 ℃ for 1 hour while hot air was blown into the layer, and then heated from 150 ℃ to 300 ℃ at a heating rate of 20 ℃/h, and then kept at 300 ℃ for 1 hour to oxidize. In this way, porous spherical infusible asphalt which is infusible to heat was obtained. Then, the porous spherical infusible pitch was activated in a static layer in a nitrogen atmosphere containing 50 vol% of water vapor at 850 ℃ until the packing density became 0.70g/ml, to obtain activated carbon.
Comparative example 1
Activated carbon was produced by the same operation as in example 1 except that the amount of pitch was 0.75kg and the amount of naphthalene was 0.25kg, and in the firing/activating step, the porous spherical infusible pitch molded body melted and could not maintain its shape (spherical shape).
Comparative example 2
As shown in table 1, activated carbon was produced by the same operation as in example 1 except that the amounts of blown asphalt and naphthalene, the spheroidizing temperature, the polyvinyl alcohol concentration and the hexane amount were adjusted, and in the firing/activating step, the porous spherical infusible asphalt molded article was melted and could not maintain its shape (spherical shape).
Comparative example 3
Activated carbon was produced by the same operation as in example 1 except that the amounts of blown asphalt and naphthalene, the spheroidization temperature, and the polyvinyl alcohol concentration were adjusted as shown in table 1. As a result, the asphalt molded body obtained in the step of molding the crosslinked and heavy asphalt has an elliptical shape.
Comparative example 4
Activated carbon was obtained in the same manner as in example 1 except that a rod-shaped molded article having a diameter of 1.0mm was crushed to a length of about 1.0mm to 1.5mm, and the amounts of blown asphalt and naphthalene, the spheroidization temperature, the polyvinyl alcohol concentration, and the hexane amount were adjusted as shown in table 1.
Comparative example 5
The same evaluation as in example 1 was performed for a globular aigret X7000H (Osaka Gas Chemical co., Ltd.).
Comparative example 6
KURARAY COAL SW (KURARAY Chemical co., Ltd.) was evaluated in the same manner as in example 1.
The results of the examples and comparative examples are summarized in tables 1 and 2.
In Table 1, "size" means the size of the rod-shaped compact, and "charged amount" means the charged amount of the rod-shaped compact. Further, the "suspending agent" is, for example, PVA. In addition, "Rhex" means a hexane mass ratio at the time of extraction, more specifically, means a mass ratio of n-hexane to spherical asphalt slurry (n-hexane amount/spherical asphalt slurry amount).
In table 2, "D1" means melting, and "D2" means both elliptical. Further, "Vp 1" means pore volume in the range of 10 to 10000nm, and "Vp 2" means pore volume in the range of 50 to 10000 nm. In addition, "Asw" means the rate of vibration abrasion in water, "Rasp" means the aspect ratio, and "Sp" means the crushing strength.
[ Table 1]
[ Table 2]
Industrial applicability of the invention
The present invention can be suitably used as activated carbon for, for example, separation processes, purification, catalyst, or solvent recovery.
Claims (11)
1. A spherical activated carbon characterized by being an integrally molded spherical activated carbon having an average particle diameter of 1.5mm to 4.0mm,
the pore volume is in the range of 0.01ml/g to 0.24ml/g in the range of 50nm to 10000 nm.
2. Spherical activated carbon according to claim 1,
the crushing strength is more than 1.20 kg/piece.
3. Spherical activated carbon according to claim 1,
the amount of dust contained in 1g of the spherical activated carbon is 2000. mu.g or less.
4. Spherical activated carbon according to claim 1,
the vibration abrasion rate in water is 5% or less.
5. Spherical activated carbon according to claim 1,
the aspect ratio is 0.7 or more, and the aspect ratio is a ratio of a short diameter to a long diameter.
6. Spherical activated carbon according to claim 1,
a base or an acid is added.
7. A method for producing a spherical activated carbon, characterized in that the spherical activated carbon according to claim 1 is produced, and the method comprises:
a step of adding a bicyclic or tricyclic aromatic compound having a boiling point of 200 ℃ or higher as an additive to a crosslinked and heavy asphalt slurry derived from a heavy hydrocarbon oil;
a step of obtaining porous spherical asphalt by melting, suspending and dispersing a mixture of the crosslinked and heavy asphalt and the additive in hot water and extracting the additive from the spherical asphalt obtained thereby using a solvent; and
a step of firing/activating the porous spherical asphalt slurry without melting,
the heavy hydrocarbon oil is one or more selected from the group consisting of petroleum tar, coal tar and ethylene tar,
the temperature of the hot water is more than 95 ℃ and less than 120 ℃,
the solvent is an aliphatic compound, and the solvent is a fatty compound,
the mass ratio of the solvent to the spherical asphalt is 7 or more.
8. A process for producing spherical activated carbon as claimed in claim 7,
the additive is added in an amount of 26 to 50 mass% assuming that the total amount of the mixture of the crosslinked and heavy asphalt and the additive is 100 mass%.
9. A process for producing spherical activated carbon as claimed in claim 7,
the additive is naphthalene.
10. A process for producing spherical activated carbon as claimed in claim 7,
the mixture of the crosslinked, heavy asphalt and the additives is melt suspended and dispersed in hot water in the presence of a suspending agent.
11. A process for producing spherical activated carbon as claimed in claim 10,
the suspending agent is one or both of polyvinyl alcohol and xanthan gum.
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| EP4206129A1 (en) * | 2020-09-23 | 2023-07-05 | Kuraray Co., Ltd. | Activated carbon and water treatment method using said activated carbon |
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