Carbonaceous material and method for producing the same, sorption filter, water purifier cartridge, water purifier, and water purification facility

Abstract

To provide a carbonaceous material and a method for producing the same, a sorption filter, a water purifier cartridge, a water purifier and a water purification facility, which are capable of achieving, at high levels, performance of removing all of free residual chlorine that can be decomposed on the surface of the carbonaceous material, relatively large molecular-size anionic surfactants, and the like.SOLUTION: In the carbonaceous material of the present invention, the iodine sorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black 5 is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the sorption isotherm of N2 at -196°C is 1,100 m2 / g or more and 1,700 m2 / g or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a carbonaceous material, a method for producing the same, an adsorption filter, a water purifier cartridge, a water purifier, and a water purification facility.

Background Art

[0002] Household water purifiers are widely used to remove harmful substances in tap water. Among such harmful substances, free residual chlorine is designated as a substance to be removed in the household product quality labeling law for household water purifiers, and it is desired to be removed from tap water.

[0003] To remove free residual chlorine, activated carbon or metal sulfite is usually used in household water purifiers. For example, in Patent Document 1, activated carbon having many small pore diameters with a pore diameter of 0.679 nm or more and 0.733 nm or less is described, and by having such a pore diameter, the performance of capturing free residual chlorine in the pores of the activated carbon is improved. Patent Document 2 describes a remover for free residual chlorine containing a metal oxide.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in recent years, for household water purifiers, there has been an increasing demand for miniaturization of the water purifier body, etc., and there is a need for higher removal performance of activated carbon. In particular, in 2019, the JIS test method for household water purifiers was revised, and in the new JIS S3201:2019, five additional substances to be removed were added. As a result, a household water purifier that removes a greater variety of harmful substances than before is desired.

[0006] In the activated carbon described in Patent Document 1, by setting the pore diameter within a predetermined range to control micropores, high removal performance for free residual chlorine is achieved, but the large pores are not controlled. Therefore, this activated carbon does not have high adsorption performance for relatively large organic substances such as the newly added anionic surfactant, and cannot remove a variety of harmful substances.

[0007] Also, in the removing agent described in Patent Document 2, high removal performance for free residual chlorine is achieved by utilizing the reducing action of metal sulfite, but the removing agent does not have pores. Therefore, this removing agent also does not have adsorption performance for anionic surfactants, etc., and cannot remove a variety of harmful substances.

[0008] The present invention has been made in view of such problems, and an object thereof is to provide a carbonaceous material, a method for producing the same, an adsorption filter, a water purifier cartridge, a water purifier, and a water purification facility capable of achieving high-level compatibility in removal performance between free residual chlorine decomposable on the surface of the carbonaceous material and relatively large molecular size anionic surfactants, etc.

Means for Solving the Problems

[0009] As a result of intensive research to solve the above object, the present inventors have found that a carbonaceous material having an iodine adsorption amount, a reactive black pentavalent, and a specific surface area within specific ranges respectively can achieve high-level compatibility in removal performance between free residual chlorine decomposable on the surface of the carbonaceous material and relatively large molecular size anionic surfactants, etc., and have completed the present invention.

[0010] The present invention includes the following embodiments. [1] A carbonaceous material having an iodine adsorption amount of 1,300 mg / g or more and 1,800 mg / g or less, a reactive black pentavalent of 1.0 g / L or more and 6.0 g / L or less, and a specific surface area of 1,100 m 2 / g or more and 1,700 m 2 / g or less, determined by the BET method from the N 2 adsorption isotherm at -196°C.

[0011] [2] The carbonaceous material according to [1], wherein the ratio (A / B) of the pore volume (A) of pores of 1.00 nm or less calculated by the QSDFT method per 1 g of the carbonaceous material from the nitrogen adsorption isotherm to the pore volume (B) of mesopores determined by the BJH method from the N 2 adsorption isotherm at -196°C is 1.0 or more and 4.0 or less.

[0012] [3] The carbonaceous material according to [1], wherein the proportion of mesopores is 4.8% or more and 15.0% or less.

[0013] [4] The carbonaceous material according to [1], wherein the pore volume of mesopores determined by the BJH method from the N 2 adsorption isotherm at -196°C is 0.06 cm 3 / g or more and 0.30 cm 3 / g or less.

[0014] [5] The carbonaceous material according to [1], wherein the total pore volume determined by the BJH method from the N 2 adsorption isotherm at -196°C is 0.25 cm 3 / g or more and 1.00 cm 3 / g or less.

[0015] [6] The carbonaceous material according to [1], wherein the packing density measured by the tapping method is 0.30 g / mL or more and 0.50 g / mL or less.

[0016] [7] The carbonaceous material according to any one of [1] to [6], which is used for removing at least free residual chlorine and anionic surfactants in water.

[0017] [8]A carbonization step of carbonizing a raw material to obtain a carbide, and an activation step of activating the carbide to obtain an activated product, the method for producing a carbonaceous material according to any one of [1] to [6].

[0018] [9]The production method according to [8], further including a washing step of washing the activated product.

[0019]

[10] The production method according to [8], wherein the raw material is coconut shell.

[0020]

[11] An adsorption filter including the carbonaceous material according to any one of [1] to [6].

[0021]

[12] A water purifier cartridge including the carbonaceous material according to any one of [1] to [6].

[0022]

[13] A water purifier including the carbonaceous material according to any one of [1] to [6].

[0023]

[14] Water purification equipment provided with the carbonaceous material according to any one of [1] to [6].

Advantages of the Invention

[0024] According to the present invention, it is possible to provide a carbonaceous material and a method for producing the same, an adsorption filter, a water purifier cartridge, a water purifier, and water purification equipment capable of achieving high-level removal performance of free residual chlorine decomposable on the surface of the carbonaceous material and anionic surfactants with relatively large molecular sizes.

Brief Description of the Drawings

[0025]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0026] Hereinafter, embodiments for implementing the present invention (hereinafter simply referred to as "the present embodiments") will be described in detail. It should be noted that the following present embodiments are examples for explaining the present invention, and the present invention is not limited to only the present embodiments.

[0027] In this specification, the pores of the carbonaceous material conform to the classification criteria of IUPAC (International Union of Pure and Applied Chemistry). According to the pore diameter (diameter), pores with a pore diameter of less than 2.0 nm are classified as micropores, pores with a pore diameter of 2.0 nm or more and 50.0 nm or less are classified as mesopores, and pores with a pore diameter exceeding 50.0 nm are classified as macropores. Mesopores are effective for the adsorption of relatively large molecular-sized anionic surfactants and the like.

[0028] [Carbonaceous material] The carbonaceous material of the present embodiment has an iodine adsorption amount of 1,300 mg / g or more and 1,800 mg / g or less, a reactive black 5 valence of 1.0 g / L or more and 6.0 g / L or less, and N at -196 °C 2 The specific surface area determined by the BET method from the adsorption isotherm of is 1,100 m 2 / g or more and 1,700 m 2 / g or less.

[0029] By the carbonaceous material having such requirements, it becomes possible to achieve both high removal performance for free residual chlorine decomposable on the surface of the carbonaceous material and relatively large molecular-sized anionic surfactants and the like at a high level. That is, since the surface area per unit mass of the carbonaceous material is controlled to be suitable for free residual chlorine decomposable on the surface of the carbonaceous material, it is possible to have high removal performance for free residual chlorine. Moreover, since the pore diameter of the carbonaceous material is controlled to be suitable for relatively large molecular-sized anionic surfactants and the like, it can have high adsorption performance for anionic surfactants and the like.

[0030] Examples of the anionic surfactant include alkyl sulfonates such as sodium linear dodecylbenzenesulfonate. The carbonaceous material of the present embodiment can preferably adsorb one or more of these anionic surfactants.

[0031] The iodine adsorption amount of the carbonaceous material is 1,300 mg / g or more and 1,800 mg / g or less. The iodine adsorption amount is an index of the surface area of pores capable of physically adsorbing anionic surfactants and the like having a relatively large molecular size present in the carbonaceous material. When the iodine adsorption amount of the carbonaceous material is within the above range, the carbonaceous material exhibits high adsorption performance particularly for anionic surfactants while maintaining the removal performance for free residual chlorine. When the iodine adsorption amount of the carbonaceous material is 1,300 mg / g or more, the pore volume of the carbonaceous material becomes sufficiently large, and the adsorption performance for anionic surfactants and the like is remarkably improved. When the iodine adsorption amount of the carbonaceous material is 1,800 mg / g or less, the pores of the carbonaceous material do not become too large, and the control of the pores for adsorbing anionic surfactants and the like becomes easy.

[0032] The iodine adsorption amount is measured and calculated in accordance with JIS K 1474 (2014). For the specific measurement and calculation method of the iodine adsorption amount, refer to the examples.

[0033] The iodine adsorption amount is preferably 1,310 mg / g or more and 1,700 mg / g or less, more preferably 1,330 mg / g or more and 1,650 mg / g or less. When the iodine adsorption amount is within the above range, there is a tendency to obtain a carbonaceous material having higher adsorption performance particularly for anionic surfactants while maintaining the removal performance for free residual chlorine.

[0034] The reactive black 5 value of the carbonaceous material is 1.0 g / L or more and 6.0 g / L or less. Reactive black 5 is a dye represented by the following formula (1) and is also referred to as C.I. Reactive Black-5.

[0035]

Chemical formula

[0036] Since Reactive Black 5 has a large molecular weight of 995.88 and a bulky structure, the pentavalent Reactive Black 5 serves as an index for the adsorption characteristics of anionic surfactants with a relatively large molecular size. When the pentavalent Reactive Black 5 is within the above range, the carbonaceous material exhibits high adsorption performance particularly for anionic surfactants while maintaining the removal performance for free residual chlorine. When the pentavalent Reactive Black 5 is 1.0 g / L or more, the cumulative pore volume in the large pores of the carbonaceous material does not become too large, and the carbonaceous material can suitably retain an effective pore volume for anionic surfactants with a relatively large molecular size while maintaining the removal performance for free residual chlorine. When the pentavalent Reactive Black 5 is 6.0 g / L or less, the pore volume suitable for the adsorption of anionic surfactants with a relatively large molecular size among the pores of the carbonaceous material is sufficient. Therefore, the adsorption performance for anionic surfactants and the like is significantly improved.

[0037] Reactive Black 5 value can be calculated, for example, as follows. That is, first, using an ultraviolet-visible spectrophotometer, under the conditions of a wavelength of 594 nm and an optical path length (cell length) of 10 mm, for a test solution containing Reactive Black 5, after mixing a carbonaceous material with the test solution and sufficiently adsorbing Reactive Black 5 onto the carbonaceous material, the absorbances of the residual solutions obtained by removing the carbonaceous material adsorbed with Reactive Black 5 are measured respectively. Then, using these absorbances, the residual rate (%) of Reactive Black 5 contained in the residual solution and the adsorption amount ( / g) of Reactive Black 5 per 1 g of the carbonaceous material are calculated. The Reactive Black 5 value (g / L) is calculated as the amount of the carbonaceous material required to remove 99% of Reactive Black 5 in 1 L of the test solution using these values. In the measurement of the Reactive Black 5 value, as the carbonaceous material, it is preferable to use a carbonaceous material whose volume-based cumulative distribution 50% particle size (D50) is adjusted to be 9.0 μm or more and 11.0 μm or less. In this specification, the 50% particle size (D50) refers to the value measured as the volume-based median diameter using a laser diffraction light scattering method particle size distribution measuring device. For the specific measurement and calculation method of the Reactive Black 5 value, reference may be made to the examples.

[0038] The Reactive Black 5 value is preferably 1.5 g / L or more and 5.5 g / L or less, more preferably 1.7 g / L or more and 4.5 g / L or less, and still more preferably 2.0 g / L or more and 4.0 g / L or less. When the Reactive Black 5 value is within the above range, while maintaining the removal performance for free residual chlorine, in particular, there is a tendency to obtain a carbonaceous material having higher adsorption performance for anionic surfactants and the like.

[0039] In the carbonaceous material, the specific surface area (hereinafter, also simply referred to as "BET specific surface area") determined by the BET method from the adsorption isotherm of N at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or more and 1,700 m 2is less than or equal to 1,100 m² / g. The BET specific surface area is the surface area per unit mass of the carbonaceous material and is an index of the surface area capable of decomposing free residual chlorine. When the BET specific surface area is within the above range, the carbonaceous material maintains the adsorption performance for anionic surfactants and the like, and in particular, exhibits high removal performance for free residual chlorine. When the BET specific surface area is 1,100 m 2 / g or more, the specific surface area of the carbonaceous material becomes sufficient. Therefore, the carbonaceous material can exhibit high removal performance for free residual chlorine, and the removal performance for free residual chlorine is significantly improved. When the BET specific surface area is 1,700 m 2 / g or less, the specific surface area of the carbonaceous material does not become too large, and thus the pore volume of the carbonaceous material is also suitable. In addition, a decrease in the amount of carbon constituting the carbon skeleton is not caused, and a suitable carbonaceous material can be obtained. Therefore, for example, even in tap water, the carbonaceous material is hardly broken and can exhibit high removal performance for free residual chlorine and anionic surfactants and the like. For the specific measurement and calculation method of the BET specific surface area, reference may be made to the examples.

[0040] The BET specific surface area is preferably 1,250 m 2 / g or more and 1,690 m 2 / g or less, more preferably 1,300 m 2 / g or more and 1,680 m 2 / g, and still more preferably 1,400 m 2 / g or more and 1,670 m 2 / g. When the BET specific surface area is within the above range, there is a tendency to obtain a carbonaceous material having higher removal performance for free residual chlorine while maintaining the adsorption performance for anionic surfactants and the like.

[0041] In the carbonaceous material, the pore volume (A) with a pore diameter of 1.0 nm or less calculated by the QSDFT method per 1 g of the carbonaceous material from the nitrogen adsorption isotherm (hereinafter, also simply referred to as "pore volume with a pore diameter of 1.00 nm or less") and N at -196 °C 2The ratio (A / B, hereinafter also simply referred to as "mesopore ratio") of the micropore volume (B) determined by the BJH method from the adsorption isotherm (hereinafter also simply referred to as "pore volume of mesopores") is preferably 1.0 or more and 4.0 or less, more preferably 1.3 or more and 3.5 or less, and still more preferably 1.5 or more and 3.0 or less. When the mesopore ratio is within the above range, a carbonaceous material having a higher removal performance particularly for free residual chlorine can be obtained while maintaining the adsorption performance for anionic surfactants and the like.

[0042] The mesopore ratio is an index indicating the proportion of pores effective for removing free residual chlorine. When the mesopore ratio is 1.0 or more, pores having a pore diameter effective for removing free residual chlorine are more sufficiently present, and tend to exhibit higher removal performance. When the mesopore ratio is 4.0 or less, the proportion of pores that are too large and not suitable for removing free residual chlorine is small, and the voids in the carbonaceous material do not become too large, so that the amount of carbon constituting the carbon skeleton does not decrease. Therefore, it tends to exhibit higher removal performance.

[0043] For the specific measurement and calculation method of the mesopore ratio, reference may be made to the examples.

[0044] The proportion of mesopores in the carbonaceous material is preferably 4.8% or more and 15.0% or less, more preferably 5.0% or more and 13.0% or less, and still more preferably 6.0% or more and 12.0% or less. When the proportion of mesopores is within the above range, a carbonaceous material having a higher adsorption performance particularly for anionic surfactants and the like can be obtained while maintaining the removal performance for free residual chlorine.

[0045] In this specification, the proportion of mesopores means, in the carbonaceous material, the ratio of the amount of N adsorbed at -196 °C to the specific surface area (i.e., BET specific surface area) determined by the BET method from the adsorption isotherm of N at -196 °C 2 of N adsorbed at -196 °C to the specific surface area (i.e., BET specific surface area) determined by the BET method from the adsorption isotherm of N at -196 °C 2It is determined by the ratio of the specific surface area obtained by the BJH method from the adsorption isotherm (hereinafter, also simply referred to as "BJH specific surface area"). Mesopores are relatively large pores among the pores contributing to adsorption in the carbonaceous material. Therefore, the larger the proportion of mesopores, the better the adsorption performance for anionic surfactants with a relatively large molecular size. For the specific measurement and calculation method of the proportion of mesopores, refer to the examples.

[0046] When the proportion of mesopores is 4.8% or more, the proportion of effective pores for anionic surfactants with a relatively large molecular size becomes sufficient. Therefore, the carbonaceous material maintains the removal performance for free residual chlorine, and in particular, the removal performance for anionic surfactants and the like is significantly improved. When the proportion of mesopores is 15.0% or less, the pores of the carbonaceous material do not become too large, and while maintaining the removal performance for free residual chlorine, it becomes easier to control the pores for adsorbing anionic surfactants and the like.

[0047] In the carbonaceous material, the pore volume of mesopores (hereinafter, also simply referred to as "pore volume of mesopores") obtained by the BJH method from the adsorption isotherm of N at -196 °C 2 is preferably 0.06 cm 3 / g or more and 0.30 cm 3 / g or less, more preferably 0.10 cm 3 / g or more and 0.25 cm 3 / g or less, and still more preferably 0.12 cm 3 / g or more and 0.22 cm 3 / g or less. When the pore volume of mesopores is within the above range, a carbonaceous material having a higher adsorption performance for anionic surfactants and the like while maintaining the removal performance for free residual chlorine tends to be obtained.

[0048] When the pore volume of mesopores is 0.06 cm 3By being 0.30 cm³ / g or more, the carbonaceous material can have many relatively large pores that are particularly effective for anionic surfactants and the like. Therefore, the carbonaceous material tends to have high adsorption performance particularly for anionic surfactants and the like while maintaining the removal performance for free residual chlorine. For the specific measurement and calculation method of the pore volume of mesopores, reference may be made to the examples. 3 By being 0.30 cm³ / g or less, the pores of the carbonaceous material do not become too large, and the carbonaceous material can have many pores effective for the adsorption of anionic surfactants and the like. Therefore, the carbonaceous material tends to have high adsorption performance particularly for anionic surfactants and the like while maintaining the removal performance for free residual chlorine. For the specific measurement and calculation method of the pore volume of mesopores, reference may be made to the examples.

[0049] In the carbonaceous material, the total pore volume (hereinafter, also simply referred to as "total pore volume") determined by the BJH method from the N₂ adsorption isotherm at -196 °C is preferably 0.25 cm³ / g or more and 1.00 cm³ / g or less, more preferably 0.35 cm³ / g or more and 0.90 cm³ / g or less, and still more preferably 0.45 cm³ / g or more and 0.85 cm³ / g or less. When the total pore volume is within the above range, a carbonaceous material having higher adsorption performance particularly for anionic surfactants and the like while maintaining the removal performance for free residual chlorine tends to be obtained. The total pore volume is calculated as the cumulative pore volume in the range where the pore diameter is 1.2 nm or more and 97.4 nm or less. 2 / g or more 1.00 cm³ / g 3 / g or less, and more preferably 0.35 cm³ / g 3 / g or more 0.90 cm³ / g 3 / g or less, and still more preferably 0.45 cm³ / g 3 / g or more 0.85 cm³ / g 3 / g or less. 3 When the total pore volume is within the above range, a carbonaceous material having higher adsorption performance particularly for anionic surfactants and the like while maintaining the removal performance for free residual chlorine tends to be obtained. The total pore volume is calculated as the cumulative pore volume in the range where the pore diameter is 1.2 nm or more and 97.4 nm or less.

[0050] By the total pore volume being 0.25 cm³ / g or more, since the pore volume of the carbonaceous material is sufficiently large, the carbonaceous material tends to exhibit higher performance particularly for anionic surfactants and the like. When the total pore volume is 1.00 cm³ / g 3 / g or more, 3By being / g or less, the carbonaceous material can have pores that do not become too large and can have many pores effective for adsorption of anionic surfactants and the like, so it tends to exhibit higher performance against anionic surfactants and the like. For the specific measurement and calculation methods of the total pore volume, reference may be made to the examples.

[0051] In the carbonaceous material, the bulk density measured by the tapping method (hereinafter, also simply referred to as "bulk density") is preferably 0.30 g / mL or more and 0.50 g / mL or less, more preferably 0.31 g / mL or more and 0.45 g / mL or less, and still more preferably 0.33 g / mL or more and 0.43 g / mL or less. By the bulk density being within the above range, the carbonaceous material tends to be able to achieve a higher level of removal performance against free residual chlorine, anionic surfactants, and the like. By the bulk density being 0.30 g / mL or more, the pores of the carbonaceous material do not become too large and can have many pores effective for free residual chlorine, anionic surfactants, and the like. Therefore, the carbonaceous material tends to have high removal performance against free residual chlorine, anionic surfactants, and the like. By the bulk density being 0.50 g / mL or less, there is a tendency for pores contributing to physical adsorption to be sufficiently present. Therefore, the carbonaceous material tends to have higher removal performance against free residual chlorine, anionic surfactants, and the like. For the specific measurement and calculation methods of the bulk density, reference may be made to the examples.

[0052] The shape of the carbonaceous material varies depending on the application and is not particularly limited. Such shapes include, for example, powdery, massive, crushed, spherical, cylindrical, ellipsoidal, distorted, elliptical cylindrical, elliptical frustum, and polygonal columns such as triangular column, square column, pentagonal column, and hexagonal column, rod-shaped, filamentous, pellet-shaped such as solid pellet and hollow pellet, crushed like powdery, substrate-shaped (sheet-shaped), woven cloth (cross)-shaped, fibrous such as felt-shaped, and block-shaped, etc.

[0053] As the shape of the carbonaceous material, it is preferable to adopt a shape applicable as the carbonaceous material in known adsorption filters. Such shapes include, for example, crushed shapes such as spherical, ellipsoidal, distorted, rod-shaped, thread-shaped, pellet-shaped, and powdery; substrate shapes (sheet shapes); woven cloth (cross) shapes; fibrous shapes; and block shapes. These shapes can be appropriately selected according to the specific usage mode. Among these, since the adsorption performance per unit volume is high, the shape of the carbonaceous material is preferably a crushed shape, more preferably a powdery shape. In the case of a powdery carbonaceous material, its dimensions are not particularly limited, and the particle size and the like can be appropriately adjusted according to the specific usage mode.

[0054] In this specification, the crushed shape refers to particles having an irregular shape and usually having any angular shape. Also, the powdery shape refers to, for example, fine powder, powder, fine granule, and granular powder, and usually, the 50% particle size (D50) of the cumulative distribution based on volume is 1 μm or more and 150 μm or less.

[0055] For example, when using the carbonaceous material as an adsorption filter of a water purifier, although it varies depending on the application and is not particularly limited, its shape is preferably cylindrical and substrate-shaped (sheet-shaped). When the carbonaceous material has such a shape, it tends to be possible to efficiently use the carbonaceous material as an adsorption filter of a water purifier.

[0056] Preferably, the carbonaceous material is activated carbon.

[0057] [Manufacturing method of carbonaceous material] The carbonaceous material of this embodiment can be obtained by a known manufacturing method.

[0058] Such methods include, for example, pyrolysis method, activation method, coating method, and vapor deposition method. As the manufacturing method, it is preferable to use the activation method. By using these manufacturing methods, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black 5 valence is 1.0 g / L or more and 6.0 g / L or less, and N at -196 °C 2The specific surface area determined by the BET method from the adsorption isotherm is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily produce a carbonaceous material.

[0059] The method for producing a carbonaceous material according to this embodiment includes a carbonization step of carbonizing a raw material to obtain a carbide, and an activation step of subjecting the carbide to an activation treatment to obtain an activated product. The method for producing a carbonaceous material according to this embodiment preferably includes a washing step of washing the activated product.

[0060] (Carbonization step) The method for producing a carbonaceous material includes a carbonization step of carbonizing a raw material to obtain a carbide. The raw material is not particularly limited as long as it can obtain a desired carbonaceous material. Examples of the raw material include plant-based raw materials or fossil-based raw materials such as wood, wood powder, fruit shells such as coconut shells, palm kernels, seeds such as ume and peach, by-products during pulp production, bagasse, molasses, coal (such as peat, lignite, brown coal, and bituminous coal), anthracite, petroleum distillation residue components, petroleum pitch, coke, and coal tar; various synthetic resins such as phenolic resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, celluloid, epoxy resin, polyurethane resin, polyester resin, acrylic resin, and polyamide resin; synthetic rubbers such as polybutylene, polybutadiene, and polychloroprene; other synthetic woods; and synthetic pulp. These raw materials can be used alone or, depending on the required specifications, two or more of them can be mixed and used in any ratio.

[0061] The raw material is preferably a natural product, more preferably a coconut shell. By using such a raw material, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black 5 valence is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the N 2 adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily produce a carbonaceous material.

[0062] The raw material may contain additives or the like as necessary. Further, additives or the like may be added to the carbide as necessary. Examples of such additives or the like include water, coal tar, tar anhydride, hard pitch, coal tar-based pitch, and petroleum-based pitch. The additives or the like may be used alone or in combination of two or more. The additives or the like are each usually blended in an amount of 1.0 part by mass or more and 50.0 parts by mass or less with respect to 100 parts by mass of the raw material or the carbide. Further, the total amount of the additives or the like is usually 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the raw material or the carbide. When mixing the raw material or the carbide and the additive, if necessary, the oxygen amount in the raw material or the carbide may be adjusted in the range of 1.0% by mass or more and 20.0% by mass or less with respect to 100% by mass of the raw material or the carbide. The adjustment of the oxygen amount can be performed, for example, by mixing the raw material or the carbide and oxygen under heating at 150°C or higher and 300°C or lower.

[0063] In the method for producing the carbonaceous material, the raw material may be pulverized or molded before carbonizing the raw material. Examples of such methods include a method in which the raw material is pulverized into a powder using a known pulverizer and then carbonized before carbonizing the raw material. Further, examples include a method in which the raw material is molded into pellets by a known method and then carbonized before carbonizing the raw material.

[0064] When the shape of the raw material is in powder form, the particle size of the powder (50% particle diameter, D50 of the cumulative distribution based on volume) is preferably 1 μm or more and 150 μm or less.

[0065] The carbonization method of the raw material is not particularly limited, and examples include a method of heating to 300°C or higher and 900°C or lower, preferably 400°C or higher and 800°C or lower, under oxygen-free conditions.

[0066] The carbonization time can be appropriately set according to the raw material and the equipment for carbonization. The carbonization time is, for example, 15 minutes or more and 20 hours or less, preferably 30 minutes or more and 10 hours or less, and more preferably 60 minutes or more and 5 hours or less. The carbonization treatment can be carried out using known manufacturing equipment such as a rotary kiln. Further, the carbonization treatment may be carried out under reduced pressure by excluding air, or may be carried out under a nitrogen atmosphere.

[0067] In the method for producing a carbonaceous material, the carbide may be pulverized into a powder using a known pulverizer. Thereby, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and N 2 The specific surface area determined by the BET method from the adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily produce a carbonaceous material. In the method for producing a carbonaceous material, after pulverizing the carbide into a powder, an additive or the like may be added to the powdered carbide as necessary and kneaded by a known method, and the obtained kneaded product may be molded by a known method.

[0068] When the shape of the carbide is in powder form, the particle size of the carbide (50% particle size of the cumulative distribution based on volume, D50) is preferably 1 μm or more and 150 μm or less.

[0069] In the method for producing a carbonaceous material, the carbide, powdered carbide, kneaded product, or powdered kneaded product may be molded into cylindrical pellets using a known method. Thereby, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and N 2 The specific surface area determined by the BET method from the adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily produce a carbonaceous material. When the carbide is in the shape of a cylindrical pellet, the diameter of the cylindrical pellet is preferably 0.1 mm or more and 4.0 mm or less. Further, the aspect ratio (diameter: height) of the cylindrical pellet is preferably 1:1 to 1:10.

[0070] By the above carbonization step, the carbide of the raw material is obtained.

[0071] The method for producing the carbonaceous material may include a washing step and / or a drying step in which, after the carbonization step, the carbide is subjected to a washing treatment and / or a drying treatment or the like. The conditions in these steps are not particularly limited, and known conditions can be adopted. Further, the following washing step and drying step may be referred to.

[0072] (Activation step) The method for producing the carbonaceous material includes an activation step of subjecting the carbide to an activation treatment to obtain an activated product.

[0073] As the activation treatment, a known method can be adopted.

[0074] For the activation treatment, known production equipment such as a rotary kiln, a fluidized furnace, and a sleep furnace (vertical furnace) can be used. Further, the activation treatment may be performed under reduced pressure by excluding air, or may be performed under a nitrogen atmosphere.

[0075] The activation treatment is preferably performed using a rotary kiln. By using a rotary kiln, the activated product whose mass has become lighter as the activation of the carbide progresses can be prevented from scattering outside the furnace and can remain in the kiln furnace. Therefore, the carbide can be more sufficiently activated, and there is a tendency to obtain an activated product in which micropores and mesopores are sufficiently developed and the ratio of these pores is controlled within a suitable range.

[0076] Further, by using a rotary kiln, it becomes possible to efficiently bring the carbide into contact with the active gas. As a result, there is a tendency to preferably produce a carbonaceous material having a higher adsorption performance for free residual chlorine, an anionic surfactant, and the like.

[0077] When performing the activation treatment using a rotary kiln, the carbide input into the rotary kiln preferably has a particle size that passes through a standard sieve wire mesh specified in JIS Z8801-1:2019, specifically, larger than 70 mesh (mesh opening size: 243 μm) and smaller than 2 mesh (mesh opening size: 10.7 mm), and more preferably, larger than 32 mesh (mesh opening size: 490 μm) and smaller than 2 mesh (mesh opening size: 10.7 mm). When the particle size of the carbide is within the above range, the activated product whose mass has become lighter as the activation of the carbide progresses stays in the kiln more, enabling more efficient activation. As the carbide, carbide whose particle size is adjusted by cutting the raw material into a desired size in advance before the carbonization process may be used, or carbide whose particle size is adjusted by crushing and classifying the carbide into a desired size may be used.

[0078] Examples of the activation treatment method include a gas activation method in which the carbide is gasified using an active gas such as water vapor gas, oxygen gas, and carbon dioxide gas, and a chemical activation method in which the carbide is activated using a chemical such as zinc chloride and phosphoric acid. As the activation treatment method, the gas activation method is preferred. By using an active gas as the gas activation method, it tends to have a more sufficient reaction rate and can control the reaction rate without further reducing the production efficiency. Therefore, it tends to be easier to obtain a carbonaceous material with developed micropores and mesopores. As a result, it tends to be possible to preferably produce a carbonaceous material having higher treatment performance against free residual chlorine and anionic surfactants. Note that an inert gas such as nitrogen may be used in combination with the active gas.

[0079] The partial pressure of the active gas is, for example, 10% or more and 100% or less, preferably 30% or more and 100% or less.

[0080] As the active gas, it is preferable to use one or more selected from the group consisting of water vapor gas and oxygen gas, and more preferably to use both water vapor gas and oxygen gas.

[0081] Steam gas tends to have a more sufficient reaction rate and can better control the reaction rate without further reducing production efficiency. Also, by using steam gas, it is possible to more easily obtain a carbonaceous material with developed mesopores and micropores without reducing production efficiency. Therefore, it is likely to preferably produce a carbonaceous material having higher adsorption performance against free residual chlorine, anionic surfactants, etc.

[0082] Also, usually, since the activation reaction is an endothermic reaction, in order to make the activation reaction proceed more efficiently, a certain amount of heat is required. To maintain that amount of heat, it is preferable to use oxygen gas together with steam gas as the active gas. By reacting and burning the volatile gas generated during the activation reaction with oxygen gas, it becomes possible to maintain the amount of heat required for activation. Note that examples of the volatile gas include combustible gases such as hydrogen gas and carbon monoxide gas generated by activating carbides.

[0083] When using steam gas and oxygen gas as the active gas, the gas partial pressure of steam is preferably more than 20.0 vol% and less than 40.0 vol%, and more preferably 25.0 vol% or more and 35.0 vol% or less. The oxygen gas partial pressure is preferably more than 1.0 vol% and less than 5.0 vol%, and more preferably 1.5 vol% or more and 3.5 vol% or less. Note that as other gases, an inert gas such as nitrogen may be included. In that case, the partial pressure of the inert gas is preferably more than 45.0 vol% and less than 89.0 vol%, and more preferably 61.5 vol% or more and 73.5 vol% or less. When their ratios are within the above ranges, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black 5 valence is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the N 2 adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and it is more likely to more easily produce a carbonaceous material.

[0084] When using water vapor gas and oxygen gas as the active gases, their flow rates are preferably 10 liters (L) or more and 300 liters (L) or less in total per minute.

[0085] The activation treatment time can be appropriately set according to conditions such as the raw material, activation temperature, and manufacturing equipment. As the activation time, for example, it is 20 minutes or more and 48 hours or less, preferably 50 minutes or more and 36 hours or less, more preferably 100 minutes or more and 24 hours or less, still more preferably 150 minutes or more and 600 minutes or less, and even more preferably 240 minutes or more and 480 minutes or less. When the activation time is within the above range, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the N 2 adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily manufacture a carbonaceous material.

[0086] The activation treatment temperature is not particularly limited, but is preferably 800 °C or more and 1,250 °C or less, more preferably 850 °C or more and 1,150 °C or less. By performing the activation treatment at such a temperature, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the N 2 adsorption isotherm at -196 °C is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily manufacture a carbonaceous material.

[0087] Examples of the activation device for performing the activation treatment include a rotary kiln as shown in FIGS. 1 and 2. FIG. 1 is a cross-sectional view I and a side view II of the rotary kiln. FIG. 2 is a schematic cross-sectional view for explaining the rotary kiln.

[0088] As shown in FIGS. 1 and 2, a rotary kiln generally includes a tubular body 1 and stirring blades A to F disposed on the inner wall surface of the tubular body 1. The active gas is usually supplied from one side to the other side, that is, in the case of a rotary kiln as shown in FIGS. 1 and 2, it is sent toward the flow direction 2 of the active gas in the tubular body 1.

[0089] The material of the tubular body 1 is not particularly limited as long as it is a material used for a rotary kiln. For example, stainless steel can be mentioned.

[0090] In FIGS. 1 and 2, the number of stirring blades is six, but it can be appropriately adjusted according to the charging amount of the carbide 5 as the raw material. The number of stirring blades is usually 1 or more and 20 or less, preferably 3 or more and 12 or less, and more preferably 5 or more and 10 or less. Also, the stirring blades are preferably installed at equal intervals around the central axis of the tubular body 1. For example, if the number of stirring blades is six, they will be installed every 60° around the central axis of the tubular body 1.

[0091] The height of the stirring blade (the height in the direction from the wall of the tubular body 1 toward the center) can be appropriately set according to the size of the tubular body 1 and the charging amount of the carbide 5, but it is preferable that the stirring blade has a height such that it can be visually recognized without being covered by the carbide 5 charged into the tubular body 1. Specifically, when the stirring blade is located at the bottommost surface of the tubular body 1 (the position of the stirring blade B in the right figure of FIG. 2), the height of the stirring blade is preferably such that it is covered by the carbide 5 by 1 / 2 or more and 2 / 3 or less from the bottommost surface. The height of the stirring blade is more preferably 10% or more and 30% or less with respect to the inner radius of the tubular body 1.

[0092] The thickness of the stirring blade (the thickness in the rotation direction 3 of the tubular body 1) can be appropriately set according to the size of the tubular body 1 and the charging amount of the carbide 5, but it is preferable that the stirring blade has a thickness such that it is not damaged by the carbide 5 charged into the tubular body 1. Specifically, the thickness of the stirring blade is usually 1% or more and 100% or less, preferably 20% or more and 90% or less, and more preferably 30% or more and 95% or less with respect to the wall thickness of the tubular body 1.

[0093] The material of the stirring blades is not particularly limited as long as it is a material used for a rotary kiln. For example, stainless steel can be mentioned.

[0094] By arranging the stirring blades in the tube body 1 in this way, the contact efficiency between the carbide 5 and the active gas tends to be further improved. From this, it tends to be possible to more easily produce a carbonaceous material having a desired specific surface area.

[0095] As shown in FIG. 2, an appropriate amount of the carbide 5 is charged inside the tube body 1. Then, as the tube body 1 rotates in the rotation direction 3 of the tube body, for example, the carbide 5 collected by the stirring blade A is lifted by the stirring blade A, and then mixed while passing over the stirring blade A toward the falling direction 4 of the carbide, and while being contacted with the active gas and activated, it is collected between the stirring blades A and B. By rotating the tube body 1 in this way, the carbide 5 is mixed while passing over the stirring blades A to F, and is efficiently and uniformly contacted with the active gas and activated. From this, it tends to be possible to more easily produce a carbonaceous material having a desired pore size distribution.

[0096] In this way, by using a rotary kiln as the activation device, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and the N 2 adsorption isotherm at -196 °C gives a specific surface area determined by the BET method of 1,100 m 2 / g or more and 1,700 m 2 / g or less, and it tends to be possible to more easily produce a carbonaceous material.

[0097] By the above activation step, an activated product is obtained.

[0098] The method for producing a carbonaceous material may include a washing step and / or a drying step, etc., in which the activated product is subjected to a washing treatment and / or a drying treatment, etc., after the activation step. The conditions in these steps are not particularly limited, and known conditions can be adopted. Also, the following washing step and drying step may be referred to.

[0099] (Washing Process) The carbonaceous material is preferably obtained through a washing process of washing the activated product obtained in the activation process. More preferably, the washing is water washing. By undergoing such a washing process, the iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black pentavalent is 1.0 g / L or more and 6.0 g / L or less, and the N 2 adsorption isotherm at -196 °C, the specific surface area determined by the BET method is 1,100 m 2 / g or more and 1,700 m 2 / g or less, and there is a tendency to more easily produce a carbonaceous material.

[0100] The temperature and time in the washing may be appropriately adjusted so that the target carbonaceous material can be obtained.

[0101] (Drying Process) The carbonaceous material is preferably obtained through a drying process of drying the washed product obtained in the washing process.

[0102] The drying method is not particularly limited, and known drying methods such as natural drying, heating drying, and hot air drying can be used. As the drying method, a method of heating and / or reducing pressure is preferred. As the method of drying by heating, from the viewpoint of no drying unevenness and stable drying, the drying method by hot air is preferred. In the drying process, it is preferable to dry until the moisture content of the carbonaceous material becomes 20.0 mass% or less, and more preferably until it becomes 10.0 mass% or less.

[0103] Examples of the heating method include heating methods using a stationary type constant temperature dryer; a stationary type hot air dryer; a vacuum dryer; a rotary evaporator; a conical dryer, a Nauta dryer, and other mixed dryers. The heating temperature may be a temperature at which the carbonaceous material hardens and does not melt, for example, 40 °C or more and 300 °C or less is preferred.

[0104] Examples of the decompression method include a decompression method using an oil pump, an oil-free pump, an aspirator, etc. The pressure in the decompression method is usually 0.00001 MPa or more and 0.05 MPa or less.

[0105] The drying time depends on the drying temperature, but is usually about 1 minute or more and 20 hours or less.

[0106] The carbonaceous material thus obtained may be used as it is, or, if necessary, by a known method, the particle size may be adjusted by crushing, pulverizing, and classifying; for example, purification by additional washing using water, an organic solvent, an aqueous acid solution, and an aqueous alkali solution; durability imparting and structure adjustment using additional heat treatment may be carried out to obtain a carbonaceous material.

[0107] It is preferable to adjust the particle size of the carbonaceous material so that its particle size (50% particle diameter of the cumulative distribution based on volume, D50) is 20 μm or more and 500 μm or less. When the particle size of the carbonaceous material is within the above range, the carbonaceous material can be suitably used for, for example, the applications exemplified below.

[0108] [Applications] The carbonaceous material can be suitably used for various applications for removing, adsorbing, concentrating, and recovering free residual chlorine, anionic surfactants, etc. Such applications may be applications that appropriately combine the operations of removal, adsorption, concentration, and recovery. Examples of such applications include water purification equipment such as adsorption filters, water purifier cartridges, water purifiers, packed towers, household drinking water treatment, water treatment and purification in industrial processes, and wastewater treatment.

[0109] The carbonaceous material is suitably used for removing free residual chlorine and anionic surfactants, etc.

[0110] [Method for removing free residual chlorine and anionic surfactants, etc.] The method for removing free residual chlorine and anionic surfactants, etc. includes a removal step of removing free residual chlorine and anionic surfactants, etc. using a carbonaceous material. The free residual chlorine is removed, for example, by being decomposed on the surface of the carbonaceous material. The anionic surfactants, etc. are removed, for example, by being adsorbed onto the carbonaceous material. In these removal methods, in addition to using the carbonaceous material of the present embodiment as the carbonaceous material, it may have the same steps as known methods for removing free residual chlorine and anionic surfactants, etc., adsorption methods, concentration methods, and recovery methods, etc. 〔Adsorption Filter〕 The adsorption filter of the present embodiment contains the carbonaceous material of the present embodiment. Also, the adsorption filter is preferably for a water purifier.

[0111] Since the adsorption filter contains a carbonaceous material, it is possible to achieve high-level removal performance of both free residual chlorine and anionic surfactants, etc. at the same time. Therefore, for example, by installing the adsorption filter in a water purifier, it is possible to efficiently remove free residual chlorine and anionic surfactants, etc. contained in water.

[0112] The adsorption filter preferably contains a carbonaceous material and a fibrous binder.

[0113] Examples of the fibrous binder include those that can entangle and shape the carbonaceous material by fibrillation. Such fibrous binders may be synthetic products or natural products. Examples of the fibrous binder include acrylic fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, cellulose fiber, nylon fiber, aramid fiber, and pulp.

[0114] The fibrous binder may be used alone or in an appropriate combination of two or more. The fibrous binder is preferably polyacrylonitrile fiber and / or pulp. By using these fibrous binders, the density of the adsorption filter and the strength of the adsorption filter can be further increased, and performance degradation can be suppressed.

[0115] Since the adsorption filter can achieve a higher level of compatibility in removing free residual chlorine and anionic surfactants, etc., the adsorption filter contains a fibrous binder preferably in an amount of 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the carbonaceous material. The lower limit is usually 0.01 parts by mass or more. In addition, when the adsorption filter contains other functional components described later, "based on 100 parts by mass of the carbonaceous material" regarding the filter composition may be read as "based on a total of 100 parts by mass of the carbonaceous material and other functional components" and applied accordingly.

[0116] The adsorption filter may contain other functional components as long as the effects of the present embodiment are not inhibited. Examples of such other functional components include lead adsorbents such as titanosilicate and zeolite-based powders capable of adsorbing and removing soluble lead; ion exchange resins; chelating resins; various adsorbents containing silver ions and / or silver compounds for imparting antibacterial properties, etc.

[0117] When water is passed through the adsorption filter, the water passage is usually carried out at a space velocity (SV) of 300 / hr or more and 6500 / hr or less so that the pressure loss does not become extremely large. The performance of the adsorption filter can be confirmed by plotting the relationship between each removal rate calculated from the concentrations of the substances to be removed in the raw water and permeated water, the amount of water (L) flowed from the start of water passage, and the ratio of the cumulative permeated water volume (L / mL) to the volume (mL) of the water purification cartridge.

[0118] (Filtration capacity) In this specification, the filtration capacity is defined as the amount of water (L) that can be passed through until the removal rate of the target substance to be removed reaches 80% when water is passed through the adsorption filter. The water passage is carried out at a space velocity (SV) of 3000 / hr.

[0119] (Free residual chlorine filtration capacity) The free residual chlorine filtration capacity can be measured using the free residual chlorine removal performance test in the test method specified in "Test Method for Domestic Water Purifiers" in JIS S3201:2019. Specifically, the test water is set to a free residual chlorine concentration of 2.0 ± 0.4 (mg / L) and a water temperature of 20°C ± 3°C, and passed through the carbonaceous material or adsorption filter. The test raw water and the filtered water are analyzed by the DPD absorptiometric method using a spectrophotometer and DPD reagent (diethyl-p-phenylenediamine), and the removal rate (%) is obtained from the test raw water concentration (mg / L) and the filtered water concentration (mg / L), and the filtration capacity can be obtained by plotting the removal rate (%) against the integrated water throughput (L). Since the adsorption filter of this embodiment is excellent in filtration capacity, usually, the free residual chlorine filtration capacity measured in accordance with JIS S3201:2019 is 17.0 L or more per 1 cm of the carbonaceous material 3 Preferably 20.0 L or more, more preferably 23.0 L or more.

[0120] (Anionic surfactant filtration capacity) The anionic surfactant filtration capacity can be measured using the anionic surfactant removal performance test in the test method specified in "Test Method for Domestic Water Purifiers" in JIS S3201:2019. Specifically, the test water is set to an anionic surfactant concentration of 0.20 ± 0.04 (mg / L) and a water temperature of 20°C ± 3°C, and passed through the carbonaceous material or adsorption filter. The test raw water and the filtered water are analyzed by solid phase extraction-high performance liquid chromatography, and the removal rate (%) is obtained from the test raw water concentration (mg / L) and the filtered water concentration (mg / L), and the filtration capacity can be obtained by plotting the removal rate (%) against the integrated water throughput (L). Since the adsorption filter of this embodiment is excellent in filtration capacity, the adsorption filter usually has an anionic surfactant filtration capacity measured in accordance with JIS S3201:2019 of 55.0 L or more per 1 cm of the carbonaceous material 3 Preferably 65.0 L or more, more preferably 75.0 L or more.

[0121] 〔Water purifier cartridge〕 The water purifier cartridge of this embodiment contains the carbonaceous material of this embodiment. The water purifier cartridge may have the same configuration as a known water purifier cartridge except that it contains the carbonaceous material of this embodiment. By containing the carbonaceous material, the water purifier cartridge can efficiently remove free residual chlorine and anionic surfactants contained in water. Therefore, for example, by installing the water purifier cartridge in a household water purifier, it is possible to efficiently remove various harmful substances described in the "Test Method for Household Water Purifiers" in JIS S3201:2019, particularly free residual chlorine and anionic surfactants.

[0122] Examples of the water purification cartridge include a cartridge filled with a carbonaceous material in a housing and a cartridge filled with an adsorption filter in a housing. In addition to the carbonaceous material or adsorption filter according to this embodiment, the water purification cartridge may also include a combination of a known non-woven fabric filter, various adsorbents, mineral additives, ceramic filter materials, and hollow fiber membranes.

[0123] [Device] The device includes a carbonaceous material. The device may have the same configuration as a known device except that the carbonaceous material of this embodiment is used as the carbonaceous material.

[0124] The functions of the carbonaceous material are utilized by the device containing the same. The device is preferably a processing device. In the present specification, the "processing device" refers to a device that can remove, adsorb, concentrate, and recover free residual chlorine, anionic surfactants, etc. contained in objects to be processed such as wastewater, waste liquid, and oil, by the carbonaceous material of the present embodiment, and is not particularly limited. Such a processing device may be a device that appropriately combines operations of removal, adsorption, concentration, and recovery. Examples of such a processing device include devices containing an adsorption filter, column, tank or bath, tube, water purifier cartridge, cylinder, and sheet (hereinafter, also simply referred to as "filter, etc. containing carbonaceous material") containing carbonaceous material, packed towers, and filtration devices, adsorption devices, and concentration devices such as water purifiers. Examples of such devices include household drinking water treatment devices, water treatment devices and purification devices in industrial processes, and wastewater treatment devices.

[0125] The device includes, for example, an adsorption section for bringing free residual chlorine, anionic surfactants, etc. into contact with the carbonaceous material. In the adsorption section, an adsorbent other than the carbonaceous material according to the present embodiment may be included as necessary. Examples of such an adsorbent include activated carbon, zeolite, silica gel, activated alumina, non-woven fabric, and porous organic compounds other than the carbonaceous material according to the present embodiment.

[0126] Examples of the filtration device include a water purifier, a cartridge type filtration device, a membrane treatment device, and an ultrafiltration membrane device containing carbonaceous material.

[0127] The processing device may be provided with other adsorption filters together with an adsorption filter, etc. containing carbonaceous material. Examples of such other adsorption filters include metal filters made of stainless steel, aluminum, bronze, copper, titanium, nickel, etc.; resin filters made of polypropylene, polyvinyl chloride, polyvinylidene chloride, polyethylene, polyamide, fluororesin, etc.

[0128] Further, the processing apparatus may be batch type or continuous type, and the carbonaceous material can be used in either mode.

[0129] 〔Water purifier〕 The water purifier of this embodiment includes the carbonaceous material of this embodiment.

[0130] The water purifier is manufactured using a carbonaceous material or an adsorption filter. By including an adsorption filter, the water purifier can achieve high-level removal performance for both free residual chlorine and anionic surfactants, etc. Therefore, the water purifier can be suitably used for faucet devices and kitchens.

[0131] The water purifier is provided with a water purification cartridge, and it is preferable that the water purification cartridge is configured using the carbonaceous material or the adsorption filter according to this embodiment. As the configuration of such a water purification cartridge, the above-mentioned water purifier cartridge may be referred to.

[0132] (Water purification method) The water purification method is not particularly limited, but it is preferable to use the water purifier of this embodiment. The water purification method has no particular limitation, and known methods can be adopted.

[0133] 〔Water purification equipment〕 The water purification equipment of this embodiment includes the carbonaceous material of this embodiment. By including the carbonaceous material, the water purification equipment can achieve high-level removal performance for both free residual chlorine and anionic surfactants, etc.

[0134] Examples of the water purification equipment include water purification equipment such as pure water production devices, ultrapure water devices, and water purification plants, wastewater treatment equipment in general industry, and water purification equipment for pharmaceuticals and foods.

Examples

[0135] Hereinafter, examples and comparative examples will be shown to more specifically explain the present invention, but the present invention is not limited by these examples in any way.

[0136] 〔Evaluation Method〕

[0137] (1) Iodine adsorption amount (iodine adsorption performance) The iodine adsorption amount (mg / g) of the carbonaceous material was measured and calculated. Specifically, the measurement of the iodine adsorption amount was carried out in accordance with JIS K 1474 (2014). That is, first, in accordance with JIS Z 8801-1, the carbonaceous material was pulverized until it passed through a 45 μm sieve by 90% or more, and then dried in a constant temperature dryer at 115 °C (DVS402 (trade name) manufactured by Yamato Scientific Co., Ltd.) for 3 hours. Thereafter, it was allowed to cool to room temperature in a desiccator using silica gel as a desiccant, and the carbonaceous material after cooling was obtained.

[0138] On the other hand, 25.0 g of potassium iodide (manufactured by Fujifilm Wako Pure Chemical Corporation) and 13.0 g of iodine (manufactured by Fujifilm Wako Pure Chemical Corporation) were dissolved in about 1 L of distilled water to prepare an iodine solution. The iodine solution was titrated with a 0.1 mol / L sodium thiosulfate solution (manufactured by Fujifilm Wako Pure Chemical Corporation), and an appropriate amount of distilled water was added to the iodine solution to prepare a 0.05 mol / L iodine solution.

[0139] Next, an arbitrary amount of the carbonaceous material after the above cooling (the amount at which the iodine residual concentration in the supernatant of the following filtrate is approximately 2.5 g / L) was weighed and placed in a 100 mL Erlenmeyer flask with a stopper, and then 50 mL of the above 0.05 mol / L iodine solution was added in full volume with a pipette. At room temperature (20 °C or higher and 30 °C or lower), using a shaker (medium-sized shaker reciprocating shaker NR-10 (trade name) manufactured by Taitec Co., Ltd.), it was shaken at 200 times / min for 15 minutes to adsorb iodine to the carbonaceous material and obtain a mixed solution. Thereafter, the mixed solution was filtered using a cellulose mixed ester membrane filter (A045A025A (trade name) manufactured by Advantec Toyo Co., Ltd.) to obtain a filtrate. 10 mL of the supernatant of the filtrate was collected in full volume with a pipette and titrated with a 0.1 mol / L sodium thiosulfate solution (manufactured by Fujifilm Wako Pure Chemical Corporation, factor: 1.000), and the iodine residual concentration was calculated by the following formula (I). Iodine residual concentration (g / L) = Amount (mL) of 0.1 mol / L sodium thiosulfate solution used in titration × Factor of 0.1 mol / L sodium thiosulfate solution × 12.69 / 10 ··· (I)

[0140] The iodine adsorption amount per 1 g of the carbonaceous material was calculated by the following formula (II). Iodine adsorption amount per 1 g of carbonaceous material = (10 × Factor of 0.05 mol / L iodine solution - Amount (mL) of 0.1 mol / L sodium thiosulfate solution used in titration × Factor of 0.1 mol / L sodium thiosulfate solution) × 12.69 × 5 / Mass (g) of carbonaceous material ··· (II)

[0141] Note that the factor of the 0.05 mol / L iodine solution was calculated by formula (III). Factor of 0.05 mol / L iodine solution = (Amount (mL) of 0.1 mol / L sodium thiosulfate solution used in titration × Factor of 0.1 mol / L sodium thiosulfate solution) / 10 ··· (III)

[0142] From the Freundlich adsorption isotherm, an adsorption isotherm was created with the iodine residual concentration on the horizontal axis and the iodine adsorption amount per 1 g of the carbonaceous material on the vertical axis, and the iodine adsorption amount per 1 g of the carbonaceous material (mg / g) at an iodine residual concentration of 2.5 g / L was calculated. That iodine adsorption amount was taken as the iodine adsorption performance.

[0143] (2) Reactive Black 5 valence The reactive black 5 valence (g / L) of the carbonaceous material was measured. Specifically, first, the carbonaceous material was pulverized so that the volume-based cumulative distribution 50% particle size (D50) was about 10.0 μm or less, and dried in a constant-temperature dryer (DVS402 (trade name) manufactured by Yamato Scientific Co., Ltd.) at 115 °C for 3 hours. Then, it was allowed to cool to room temperature in a desiccator using silica gel as a desiccant, and the carbonaceous material after cooling was obtained.

[0144] On one hand, a test solution A containing a phosphate buffer and reactive black 5 (manufactured by Sigma-Aldrich) was prepared as follows. That is, first, 7.26 g of potassium dihydrogen phosphate (manufactured by Fujifilm Wako Pure Chemical Corporation) and 28.66 g of disodium hydrogen phosphate dodecahydrate (manufactured by Fujifilm Wako Pure Chemical Corporation) were dissolved in 2 L of distilled water to prepare a phosphate buffer (pH: 7.0). Then, for 1 L of the obtained phosphate buffer, reactive black 5 was added in the range of about 0.5 g or more and 1.2 g or less to prepare test solution A. At that time, the amount of reactive black 5 was adjusted as follows. That is, the amount of reactive black 5 added to 1 L of the phosphate buffer was appropriately adjusted so that the absorbance of the solution obtained by diluting the obtained test solution A 20-fold with distilled water was in the range of 1.18 or more and 1.23 or less. The absorbance was the absorbance at a wavelength of 594 nm and was measured with an ultraviolet-visible spectrophotometer (double-beam spectrophotometer U-2910 (trade name) manufactured by Hitachi High-Tech Corporation) using a glass cell with an optical path length of 10 mm. In addition, the solution obtained by diluting the test solution A obtained as described above 20-fold was used as test solution B, and test solution B was used for the following absorbance measurement.

[0145] Next, an arbitrary mass (the amount at which the residual rate of reactive black 5 contained in the filtrate is about 10% according to the following formula (V)) of the above-mentioned carbonaceous material after cooling was taken into a 100 mL conical flask with a stopper, and the carbonaceous material was added to 50 mL of test solution A prepared above. Using a shaking thermostatic bath (water bath shaker MM-10 (trade name) manufactured by Taitec Corporation), it was shaken in a water bath at 40°C at a speed of 150 times / min for 5 hours to obtain a mixed solution. Then, the mixed solution was filtered using a membrane filter (DISMIC (registered trademark) 25HP045AN (trade name) manufactured by Advantec Toyo Co., Ltd.) to obtain a filtrate.

[0146] Using a glass cell with an optical path length of 10 mm, the absorbances of the obtained test solution B and the filtrate were measured at a wavelength of 594 nm each with an ultraviolet-visible spectrophotometer (double-beam spectrophotometer U-2910 (trade name) manufactured by Hitachi High-Tech Corporation). Using these absorbances, the adsorption amount of reactive black 5 per 1 g of the carbonaceous material (hereinafter simply referred to as "RB5 adsorption amount per 1 g of carbonaceous material ( / g)") was calculated by the following formula (IV). RB5 adsorption amount per 1 g of carbonaceous material ( / g) = (absorbance of test solution B at a wavelength of 594 nm × 20 - absorbance of filtrate at a wavelength of 594 nm) / mass of carbonaceous material (g) ··· (IV)

[0147] Also, the residual rate of reactive black 5 contained in the filtrate (hereinafter simply referred to as "RB5 residual rate (%)") was calculated by the following formula (V). RB5 residual rate (%) = (absorbance of filtrate at a wavelength of 594 nm / absorbance of test solution B at a wavelength of 594 nm × 20) × 100 ··· (V)

[0148] Next, a power approximation curve was created using the RB5 residual rate (%) on the horizontal axis and the RB5 adsorption amount per 1 g of the carbonaceous material ( / g) on the vertical axis. Using the power approximation formula, the adsorption amount of reactive black 5 at an RB5 residual rate of 1% (hereinafter simply referred to as "RB5 adsorption amount at an RB5 residual rate of 1% ( / g)") was obtained, and the reactive black 5 valence (g / L) was calculated by formula (VI). Reactive black 5 valence (g / L) = (absorbance of test solution B at a wavelength of 594 nm × 20 × 0.99 / RB5 adsorption amount at an RB5 residual rate of 1% ( / g)) / 0.05 (L) ··· (VI) Note that 0.05 (L) in formula (VI) is the amount of the test solution.

[0149] (3) BET specific surface area - The specific surface area (m 2 / g) of the carbonaceous material determined by the BET method from the N 2 adsorption isotherm at -196 °C was measured. Specifically, the BET specific surface area (m2 / g) was determined as follows. First, using a specific surface area / pore size distribution measuring device (BELSORP (registered trademark)-miniII (product name) manufactured by MicrotracBEL Corp.), the carbonaceous material was heated at 250 °C for 3 hours under reduced pressure (vacuum degree: 0.1 kPa or less), and then the nitrogen adsorption isotherm of the carbonaceous material at -196 °C was measured. Using the obtained nitrogen adsorption isotherm, by BET analysis, a straight line in the region of relative pressure P / P0 = 0.01 or more and 0.10 or less was obtained from the obtained curve by the multi-point method, and the BET specific surface area was calculated from this straight line.

[0150] (4) Mesopore ratio · Measurement of nitrogen gas adsorption isotherm using BELSORP-MAX Using a specific surface area / pore size distribution measuring device (BELSORP (registered trademark)-MAX (product name) manufactured by MicrotracBEL Corp.), after heating the carbonaceous material at 300 °C for 3 hours under vacuum conditions, the nitrogen gas adsorption isotherm under the condition of a temperature of 77 K was measured.

[0151] · Measurement of pore volume with pore diameter of 1.00 nm or less The pore volume (cm 3 / g) of pores with a pore diameter of 1.00 nm or less among the micropores calculated by the QSDFT method per 1 g of the carbonaceous material from the nitrogen adsorption isotherm was calculated as follows. Specifically, using the values of the nitrogen gas adsorption isotherm obtained by the above-mentioned "Measurement of nitrogen gas adsorption isotherm using BELSORP-MAX", by applying N 2 at 77K carbon[slit pore / cyl.pore (QSDFT Ads.model)] to calculate the pore size distribution, the pore volume (cm 3 / g) of pores with a pore diameter of 1.00 nm or less was calculated.

[0152] · Measurement of mesopore volume The mesopore volume (cm 2 of the carbonaceous material determined by the BJH method from the adsorption isotherm of N 3)(g) was measured. Specifically, using the nitrogen adsorption isotherm used in the above measurement of the BET specific surface area, a curve was obtained by BJH analysis in the region where the relative pressure P / P0 is 0.385 or more and 0.99 or less. From the obtained curve, the cumulative pore volume for each pore diameter was calculated, and the cumulative pore volume up to a pore diameter of 50.0 nm was subtracted from the cumulative pore volume up to a pore diameter of 2.0 nm to calculate the pore volume of mesopores with a pore diameter of 2.0 nm or more and 50.0 nm or less.

[0153] ·Calculation of mesopore ratio The mesopore ratio of the carbonaceous material was calculated. Specifically, the mesopore ratio (A / B) of the carbonaceous material is the pore volume (cm 3 / g) (A) with a pore diameter of 1.00 nm or less and the pore volume (cm 3 / g) (B) of mesopores, and was calculated from the following formula (VII). Mesopore ratio (A / B) of carbonaceous material = Pore volume (A) with a pore diameter of 1.00 nm or less / Pore volume (B) of mesopores ··· (VII)

[0154] (5) Ratio of mesopores ·BJH specific surface area - The specific surface area (m 2 / g) of the carbonaceous material determined by the BJH method from the adsorption isotherm of N 2 at -196 °C was measured. The BJH specific surface area is the specific surface area determined from the pore volume and pore diameter of the carbonaceous material measured based on the BJH method. Specifically, using the nitrogen adsorption isotherm used in the above calculation of the BET specific surface area, a curve was obtained by BJH analysis in the region where the relative pressure P / P0 is 0.385 or more and 0.99 or less. From the obtained curve, the pore volume of mesopores was calculated for each pore diameter in the range of 2.0 nm or more and 50.0 nm or less, and the specific surface area was calculated using these values and the following formula (VIII). The BJH specific surface area of the carbonaceous material was calculated by adding up the specific surface areas for each obtained pore diameter. Ap = 2 × Vp / (rp × 10 7 ) × 0.0001 ··· (VIII) In formula (VIII), Ap is the specific surface area (m2 / g) indicates, and Vp represents the pore volume (cm 3 / g), and rp represents the pore diameter (nm).

[0155] ·Calculation of the proportion of mesopores The proportion (%) of mesopores in the carbonaceous material was calculated. Specifically, the proportion (%) of mesopores in the carbonaceous material was calculated from the BET specific surface area (m 2 / g) and the BJH specific surface area (m 2 / g) obtained above using the following formula (IX). Proportion of mesopores = BJH specific surface area / BET specific surface area × 100 ··· (IX)

[0156] (6) Pore volume of mesopores The pore volume (cm 2 of mesopores in the carbonaceous material determined by the BJH method from the N 3 adsorption isotherm at -196°C was measured and calculated by the "Measurement of pore volume of mesopores" in the above mesopore ratio.

[0157] (7) Total pore volume The total pore volume (cm 2 of the carbonaceous material determined by the BJH method from the N 3 adsorption isotherm at -196°C was measured. Specifically, using the nitrogen adsorption isotherm used in the above calculation of the BET specific surface area, a curve was obtained by BJH analysis in the region where the relative pressure P / P0 is 0.385 or more and 0.99 or less. From the obtained curve, the cumulative pore volume with a pore diameter of 1.2 nm or more and 97.4 nm or less was calculated, and this value was taken as the total pore volume of the carbonaceous material.

[0158] (8) Packing density The packing density (g / mL) of the carbonaceous material measured by the tapping method was calculated. Specifically, first, the carbonaceous material was dried in a constant-temperature dryer at 115°C (DVS402 (trade name) manufactured by Yamato Scientific Co., Ltd.) for 3 hours. Then, it was allowed to cool to room temperature in a desiccator using silica gel as a desiccant, and the carbonaceous material after cooling was obtained.

[0159] Weighed 5.0 g of the carbonaceous material after the above-mentioned cooling, roughly divided it into three equal parts, and put a part (about 1 / 3 of the amount) of the carbonaceous material into a 150 mL graduated cylinder (inner diameter: 31 mm, manufactured by Tsutsui Rikagaku Kikai Co., Ltd.). A rubber stopper was attached to the graduated cylinder and set on an automatic tapping device (powder reduction degree measuring machine TPM-3A type (trade name) manufactured by Tsutsui Rikagaku Kikai Co., Ltd.), and tapping was performed for 1 minute at a vibration amplitude of 45 mm and a vibration frequency of 35 - 36 times / min. After the tapping was completed, another part (about 1 / 3 of the amount) of the carbonaceous material from the previously divided three equal parts was further added to the graduated cylinder, a rubber stopper was attached, and tapping was performed for 1 minute under the same conditions as above. Then, the last part (about 1 / 3 of the amount) of the carbonaceous material from the previously divided three equal parts was further added to the graduated cylinder, a rubber stopper was attached, and tapping was performed for 30 minutes under the same conditions as above.

[0160] After the tapping was completed, the rubber stopper was removed, and the upper surface of the sample in the graduated cylinder was flattened with a spatula or the like, and the sample volume (mL) was visually measured from the scale of the graduated cylinder. Using the measured sample volume, the packing density measured by the tapping method was calculated according to the following formula (X). Packing density (g / mL) = mass of carbonaceous material (g) / measured sample volume (mL) ··· (X)

[0161] (9) Free residual chlorine filtration capacity Under the test conditions of the free residual chlorine filtration capacity test specified in "Test Methods for Domestic Water Purifiers" in JIS S3201:2019, the free residual chlorine filtration capacity (L / cm 3 ) of the carbonaceous material was calculated. Note that for the filtration capacity test, a downward-flow water column made of Duracon (registered trademark) (polyacetal) (self-designed and machined product, inner diameter φ50 mm, and height 60 mm) was filled with 50 cm of the carbonaceous material 3 and the test was carried out at a filtration flow rate of 3.0 L / min.

[0162] (10) Anionic surfactant filtration capacity Under the test conditions of the anionic surfactant filtration capacity test specified in the "Test Method for Household Water Purifiers" in JIS S3201:2019, the anionic surfactant filtration capacity (L / cm 3 ) of the carbonaceous material was calculated. In addition, for the filtration capacity test, a downward-flow water column made of Duracon (registered trademark) (polyacetal) (self-designed and machined product, inner diameter φ50 mm, and height 60 mm) was filled with 50 cm of the carbonaceous material 3 and the test was carried out at a filtration flow rate of 3.0 L / min.

[0163] [Example 1] (Carbonization process) The carbonization of the coconut shell produced in the Philippines was carried out at a temperature of 600 °C for about 2 hours to obtain a carbide.

[0164] (Activation treatment) The obtained carbide was introduced into a rotary kiln equipped with stirring blades in a furnace heated to 900 °C as shown in FIGS. 1 and 2 at about 0.06 times the volume of the rotary kiln of 1 m 3 . Then, while rotating the kiln at a rotational speed of 3.0 rpm, a gas (30.0 vol% water vapor, 2.5 vol% oxygen, and 67.5 vol% nitrogen) was introduced into the kiln, and an activation treatment was carried out for 260 minutes to obtain an activated product.

[0165] In the used rotary kiln, six stirring blades were installed at 60° intervals around the central axis of the pipe body. Also, the height of the stirring blade was 15% or more and 25% or less with respect to the inner radius of the pipe body, and the thickness of the stirring blade was 40% or more and 80% or less with respect to the thickness of the pipe body.

[0166] (Washing process and drying process, etc.) The obtained activated product was thoroughly washed with water and dried to obtain a dried product. Subsequently, the obtained dried product was pulverized, and using a wire mesh for standard sieves defined in JIS Z8801-1:2019, the fraction passing through a 60-mesh sieve (aperture size: 233 μm, Tokyo Screen Co., Ltd.) and retained on a 140-mesh sieve (aperture size: 106 μm, Tokyo Screen Co., Ltd.) was adjusted so that the particle size (50% particle diameter of the cumulative distribution based on volume, D50) became 210 μm, thereby obtaining a pulverized carbonaceous material 1 which is activated carbon.

[0167] [Example 2] In the activation step, a pulverized carbonaceous material 2 which is activated carbon was obtained in the same manner as in Example 1, except that the activation treatment was performed for 390 minutes.

[0168] [Example 3] In the activation step, a pulverized carbonaceous material 3 which is activated carbon was obtained in the same manner as in Example 1, except that the activation treatment was performed for 420 minutes.

[0169] [Comparative Example 1] (Carbonization step) The coconut shells produced in the Philippines were carbonized at a temperature of 600 °C for about 2 hours to obtain a carbide.

[0170] (Activation treatment) The obtained carbide was introduced into a rotary kiln equipped with stirring blades in a furnace heated to 900 °C as shown in FIGS. 1 and 2, at a rate of about 0.06 times the volume of the rotary kiln (1 m 3 ). Then, while rotating the kiln at a rotational speed of 3.0 rpm, a gas (40.0 vol% steam, 5.0 vol% oxygen, and 55.0 vol% nitrogen) was introduced into the kiln, and an activation treatment was performed for 130 minutes to obtain an activated product.

[0171] In the used rotary kiln, six stirring blades were installed at 60° intervals around the central axis of the pipe body. Also, the height of the stirring blades was 15% or more and 25% or less with respect to the inner radius of the pipe body, and the thickness of the stirring blades was 40% or more and 80% or less with respect to the thickness of the pipe body.

[0172] (Washing process, drying process, etc.) The obtained activated product was thoroughly washed with water and dried to obtain a dried product. Then, the obtained dried product was pulverized, and using a wire mesh for standard sieves specified in JIS Z8801-1:2019, the fraction passing through a 140-mesh sieve (aperture size: 106 μm, Tokyo Screen Co., Ltd.) and retained on a 60-mesh sieve (aperture size: 233 μm, Tokyo Screen Co., Ltd.) was adjusted so that the particle size (50% particle diameter of the cumulative distribution based on volume, D50) became 210 μm, thereby obtaining a pulverized carbonaceous material 4 which is activated carbon.

[0173] 〔Comparative Example 2〕 In the activation process, a pulverized carbonaceous material 5 which is activated carbon was obtained in the same manner as in Comparative Example 1, except that the activation treatment was carried out for 200 minutes.

[0174] 〔Comparative Example 3〕 In the activation process, a pulverized carbonaceous material 6 which is activated carbon was obtained in the same manner as in Comparative Example 1, except that the activation treatment was carried out for 250 minutes.

[0175] 〔Comparative Example 4〕 In the activation process, a pulverized carbonaceous material 7 which is activated carbon was obtained in the same manner as in Comparative Example 1, except that the activation treatment was carried out for 280 minutes.

[0176] 〔Comparative Example 5〕 (Carbonization process) Carbide 1 was obtained by carbonizing coconut shells produced in the Philippines at a temperature of 600 °C for about 2 hours. The obtained carbide 1 was pulverized so that the average particle size became 20 μm or more and 80 μm or less to obtain a pulverized product. Then, into a mixer (manufactured by Universe Co., Ltd., high-speed mixer DH-5 (trade name)), 1000 g of the obtained pulverized product, an aqueous calcium chloride solution prepared by dissolving 25 g of calcium chloride (special grade reagent, manufactured by FUJIFILM Wako Pure Chemical Corporation) in 57 g of water, 250 g of hard pitch (softening point: 110 °C, PK-M flakes (trade name) manufactured by JFE Chemical Corporation), 80 g of creosote (creosote oil (naphthalene B) (trade name) manufactured by JFE Chemical Corporation), 15 g of lignin (Sun Extract (registered trademark) M (trade name) manufactured by Nippon Paper Industries Co., Ltd.), and 73 g of water were charged and mixed for 25 minutes to obtain a mixture. Then, the obtained mixture was charged into an extrusion granulator (Disk Pelletizer (trade name) manufactured by Fuji Paudal Co., Ltd.) with a pore diameter of 4.0 mm and extrusion molded to obtain a granulated product. Carbide 2 was obtained by carbonizing the obtained granulated product at a temperature of 650 °C for about 30 minutes.

[0177] (Activation treatment) The obtained carbide 2 was charged into a rotary kiln equipped with stirring blades in a furnace heated to 900 °C as shown in FIGS. 1 and 2, at about 0.06 times the volume of the rotary kiln of 1 m 3 . Then, while rotating the kiln at a rotation speed of 3.0 rpm, a gas (40.0 vol% water vapor, 5.0 vol% oxygen, and 55.0 vol% nitrogen) was introduced into the kiln, and an activation treatment was performed for 150 minutes to obtain an activated product.

[0178] In the rotary kiln used, six stirring blades were installed at 60° intervals around the central axis of the pipe body. Also, the height of the stirring blade was 15% or more and 25% or less with respect to the inner radius of the pipe body, and the thickness of the stirring blade was 40% or more and 80% or less with respect to the thickness of the pipe body.

[0179] (Washing process and drying process, etc.) The obtained activated product was washed with dilute hydrochloric acid, and then thoroughly washed and dried with water to remove the remaining hydrochloric acid, obtaining a dried product. Subsequently, the obtained dried product was pulverized, and using a wire mesh for standard sieves specified in JIS Z8801-1:2019, the fraction passing through a 60-mesh sieve (aperture size: 233 μm, Tokyo Screen Co., Ltd.) and retained on a 140-mesh sieve (aperture size: 106 μm, Tokyo Screen Co., Ltd.) was adjusted so that the particle size (50% particle diameter of the cumulative distribution based on volume, D50) became 210 μm, thereby obtaining a pulverized carbonaceous material 8 which is activated carbon.

[0180]

Table 1

Industrial Applicability

[0181] The carbonaceous material of the present embodiment can be suitably used for various applications such as removing, adsorbing, concentrating, and recovering free residual chlorine decomposable on the surface of the carbonaceous material and anionic surfactants with relatively large molecular sizes.

Explanation of Reference Numerals

[0182] A, B, C, D, E, F... stirring blades, 1... tube body, 2... flow direction of active gas, 3... rotation direction of tube body, 4... falling direction of carbide, 5... carbide.

Claims

1. The iodine adsorption amount is 1,300 mg / g or more and 1,800 mg / g or less, the reactive black 5 valence is 1.0 g / L or more and 6.0 g / L or less, and the specific surface area determined by the BET method from the adsorption isotherm of N ２ at -196 °C is 1,100 m ２ / g or more and 1,700 m ２ / g or less, a carbonaceous material.

2. The ratio (A / B) of the pore volume (A) of 1.00 nm or less calculated by the QSDFT method per 1 g of the carbonaceous material from the nitrogen adsorption isotherm to the pore volume (B) of the mesopores determined by the BJH method from the adsorption isotherm of N at -196°C is 1.0 or more and 4.0 or less. The carbonaceous material according to claim 1. ２ ​

3. The carbonaceous material according to claim 1, wherein the ratio of mesopores is 4.8% or more and 15.0% or less.

4. - The pore volume of mesopores determined by the BJH method from the adsorption isotherm of N at -196 °C is 0.06 cm ２ / g or more and 0.30 cm ３ / g or less. The carbonaceous material according to claim 1. ３ ​

5. - The total pore volume determined by the BJH method from the adsorption isotherm of N at -196 °C is 0.25 cm ２ / g or more and 1.00 cm ３ / g or less. The carbonaceous material according to claim 1. ３ ​

6. The carbonaceous material according to claim 1, wherein the bulk density measured by the tapping method is 0.30 g / mL or more and 0.50 g / mL or less.

7. The carbonaceous material according to any one of claims 1 to 6, which is used for removing at least free residual chlorine and anionic surfactant in water.

8. A carbonization step of carbonizing a raw material to obtain a carbide, and An activation step of subjecting the carbide to an activation treatment to obtain an activated product, the method for producing a carbonaceous material according to any one of claims 1 to 6.

9. The production method according to claim 8, further comprising a washing step of washing the activated product.

10. The production method according to claim 8, wherein the raw material is a coconut shell.

11. An adsorption filter comprising the carbonaceous material according to any one of claims 1 to 6.

12. A water purifier cartridge comprising the carbonaceous material according to any one of claims 1 to 6.

13. A water purifier comprising the carbonaceous material according to any one of claims 1 to 6.

14. A water purification facility comprising the carbonaceous material according to any one of claims 1 to 6.

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