Carbonaceous material and manufacturing method thereof, adsorption filter, water purifier filter element, water purifier and water purification equipment

Abstract

This carbonaceous material has an iodine adsorption amount of 1300 mg / g to 1800 mg / g, an active black 5 value of 1.0 g / L to 6.0 g / L, and a specific surface area of 1100 m2 / g to 1700 m2 / g as determined by the BET method on the basis of an N2 adsorption isotherm at-196 DEG C.

Description

Technical Field

[0001] This invention relates to a carbonaceous material and its manufacturing method, an adsorption filter, a water purifier filter element, a water purifier, and water purification equipment. Background Technology

[0002] Household water purifiers are widely used to remove harmful substances from tap water. Among these harmful substances, free residual chlorine is designated as a target for removal in the Household Product Quality Labelling Law for household water purifiers, aiming to remove free residual chlorine from tap water.

[0003] To remove free residual chlorine, activated carbon and metal sulfites are commonly used in household water purifiers. For example, Patent Document 1 describes an activated carbon with numerous small pores, the pore size being 0.679 nm to 0.733 nm. This pore size enhances the ability to capture free residual chlorine within the pores of the activated carbon. Patent Document 2 describes a free residual chlorine removal agent containing metal sulfites.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2020-157242

[0007] Patent Document 2: Japanese Patent Application Publication No. 2004-113869 Summary of the Invention

[0008] -The technical problem the invention aims to solve-

[0009] In recent years, the demand for miniaturization of the main body of water purifiers has increased in the household water purifier sector, along with requirements for improved removal performance of activated carbon. In particular, in 2019, the JIS test methods for household water purifiers were revised, and five new substances were added to the new Japanese Industrial Standard JIS S3201:2019. This has led to a desire for household water purifiers capable of removing a wider variety of harmful substances compared to previous models.

[0010] In the activated carbon described in Patent Document 1, high removal performance for free residual chlorine is achieved by controlling the micropores by setting the pore size within a specified range; however, larger pores are not controlled. Therefore, this activated carbon does not have high adsorption performance for relatively large organic substances such as newly added anionic surfactants and cannot remove a variety of harmful substances.

[0011] Furthermore, the removal agent described in Patent Document 2 utilizes the reducing effect of metal sulfites to achieve high removal performance for free residual chlorine, but this removal agent lacks pores. Therefore, it also lacks adsorption properties for anionic surfactants and cannot remove a variety of harmful substances.

[0012] This invention was made to solve the above-mentioned technical problems. Its purpose is to provide a carbonaceous material and its manufacturing method, an adsorption filter, a water purifier filter element, a water purifier and water purification equipment, which can achieve a high level of removal performance for free residual chlorine that can be decomposed on the surface of carbonaceous materials and anionic surfactants with relatively large molecular sizes.

[0013] - Technical solutions used to solve technical problems -

[0014] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that carbonaceous materials with iodine adsorption capacity, active black 5 value and specific surface area within a specific range can achieve a high level of performance in removing free residual chlorine that can be decomposed on the surface of carbonaceous materials and anionic surfactants with relatively large molecular size, thus completing the present invention.

[0015] The present invention includes the following embodiments.

[0016] [1] A carbonaceous material, wherein the iodine adsorption capacity of the carbonaceous material is above 1300 mg / g and below 1800 mg / g, the active black 5 value is above 1.0 g / L and below 6.0 g / L, and the specific surface area calculated by the BET (Brunauer-Emmett-Teller) method based on the N2 adsorption isotherm at -196℃ is 1100 m². 2 / g or more and 1700m 2 / g or less.

[0017] [2] Based on the carbonaceous material described in [1], the ratio (A / B) of the pore volume (A) of less than 1.00 nm in each 1g of carbonaceous material calculated by QSDFT (Quenched Solid Density Functional Theory) based on the nitrogen adsorption isotherm to the pore volume (B) of the mesopores obtained by BJH (Barrett-Joyner-Halenda) based on the N2 adsorption isotherm at -196℃ is greater than 1.0 and less than 4.0.

[0018] [3] Based on the carbonaceous material described in [1], the proportion of mesoporous material is 4.8% or more and 15.0% or less.

[0019] [4] Based on the carbonaceous material described in [1], the pore volume of the mesopores, determined by the BJH method based on the N2 adsorption isotherm at -196℃, is 0.06 cm³. 3 / g or more and 0.30cm 3 / g or less.

[0020] [5] Based on the carbonaceous material described in [1], the total pore volume calculated by the BJH method based on the N2 adsorption isotherm at -196℃ is 0.25 cm³. 3 / g or more and 1.00cm 3 / g or less.

[0021] [6] Based on the carbonaceous material described in [1], the filling density measured by the tapping method is above 0.30 g / mL and below 0.50 g / mL.

[0022] [7] Based on any one of [1] to [6], the carbonaceous material is used in water to remove at least free residual chlorine and anionic surfactants.

[0023] [8] A method for manufacturing a carbonaceous material, wherein the carbonaceous material is any one of [1] to [6], the method comprising: a carbonization step of carbonizing a raw material to obtain a carbide, and an activation step of activating the carbide to obtain an activated material.

[0024] [9] Based on the manufacturing method described in [8], the manufacturing method further includes a cleaning step for cleaning the activated material.

[0025]

[10] Based on the manufacturing method described in [8], the raw material is coconut shell.

[0026]

[11] An adsorption filter comprising any one of [1] to [6] carbonaceous material.

[0027]

[12] A water purifier filter element, the water purifier filter element comprising any one of [1] to [6] carbonaceous material.

[0028]

[13] A water purifier comprising any one of [1] to [6] carbonaceous material.

[0029]

[14] A water purification device, the water purification device comprising any one of [1] to [6] carbonaceous materials.

[0030] -The effects of the invention-

[0031] According to the present invention, a carbonaceous material and its manufacturing method, an adsorption filter, a water purifier filter element, a water purifier, and a water purification device can be provided, which can achieve a high level of removal performance for free residual chlorine that can be decomposed on the surface of the carbonaceous material and anionic surfactants with relatively large molecular sizes. Attached Figure Description

[0032] Figure 1 The number I is a schematic cross-sectional view of a rotary kiln. Figure 1 II is a schematic side view of the rotary kiln.

[0033] Figure 2 This is a schematic cross-sectional view used to illustrate a rotary kiln. Detailed Implementation

[0034] The following describes in detail the methods for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the following embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0035] In this specification, following the classification criteria of IUPAC (International Union of Pure and Applied Chemistry), the pores of carbonaceous materials are classified according to their pore size (diameter): pores with a diameter less than 2.0 nm are "micropores," pores with a diameter between 2.0 nm and 50.0 nm are "mesopores," and pores with a diameter greater than 50.0 nm are "macropores." Mesopores are very effective for the adsorption of anionic surfactants and other relatively large molecules.

[0036] [Carbon-based materials]

[0037] Regarding the carbonaceous material of this embodiment, its iodine adsorption capacity is 1300 mg / g or more and 1800 mg / g or less, its active black 5 value is 1.0 g / L or more and 6.0 g / L or less, and its specific surface area, calculated by the BET method based on the N2 adsorption isotherm at -196°C, is 1100 m². 2 / g or more and 1700m 2 / g or less.

[0038] Carbonaceous materials, by possessing certain characteristics, can achieve a high level of removal performance for both free residual chlorine that can decompose on their surface and anionic surfactants with relatively large molecular sizes. In other words, the surface area per unit mass of the carbonaceous material is controlled to be suitable for free residual chlorine that can decompose on its surface, thus achieving high removal performance for free residual chlorine. Furthermore, the pore size of the carbonaceous material is controlled to be suitable for anionic surfactants with relatively large molecular sizes, thus achieving high adsorption performance for anionic surfactants.

[0039] Examples of anionic surfactants include alkyl sulfonates such as sodium linear dodecylbenzenesulfonate. The carbonaceous material of this embodiment is capable of appropriately adsorbing one or more of these anionic surfactants.

[0040] The iodine adsorption capacity of carbonaceous materials is above 1300 mg / g and below 1800 mg / g.

[0041] Iodine adsorption capacity is an indicator of the surface area of ​​the pores in carbonaceous materials that can physically adsorb anionic surfactants with relatively large molecular sizes. By keeping the iodine adsorption capacity of carbonaceous materials within the aforementioned range, the materials maintain their performance in removing free residual chlorine while exhibiting particularly high adsorption capacity for anionic surfactants. By setting the iodine adsorption capacity to 1300 mg / g or higher, the pore volume of the carbonaceous material becomes sufficiently large, significantly improving the adsorption performance of anionic surfactants. By setting the iodine adsorption capacity to 1800 mg / g or lower, the pores of the carbonaceous material do not become excessively large, making it easier to control the pore size for adsorbing anionic surfactants.

[0042] The iodine adsorption capacity was measured and calculated according to Japanese Industrial Standard JIS K 1474 (2014). For specific measurement and calculation methods for iodine adsorption capacity, please refer to the examples.

[0043] The iodine adsorption capacity is preferably 1310 mg / g or more and 1700 mg / g or less, more preferably 1330 mg / g or more and 1650 mg / g or less. When the iodine adsorption capacity is within the above range, it is preferable to obtain a carbonaceous material that maintains the removal performance for free residual chlorine while exhibiting higher adsorption performance, especially for anionic surfactants.

[0044] The reactive black 5 value for carbonaceous materials is above 1.0 g / L and below 6.0 g / L. Reactive black 5 is a dye represented by the following formula (1), and is also known as CI reactive black 5.

[0045] [Chemical Formula 1]

[0046]

[0047] Reactive Black 5 has a relatively large molecular weight of 995.88 and a large volumetric structure. Therefore, the Reactive Black 5 value becomes an indicator of the adsorption characteristics of anionic surfactants and the like, which have relatively large molecular sizes. By keeping the Reactive Black 5 value within the aforementioned range, carbonaceous materials can maintain their removal performance for free residual chlorine while exhibiting high adsorption performance, especially for anionic surfactants. By keeping the Reactive Black 5 value above 1.0 g / L, the cumulative pore volume of the larger pores in the carbonaceous material does not become excessive, allowing the carbonaceous material to maintain its removal performance for free residual chlorine while appropriately maintaining an effective amount of porosity for anionic surfactants and the like, which have relatively large molecular sizes. By keeping the Reactive Black 5 value below 6.0 g / L, the amount of pores in the carbonaceous material suitable for adsorbing anionic surfactants and the like, which have relatively large molecular sizes, is sufficient. Therefore, the adsorption performance for anionic surfactants and the like is significantly improved.

[0048] The Reactive Black 5 value can be calculated, for example, as follows: First, using a UV-Vis spectrophotometer, at a wavelength of 594 nm and a path length (cuvette length) of 10 mm, the absorbance of the test solution containing Reactive Black 5 and the absorbance of the residual liquid obtained after removing the carbonaceous material that has been mixed into the test solution and allowed to fully adsorb Reactive Black 5 are calculated. Then, using these absorbance values, the residual percentage of Reactive Black 5 in the residual liquid and the amount of Reactive Black 5 adsorbed per 1 g of carbonaceous material are calculated. Using these values, the amount of carbonaceous material required to remove 99% of the Reactive Black 5 from 1 L of test solution is calculated as the Reactive Black 5 value (g / L). It should be noted that, in the measurement of the Reactive Black 5 value, the carbonaceous material preferably used has its 50% particle size (D50) in the cumulative distribution based on volume adjusted to be 9.0 μm or more and 11.0 μm or less. In this specification, 50% particle size (D50) refers to the median diameter based on a volume reference, measured using a laser diffraction light scattering particle size distribution measurement device. For specific measurement and calculation methods of the Reactive Black D50 value, please refer to the examples.

[0049] The active black 5-value is preferably 1.5 g / L or higher and 5.5 g / L or lower, more preferably 1.7 g / L or higher and 4.5 g / L or lower, and even more preferably 2.0 g / L or higher and 4.0 g / L or lower. When the active black 5-value is within the above range, it is preferable to obtain a carbonaceous material that maintains the removal performance for free residual chlorine while exhibiting higher adsorption performance, especially for anionic surfactants.

[0050] In carbonaceous materials, the specific surface area (hereinafter referred to as "BET specific surface area") calculated by the BET method based on the N2 adsorption isotherm at -196℃ is 1100 m².2 / g or more and 1700m 2 / g or less. BET specific surface area is the surface area retained per unit mass of carbonaceous material, and is an indicator of the surface area capable of decomposing free residual chlorine. By maintaining the BET specific surface area within the above range, carbonaceous materials can maintain their adsorption performance for anionic surfactants, etc., while exhibiting particularly high removal performance for free residual chlorine. By achieving a BET specific surface area of ​​1100 m²... 2 With a specific surface area exceeding 1700 m² / g, the carbonaceous material exhibits a sufficiently large surface area. Therefore, it demonstrates high removal performance for free residual chlorine, resulting in a significantly improved removal efficiency. This is achieved by achieving a BET specific surface area of ​​1700 m² / g. 2 With a surface area below / g, the specific surface area of ​​the carbonaceous material does not become excessively large, resulting in a suitable pore volume. Furthermore, it does not lead to a decrease in the carbon content constituting the carbon skeleton, thus yielding an appropriate carbonaceous material. Therefore, for example, even in tap water, the carbonaceous material is not easily damaged, and it can exhibit high removal performance for free residual chlorine and anionic surfactants. For specific methods of measuring and calculating the BET specific surface area, please refer to the examples.

[0051] The preferred specific surface area for BET is 1250m². 2 / g or more and 1690m 2 / g or less, more preferably 1300m 2 / g or more and 1680m 2 / g or less, more preferably 1400m 2 / g or more and 1670m 2 / g or less. When the BET specific surface area is within the above range, it is likely that a carbonaceous material can be obtained that maintains the adsorption performance for anionic surfactants, etc., while having a higher removal performance, especially for free residual chlorine.

[0052] In carbonaceous materials, the ratio (A / B, hereinafter also referred to as "mesopore ratio") of the pore volume (A) with a pore size of 1.0 nm or less per 1 g of carbonaceous material calculated by the QSDFT method based on the nitrogen adsorption isotherm to the mesopore volume (B) (hereinafter also referred to as "mesopore volume") determined by the BJH method based on the N2 adsorption isotherm at -196°C is preferably 1.0 or more and 4.0 or less, more preferably 1.3 or more and 3.5 or less, and even more preferably 1.5 or more and 3.0 or less. When the mesopore ratio is within the above range, it is preferable to obtain carbonaceous materials that maintain adsorption performance for anionic surfactants, etc., while exhibiting higher removal performance, especially for free residual chlorine.

[0053] Mesopority ratio is an indicator of the proportion of pores effective for removing free residual chlorine. By setting the mesopority ratio to 1.0 or higher, more pores with effective chlorine removal sizes are present, tending to achieve higher removal performance. By setting the mesopority ratio to 4.0 or lower, the proportion of excessively large pores unsuitable for removing free residual chlorine is small, and the porosity in carbonaceous materials does not become excessively large, thus preventing a decrease in the carbon content constituting the carbon skeleton. Therefore, higher removal performance is tended to be achieved.

[0054] For specific methods of measuring and calculating the mesoporous ratio, please refer to the examples.

[0055] The proportion of mesoporous material 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 even more preferably 6.0% or more and 12.0% or less. When the proportion of mesoporous material is within the above range, it is preferable to obtain a carbonaceous material that maintains the removal performance for free residual chlorine while exhibiting higher adsorption performance, especially for anionic surfactants.

[0056] In this specification, the mesopore ratio refers to the ratio of the specific surface area (hereinafter also referred to as "BJH specific surface area") calculated using the BJH method based on the N2 adsorption isotherm at -196°C in carbonaceous materials to the specific surface area (i.e., BET specific surface area) calculated using the BET method based on the N2 adsorption isotherm at -196°C. Mesopores are relatively large pores among the pores in carbonaceous materials that facilitate adsorption. Therefore, a larger mesopore ratio indicates better adsorption performance for anionic surfactants and the like, which have relatively large molecular sizes. For specific measurement and calculation methods regarding the mesopore ratio, please refer to the examples.

[0057] By maintaining a mesoporous content of 4.8% or more, the proportion of effective pores for anionic surfactants with relatively large molecular sizes is sufficiently large. Therefore, while maintaining the removal performance of free residual chlorine, the removal performance of carbonaceous materials is significantly improved, especially for anionic surfactants. By maintaining a mesoporous content of 15.0% or less, the pores of the carbonaceous material do not become excessively large, and the control of pore size for adsorbing anionic surfactants becomes easier while maintaining the removal performance of free residual chlorine.

[0058] In carbonaceous materials, the pore volume of mesopores (hereinafter also referred to as "mesopore volume") determined by the BJH method based on the N2 adsorption isotherm at -196℃ is preferably 0.06 cm³. 3 / g or more and 0.30cm 3 / g or less, more preferably 0.10cm 3 / g or more and 0.25cm 3 / g or less, more preferably 0.12cm 3 / g or more and 0.22cm 3 / g or less. When the pore volume of the mesopores is within the above range, it is likely that carbonaceous materials can be obtained that maintain the removal performance for free residual chlorine, and have higher adsorption performance, especially for anionic surfactants.

[0059] By making the pore volume of the mesopore 0.06 cm³ 3 With a pore volume of 0.30 cm³ / g or more, carbonaceous materials can retain a relatively large number of pores, especially effective for anionic surfactants. Therefore, carbonaceous materials tend to maintain their free residual chlorine removal performance while exhibiting high adsorption capacity, particularly for anionic surfactants. 3 With a volume of / g or less, the pores of the carbonaceous material do not become excessively large, allowing it to retain a significant number of pores, particularly effective for the adsorption of anionic surfactants. Therefore, carbonaceous materials tend to maintain high adsorption performance, especially for anionic surfactants, while retaining their ability to remove free residual chlorine. For specific methods of measuring and calculating the pore volume of the mesopores, please refer to the examples.

[0060] In carbonaceous materials, the total pore volume (hereinafter referred to as "total pore volume") determined by the BJH method based on the N2 adsorption isotherm at -196℃ is preferably 0.25 cm³. 3 / g or more and 1.00cm 3 / g or less, more preferably 0.35cm 3 / g or more and 0.90cm 3 / g or less, more preferably 0.45cm 3 / g or more and 0.85cm 3 / g or less. When the total pore volume is within the above range, it is generally possible to obtain carbonaceous materials that maintain the removal performance for free residual chlorine, and especially have higher adsorption performance for anionic surfactants. It should be noted that the total pore volume is the cumulative pore volume in the range of pore size from 1.2 nm to 97.4 nm.

[0061] By making the total pore volume 0.25 cm³ 3 With a total pore volume of 1.00 cm³ / g or more, the carbonaceous material exhibits a sufficiently large pore volume, thus tending to perform better, especially with anionic surfactants. 3With a volume of less than / g, the pores of the carbonaceous material do not become excessively large. The carbonaceous material retains a relatively large number of pores effective for adsorbing anionic surfactants, thus tending to exhibit higher performance with anionic surfactants. For specific methods of measuring and calculating the total pore volume, please refer to the examples.

[0062] In carbonaceous materials, the packing density (hereinafter also referred to as "packing density") measured by the tapping method 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 even more preferably 0.33 g / mL or more and 0.43 g / mL or less. By keeping the packing density within the above range, carbonaceous materials tend to achieve higher levels of removal performance for free residual chlorine and anionic surfactants. By keeping the packing density at 0.30 g / mL or more, the pores of the carbonaceous material do not become excessively large, and the carbonaceous material can retain more pores effective for free residual chlorine and anionic surfactants. Therefore, carbonaceous materials tend to have high removal performance for free residual chlorine and anionic surfactants. By keeping the packing density at 0.50 g / mL or less, sufficient pores conducive to physical adsorption tend to exist. Therefore, carbonaceous materials tend to have even higher removal performance for free residual chlorine and anionic surfactants. For specific methods of measuring and calculating filling density, please refer to the examples.

[0063] The shape of carbonaceous materials varies depending on their application and is not particularly limited. Examples of such shapes include: powder, block, crushed, spherical, cylindrical, ellipsoidal sphere, distorted, elliptical cylinder, elliptical cone, and multi-faceted prisms such as triangular prisms, quadrangular prisms, pentagonal prisms, and hexagonal prisms; granular, solid, and hollow granules; crushed, powdery, substrate-like (sheet-like), woven fabric-like, felt-like, and block-like materials.

[0064] The shape of the carbonaceous material is preferably one that can be used in known adsorption filters. Examples of such shapes include: spherical, ellipsoidal, distorted, rod-shaped, filamentous, granular, powdered, and other broken forms, substrate-like (sheet-like), woven fabric-like, fibrous, and block-like. These shapes can be appropriately selected depending on the specific application. Among these shapes, from the viewpoint of high adsorption performance per unit volume, a broken shape is preferred for the carbonaceous material, and a powdered shape is more preferred. In the case of powdered carbonaceous material, its size is not particularly limited; the particle size can be appropriately adjusted according to the specific application.

[0065] In this specification, "fragmented" refers to particles of any shape that are not fixed in shape and are usually angular. Additionally, "powdered" refers to powders such as micro-powder, powder, fine granules, and granules, typically with 50% of the particle size (D50) in the cumulative distribution based on volume being 1 μm or more and 150 μm or less.

[0066] For example, when carbonaceous materials are used as adsorption filters in water purifiers, their shape varies depending on the application and is not particularly limited, but cylindrical or substrate-like (sheet-like) shapes are preferred. When carbonaceous materials are in such shapes, they tend to be used efficiently as adsorption filters in water purifiers.

[0067] Activated carbon is the preferred carbonaceous material.

[0068] [Manufacturing methods for carbonaceous materials]

[0069] The carbonaceous material of this embodiment can be obtained by known manufacturing methods.

[0070] Examples of such methods include thermal decomposition, activation, coating, and vapor deposition. Activation is preferred as the manufacturing method. By using these methods, it is easier to manufacture products with an iodine adsorption capacity of 1300 mg / g or more and 1800 mg / g or less, an active black 5-value of 1.0 g / L or more and 6.0 g / L or less, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0071] The method for manufacturing carbonaceous materials according to this embodiment includes a carbonization step of carbonizing raw materials to obtain carbides, and an activation step of activating the carbides to obtain activated materials. Preferably, the method for manufacturing carbonaceous materials according to this embodiment includes a cleaning step of cleaning the activated materials.

[0072] (Carbonization process)

[0073] The manufacturing method of carbonaceous materials includes a carbonization process that carbonizes raw materials to obtain carbides.

[0074] As raw materials, there are no particular limitations on any material that can produce the desired carbonaceous material. Examples of raw materials include: wood, wood flour, fruit shells such as coconut shells, palm kernels, plum and peach seeds, byproducts of pulp production, bagasse, molasses waste, coal (peat, sub-bituminous coal, lignite, and bituminous coal, etc.), anthracite, petroleum distillation residues, petroleum asphalt, coke, and coal tar, as well as other plant-based or fossil-based raw materials; 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 polybutene, polybutadiene, and polychloroprene; other synthetic woods; and synthetic pulp. These raw materials can be used individually or in any proportion of two or more depending on the required specifications.

[0075] The raw material is preferably a natural product, more preferably coconut shell. Using such a raw material, it is easier to produce iodine adsorption capacity of 1300 mg / g or higher and 1800 mg / g or lower, an Active Black 5-value of 1.0 g / L or higher and 6.0 g / L or lower, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0076] The raw materials may also contain additives, etc., as needed. In addition, additives, etc., may be added to the carbides as needed.

[0077] Examples of such additives include: water, coal tar, anhydrous tar, hard pitch, coal tar-based pitch, and petroleum-based pitch. Additives can be used alone or in combination of two or more.

[0078] Typically, additives, etc., are added in amounts of 1.0 part by mass and 50.0 parts by mass relative to 100 parts by mass of the raw material or carbide. Furthermore, the total amount of additives, etc., is typically 1 part by mass and 100 parts by mass relative to 100 parts by mass of the raw material or carbide. When mixing the raw material or carbide with additives, the oxygen content in the raw material or carbide may be pre-adjusted to a range of 1.0% by mass and 20.0% by mass relative to 100% by mass, as needed. Oxygen content adjustment can be achieved, for example, by mixing the raw material or carbide with oxygen under heating conditions of 150°C to 300°C.

[0079] In methods for manufacturing carbonaceous materials, the raw materials may be pulverized or shaped before carbonization. One example of such a method is to pulverize the raw materials into powder using a known pulverizer before carbonization. Another example is to shape the raw materials into granules using a known method before carbonization.

[0080] When the raw material is in powder form, the particle size of the powder (50% particle size in the cumulative distribution based on volume, D50) is preferably 1 μm or more and 150 μm or less.

[0081] There are no particular limitations on the carbonization method of the raw materials. For example, heating to above 300°C and below 900°C under anaerobic conditions, preferably above 400°C and below 800°C, can be cited.

[0082] The carbonization time can be appropriately set according to the raw materials and the equipment used for carbonization. For example, a carbonization time of 15 minutes or more and 20 hours or less is preferred, 30 minutes or more and 10 hours or less is more preferably 60 minutes or more and 5 hours or less. The carbonization process can be performed using known manufacturing equipment such as a rotary kiln. Furthermore, the carbonization process can also be performed under reduced pressure with air removal or under a nitrogen atmosphere.

[0083] In the manufacturing methods of carbonaceous materials, a known pulverizer can be used to pulverize the carbides into powder. Therefore, it is easier to manufacture materials with an iodine adsorption capacity of 1300 mg / g or higher and 1800 mg / g or lower, an active black 5-value of 1.0 g / L or higher and 6.0 g / L or lower, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g. In the manufacturing method of carbonaceous materials, after the carbide is pulverized into powder, additives or the like are added to the powdered carbide as needed and mixed using known methods, and then the resulting mixture is shaped using known methods.

[0084] When the carbide is in powder form, the particle size of the carbide (50% of the particle size in the cumulative distribution based on volume, D50) is preferably 1 μm or more and 150 μm or less.

[0085] In the manufacturing methods of carbonaceous materials, known methods can also be used to shape carbides, powdered carbides, mixtures, or powdered mixtures into cylindrical granules. Therefore, it is easier to manufacture materials with an iodine adsorption capacity of 1300 mg / g or more and 1800 mg / g or less, an active black 5-value of 1.0 g / L or more and 6.0 g / L or less, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0086] When the carbide is shaped into cylindrical granules, the diameter of the cylindrical granules is preferably 0.1 mm or more and 4.0 mm or less. In addition, the aspect ratio (diameter:height) of the cylindrical granules is preferably 1:1 to 1:10.

[0087] The carbonization process described above yields carbonized materials.

[0088] The manufacturing method of carbonaceous materials may also include a cleaning process to clean the carbides and / or a drying process to dry the carbides after the carbonization process. There are no particular limitations on the conditions in these processes, and known conditions can be used. Alternatively, the cleaning and drying processes described below can also be referenced.

[0089] (Activation process)

[0090] The manufacturing method of carbonaceous materials includes an activation process that activates carbides to obtain activated materials.

[0091] As an activation treatment, known methods can be used.

[0092] The activation process can be performed using known manufacturing equipment such as rotary kilns, fluidized bed furnaces, and Sleip furnaces (vertical furnaces). Alternatively, the activation process can be carried out under reduced pressure with air removal or under a nitrogen atmosphere.

[0093] The activation treatment is preferably carried out using a rotary kiln. By using a rotary kiln, the activated material, which becomes lighter as the carbides are activated, does not escape from the furnace and remains inside. Therefore, the carbides can be activated more thoroughly, and thus tend to produce activated material with well-developed micropores and mesopores, and the proportion of these pores is controlled within an appropriate range.

[0094] Furthermore, the use of a rotary kiln allows for efficient contact between carbides and reactive gases. As a result, it is easier to manufacture carbonaceous materials with higher adsorption performance for free residual chlorine and anionic surfactants.

[0095] When using a rotary kiln for activation treatment, the carbides fed into the kiln are sieved using a standard metal mesh sieve as specified in Japanese Industrial Standard JIS Z8801-1:2019. Preferably, the particle size is between 70 mesh (sieve aperture size: 243 μm) and 2 mesh (sieve aperture size: 10.7 mm), and more preferably, between 32 mesh (sieve aperture size: 490 μm) and 2 mesh (sieve aperture size: 10.7 mm). By ensuring the particle size of the carbides is within the above range, the activated material, which becomes lighter as activation progresses, remains in the kiln, enabling more efficient activation. The carbides can be either those whose particle size has been adjusted by pre-cutting the raw material to the desired size before the carbonization process, or those whose particle size has been adjusted by crushing and grading the carbides to the desired size.

[0096] Examples of activation methods include gas activation, which uses reactive gases such as water vapor, oxygen, and carbon dioxide to vaporize the carbides, and chemical activation, which uses reagents such as zinc chloride and phosphoric acid to activate the carbides. Gas activation is preferred as the activation method. Using reactive gases in gas activation results in a more efficient reaction rate, and the reaction rate can be controlled without reducing production efficiency. Therefore, it is easier to obtain carbonaceous materials with well-developed micropores and mesopores. Consequently, it is easier to manufacture carbonaceous materials with higher processing performance to free residual chlorine and anionic surfactants. It should be noted that inert gases such as nitrogen can also be used simultaneously with reactive gases.

[0097] 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.

[0098] As an active gas, it is preferable to use one or more selected from the group consisting of water vapor and oxygen, and more preferably to use both water vapor and oxygen.

[0099] Water vapor offers a more efficient reaction rate, allowing for further control of the reaction rate without reducing production efficiency. Furthermore, the use of water vapor makes it easier to obtain carbonaceous materials with well-developed mesoporous and microporous structures without compromising production efficiency. Therefore, it is preferable to manufacture carbonaceous materials with higher adsorption performance for free residual chlorine and anionic surfactants.

[0100] Furthermore, activation reactions are typically endothermic; therefore, a certain amount of heat is required for the activation reaction to proceed more efficiently. To maintain this heat, it is preferable to use oxygen as an active gas in addition to water vapor. The volatile gases produced during the activation reaction react with the oxygen and burn, thereby maintaining the heat required for activation. It should be noted that flammable gases such as hydrogen and carbon monoxide produced during the activation of carbides can be cited as examples of volatile gases.

[0101] When using water vapor and oxygen as the active gases, the partial pressure of water vapor is preferably greater than 20.0% by volume and less than 40.0% by volume, more preferably greater than 25.0% by volume and less than 35.0% by volume. The partial pressure of oxygen is preferably greater than 1.0% by volume and less than 5.0% by volume, more preferably greater than 1.5% by volume and less than 3.5% by volume. It should be noted that inert gases such as nitrogen may also be included as other gases. In this case, the partial pressure of the inert gas is preferably greater than 45.0% by volume and less than 89.0% by volume, more preferably greater than 61.5% by volume and less than 73.5% by volume. By keeping these proportions within the above ranges, it is easier to manufacture iodine adsorption capacity of 1300 mg / g or more and less than 1800 mg / g, active black 5 value of 1.0 g / L or more and less than 6.0 g / L, and specific surface area of ​​1100 m² based on the N₂ adsorption isotherm at -196 °C determined by the BET method. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0102] When using water vapor and oxygen as active gases, their flow rates are preferably a total of 10 liters (L) or more and 300 liters (L) or less per minute.

[0103] The activation time can be appropriately set according to conditions such as raw materials, activation temperature, and manufacturing equipment. For example, the activation time 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, further preferably 150 minutes or more and 600 minutes or less, and even more preferably 240 minutes or more and 480 minutes or less. By keeping the activation time within the above range, it is easier to manufacture products with an iodine adsorption capacity of 1300 mg / g or more and 1800 mg / g or less, an Active Black 5-value of 1.0 g / L or more and 6.0 g / L or less, and a specific surface area of ​​1100 m² / g determined by the BET method based on the N₂ adsorption isotherm at -196°C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0104] The activation temperature is not particularly limited, but is preferably 800°C or higher and 1250°C or lower, more preferably 850°C or higher and 1150°C or lower. Activation at such temperatures tends to more easily produce iodine adsorption capacities of 1300 mg / g or higher and 1800 mg / g or lower, an Active Black 5-value of 1.0 g / L or higher and 6.0 g / L or lower, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196°C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0105] An example of an activation device for performing an activation process is... Figure 1 and Figure 2 A rotary kiln as shown. Figure 1 These are cross-sectional view I and side view II of the rotary kiln. Figure 2 This is a schematic cross-sectional view used to illustrate a rotary kiln.

[0106] like Figure 1 and 2 As shown, a rotary kiln typically includes a tube body 1 and stirring blades A to F arranged on the inner wall of the tube body 1. The active gas is usually transported from one side to the other, i.e., in... Figure 1 and 2 In the rotary kiln shown, the active gas is conveyed in the direction 2 of the tube body 1.

[0107] The material of tube 1 is not particularly limited as long as it is the same material used in rotary kilns; for example, stainless steel can be used.

[0108] exist Figure 1 and Figure 2 The number of stirring blades is six, but can be appropriately adjusted according to the amount of carbide 5 used as raw material. The number of stirring blades is typically one to twenty, preferably three to twelve, and more preferably five to ten. Furthermore, the stirring blades are preferably arranged at equal intervals around the central axis of the tube body 1. For example, if the number of stirring blades is six, one blade is arranged every 60° around the central axis of the tube body 1.

[0109] The height of the stirring blade (the height from the wall of the tube 1 towards the center) can be appropriately set according to the size of the tube 1 and the amount of carbide 5 loaded. Preferably, the height of the stirring blade is such that it is not covered by the carbide 5 loaded into the tube 1, but is still visible. Specifically, the preferred height of the stirring blade is as follows: when the stirring blade is located at the bottom surface of the tube 1 (… Figure 2In the case of the stirring blade B in the right figure, the portion of the stirring blade from the bottom surface to a point at least 1 / 2 and less than 2 / 3 of its height is covered by carbide 5. More preferably, the height of the stirring blade is at least 10% and less than 30% of the inner radius of the tube body 1.

[0110] The thickness of the stirring blade (the thickness of the tube 1 in the rotation direction 3) can be appropriately set according to the size of the tube 1 and the amount of carbide 5 loaded. The thickness of the stirring blade is preferably such that the stirring blade has strength sufficient to prevent it from breaking due to the carbide 5 loaded into the tube 1. Specifically, the thickness of the stirring blade is generally 1% or more and 100% or less relative to the wall thickness of the tube 1, preferably 20% or more and 90% or less, and more preferably 30% or more and 95% or less.

[0111] The material of the stirring blades is not particularly limited as long as it is the same material used in rotary kilns; for example, stainless steel can be used.

[0112] By arranging the stirring blades within tube 1 in this way, the contact efficiency between carbide 5 and the active gas is tended to be further improved. Therefore, it is easier to manufacture carbonaceous materials with the desired specific surface area.

[0113] like Figure 2 As shown, carbide 5 has been appropriately loaded into the interior of tube 1. Then, tube 1 rotates in the rotation direction 3, thereby lifting, for example, the carbide 5 already captured by stirring blade A, and then mixing while passing over stirring blade A in the direction of carbide descent 4, and being activated while contacting the active gas, and being captured between stirring blade A and stirring blade B. In this way, by rotating tube 1, carbide 5 is mixed while passing over stirring blades A to F, and is activated by efficient and uniform contact with the active gas. Therefore, it is easier to manufacture carbonaceous materials with the desired pore size distribution.

[0114] In this way, by using a rotary kiln as the activation device, it is easier to produce iodine adsorption capacities of 1300 mg / g or higher and 1800 mg / g or lower, active black 5-values ​​of 1.0 g / L or higher and 6.0 g / L or lower, and specific surface areas of 1100 m² / g as determined by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0115] The activated material is obtained through the above activation process.

[0116] The manufacturing method of carbonaceous materials may also include a cleaning process for rinsing the activated material and / or a drying process for drying the activated material after the activation process. The conditions in these processes are not particularly limited, and known conditions can be used. Alternatively, the cleaning and drying processes described below can also be referenced.

[0117] (Cleaning process)

[0118] The carbonaceous material is preferably obtained through a cleaning process that cleans the activated material obtained in the activation process. Water washing is more preferred as the cleaning method. This cleaning process tends to more easily produce materials with an iodine adsorption capacity of 1300 mg / g or more and 1800 mg / g or less, an active black 5-value of 1.0 g / L or more and 6.0 g / L or less, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 Carbonaceous materials with a density of less than / g.

[0119] The temperature and time during cleaning should be adjusted appropriately to obtain the desired carbonaceous material.

[0120] (Drying process)

[0121] The carbonaceous material is preferably obtained by a drying process in which the cleaned material obtained in the cleaning process is dried.

[0122] There are no particular limitations on the drying method; known drying methods such as natural drying, heated drying, and hot air drying can be used. Heating and / or depressurization are preferred methods. From the viewpoint of achieving uniform and stable drying, hot air drying is preferred as a heating method. In the drying process, it is preferable to dry the carbonaceous material until the moisture content is 20.0% by mass or less, more preferably until the moisture content is 10.0% by mass or less.

[0123] Examples of heating methods include those using the following dryers: static constant temperature dryer; static hot air dryer; vacuum dryer; rotary evaporator; conical dryer; Nota dryer; and other mixed dryers. The heating temperature should be such that the carbonaceous material solidifies without melting, preferably between 40°C and 300°C.

[0124] Examples of pressure reduction methods include those using oil pumps, oilless pumps, and suction devices. The pressure in these methods is typically between 0.00001 MPa and 0.05 MPa.

[0125] The drying time varies depending on the drying temperature, and is usually between 1 minute and 20 hours.

[0126] The resulting carbonaceous material can be used directly, or, as needed, the particle size can be adjusted by crushing, pulverizing, and classifying using known methods; additional cleaning can be performed using, for example, water, organic solvents, acidic aqueous solutions, and alkaline aqueous solutions to improve purity; and additional heat treatment can be used to impart durability and adjust the structure, thereby obtaining the carbonaceous material.

[0127] The particle size (50% of the particle size in the cumulative distribution based on volume, D50) of the carbonaceous material is preferably adjusted to be 20 μm or more and 500 μm or less. By keeping the particle size of the carbonaceous material within the above range, the carbonaceous material can be suitably used for applications, such as those described below.

[0128] [use]

[0129] Carbonaceous materials can be appropriately used for various applications involving the removal, adsorption, concentration, and recovery of free residual chlorine and anionic surfactants. Such applications can also involve appropriately combining removal, adsorption, concentration, and recovery operations. Examples of such applications include: adsorption filters, water purifier filter cartridges, water purifiers, packed towers, and water purification equipment encompassing domestic drinking water treatment, water treatment and purification in industrial processes, and wastewater treatment.

[0130] Carbonaceous materials are appropriately used to remove free residual chlorine and anionic surfactants, etc.

[0131] [Methods for removing free residual chlorine and anionic surfactants, etc.]

[0132] Methods for removing free residual chlorine and anionic surfactants include a removal step using a carbonaceous material. Free residual chlorine is removed, for example, by decomposition on the surface of the carbonaceous material. Anionic surfactants are removed, for example, by adsorption onto the carbonaceous material. In these removal methods, besides using the carbonaceous material described in this embodiment, the same steps as known methods for removing free residual chlorine and anionic surfactants, adsorption methods, concentration methods, and recovery methods may be included.

[0133] [Adsorption Filter]

[0134] The adsorption filter of this embodiment contains the carbonaceous material of this embodiment. Furthermore, the adsorption filter is preferably for use in a water purifier.

[0135] Adsorption filters contain carbonaceous materials, thus achieving a high level of removal performance for both free residual chlorine and anionic surfactants. Therefore, by installing an adsorption filter in a water purifier, free residual chlorine and anionic surfactants contained in water can be removed efficiently.

[0136] The adsorption filter preferably comprises carbonaceous material and fibrous binder.

[0137] Examples of fibrous binders include those capable of winding and shaping carbonaceous materials through fibrillation. Such fibrous binders can be either synthetic or natural. Examples of fibrous binders include acrylic fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, cellulose fibers, nylon fibers, aramid fibers, and pulp.

[0138] The fibrous binder can be used alone or in combination of two or more. Preferred fibrous binders are polyacrylonitrile fibers and / or pulp. Using these fibrous binders can further improve the density and strength of the adsorption filter, and suppress performance degradation.

[0139] From the viewpoint of achieving a high level of removal performance for both free residual chlorine and anionic surfactants, the adsorption filter preferably contains 20 parts by weight or less of a fibrous binder relative to 100 parts by weight of carbonaceous material, and more preferably 10 parts by weight or less of a fibrous binder. As a lower limit, it is typically 0.01 parts by weight or more.

[0140] It should be noted that, in cases where the adsorption filter contains other functional components described later, the phrase "100 parts by mass relative to the carbonaceous material" regarding the filter composition should be replaced with "100 parts by mass relative to the total of the carbonaceous material and other functional components".

[0141] The adsorption filter may also contain other functional components, provided that the effectiveness of this embodiment is not impaired. Examples of such other functional components include: lead adsorption materials such as titanosilicon and zeolite powders capable of adsorbing and removing dissolved lead; ion exchange resins; chelating resins; and various adsorption materials containing silver ions and / or silver compounds to impart antibacterial properties.

[0142] When water is pumped into the adsorption filter, to avoid excessive pressure loss, the water flow is typically carried out at a space velocity (SV) of 300 rpm or higher and 6500 rpm or lower. The performance of the adsorption filter can be confirmed by plotting the relationship between the removal rates calculated based on the concentrations of the target substances in the raw water and the permeate, and the ratio of the volume of water flowing through from the start of the water flow (L) to the volume of the purified water filter cartridge (mL) (cumulative permeate volume L / mL).

[0143] (Filtering capacity)

[0144] In this specification, filtration capacity is defined as the volume (L) of water that can be pumped through the adsorption filter until the removal rate of the target substance reaches 80%. Water flow is carried out at a spatial velocity (SV) of 3000 / hr.

[0145] (Free residual chlorine filtration capacity)

[0146] The filtration capacity for free residual chlorine can be measured using the free residual chlorine removal performance test specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019. Specifically, the free residual chlorine concentration of the test water is set to 2.0 ± 0.4 (mg / L), and the water temperature is set to 20℃ ± 3℃. The test water is then passed through a carbonaceous material or adsorption filter. The raw test water and the filtered water are analyzed using a spectrophotometer and the DPD reagent (diethyl-p-phenylenediamine) using the DPD spectrophotometric method. The removal rate (%) is calculated based on the concentration of the raw test water (mg / L) and the concentration of the filtered water (mg / L). The relationship between the removal rate (%) and the cumulative water flow (L) is plotted to determine the filtration capacity.

[0147] The adsorption filter of this embodiment has excellent filtration capacity; therefore, the filtration capacity of free residual chlorine, measured according to Japanese Industrial Standard JIS S3201:2019, is typically 1 cm³ / s. 3 The carbonaceous material is 17.0L or more, preferably 20.0L or more, and more preferably 23.0L or more.

[0148] (Filtration capability of anionic surfactants)

[0149] The filtration capacity of anionic surfactants can be measured using the anionic surfactant removal performance test specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019. Specifically, the concentration of anionic surfactant in the test water is set to 0.20 ± 0.04 mg / L, and the water temperature is set to 20℃ ± 3℃. The test water is then passed through a carbonaceous material or adsorption filter. Solid-phase extraction-high performance liquid chromatography (SPE-HPLC) is used to analyze the raw water and filtered water. The removal rate (%) is calculated based on the concentrations of the raw water (mg / L) and filtered water (mg / L). The relationship between the removal rate (%) and the cumulative water flow rate (L) is plotted to determine the filtration capacity.

[0150] The adsorption filter of this embodiment has excellent filtration capacity; therefore, the anionic surfactant filtration capacity of the adsorption filter, measured according to Japanese Industrial Standard JIS S3201:2019, is typically [value missing] per 1 cm³. 3 The carbonaceous material has a volume of 55.0L or more, preferably 65.0L or more, and more preferably 75.0L or more.

[0151] [Water purifier filter cartridge]

[0152] The water purifier filter element of this embodiment includes the carbonaceous material of this embodiment. Besides including the carbonaceous material of this embodiment, the water purifier filter element may also have the same structure as known water purifier filter elements. By including the carbonaceous material, the water purifier filter element can efficiently remove free residual chlorine and anionic surfactants contained in water. By installing the water purifier filter element in a household water purifier, it is possible to efficiently remove various harmful substances, especially free residual chlorine and anionic surfactants, as described in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019.

[0153] Examples of water purification filter cartridges include those formed by filling a housing with carbonaceous material and those formed by filling a housing with an adsorption filter. In addition to the carbonaceous material or adsorption filter described in this embodiment, water purification filter cartridges may also include known nonwoven filters, various adsorption materials, mineral additives, ceramic filter materials, and hollow fiber membranes.

[0154] [Apparatus]

[0155] The device is made of carbonaceous material. Besides using the carbonaceous material of this embodiment, the device may also have the same structure as known devices.

[0156] The function of the carbonaceous material is utilized by a device containing the carbonaceous material. The device is preferably a processing device. It should be noted that, in this specification, "processing device" is not particularly limited to any device capable of removing, adsorbing, concentrating, and recovering free residual chlorine and anionic surfactants contained in wastewater, waste liquid, and oil, etc., using the carbonaceous material of this embodiment. Such a processing device can also be a device that appropriately combines the operations of removal, adsorption, concentration, and recovery. Examples of such processing devices include: devices containing carbonaceous materials, including adsorption filters, columns, tanks or baths, pipes, water purifier filter cartridges, cylinders, and sheets (hereinafter also simply referred to as "filters containing carbonaceous materials"), packed towers, water purifiers, and other filtration devices, adsorption devices, and concentration devices. Examples of such devices include: domestic drinking water treatment devices, water treatment and purification devices in industrial processes, and wastewater treatment devices.

[0157] The apparatus, for example, includes an adsorption section for contacting free residual chlorine and anionic surfactants with carbonaceous materials. The adsorption section may also include, as needed, an adsorption material other than the carbonaceous material described in this embodiment. Examples of such adsorption materials include activated carbon, zeolite, silica gel, activated alumina, nonwoven fabric, and porous organic compounds, other than the carbonaceous material described in this embodiment.

[0158] Examples of filtration devices include: water purifiers containing carbonaceous materials, cartridge filters, membrane treatment devices, and ultrafiltration membrane devices.

[0159] In the processing device, in addition to an adsorption filter containing carbonaceous materials, other adsorption filters may also be included. Examples of such other adsorption filters include: metal filters made of stainless steel, aluminum, bronze, copper, titanium, and nickel; and resin filters made of polypropylene, polyvinyl chloride, polyvinylidene chloride, polyethylene, polyamide, and fluoropolymers.

[0160] In addition, the processing device can be intermittent or continuous, and carbonaceous materials can be used in either mode.

[0161] [Water purifier]

[0162] The water purifier of this embodiment contains the carbonaceous material of this embodiment.

[0163] Water purifiers are manufactured using carbonaceous materials or adsorption filters. By incorporating adsorption filters, water purifiers can achieve a high level of removal performance for free residual chlorine and anionic surfactants. Therefore, water purifiers are suitable for use in faucets and kitchens.

[0164] The water purifier includes a water purification filter element, which is preferably constructed using the carbonaceous material or adsorption filter described in this embodiment. The structure of such a water purification filter element can be referenced from the water purifier filter element described above.

[0165] (Water purification method)

[0166] There are no particular limitations on the water purification method, but the water purifier of this embodiment is preferred. There are no particular limitations on the water purification method; any known method can be used.

[0167] [Water purification equipment]

[0168] The water purification device of this embodiment incorporates the carbonaceous material of this embodiment. By incorporating the carbonaceous material, the water purification device can achieve a high level of removal performance for free residual chlorine and anionic surfactants.

[0169] Examples of water purification equipment include: pure water production equipment, ultrapure water equipment, and water purification plants; general industrial wastewater treatment equipment; and refining equipment for pharmaceutical and food water.

[0170] Example

[0171] The following examples and comparative examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

[0172] [Evaluation Method]

[0173] (1) Iodine adsorption capacity (iodine adsorption performance)

[0174] The iodine adsorption capacity (mg / g) of carbonaceous materials was measured and calculated.

[0175] Specifically, the iodine adsorption capacity was measured according to Japanese Industrial Standard JIS K 1474 (2014). First, according to Japanese Industrial Standard JIS Z 8801-1, the carbonaceous material was pulverized until more than 90% of it could pass through a 45μm sieve, and then dried for 3 hours in a constant-temperature dryer (Yamato Scientific Co., Ltd. DVS402 (trade name)) at 115°C. Then, it was naturally cooled to room temperature in a dryer using silica gel as a desiccant to obtain the naturally cooled carbonaceous material.

[0176] 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 distilled water was added appropriately to prepare a 0.05 mol / L iodine solution.

[0177] Next, weigh an arbitrary amount (enough to make the residual iodine concentration in the supernatant of the filtrate approximately 2.5 g / L) of the naturally cooled carbonaceous material and place it in a stoppered 100 mL Erlenmeyer flask. Then, using a full-volume pipette, add 50 mL of the aforementioned 0.05 mol / L iodine solution. At room temperature (above 20°C and below 30°C), shake the mixture at 200 vibrations per minute for 15 minutes using a shaker (TAITECCORPORATION Recipro Shaker NR-10, a medium-sized shaker, trade name) to allow the carbonaceous material to adsorb iodine, resulting in a mixture. Then, filter the mixture using a mixed cellulose ester membrane filter (Advantec ToyoKaisha, Ltd., A045A025A, trade name) to obtain the filtrate. Take 10 mL of the supernatant from the filtrate using a full-volume pipette, titrate it with 0.1 mol / L sodium thiosulfate solution (prepared by FUJIFILM Wako Pure Chemical Corporation, correction factor: 1.000), and calculate the iodine residual concentration using the following formula (I).

[0178] Iodine residual concentration (g / L) = Volume of 0.1 mol / L sodium thiosulfate solution used for titration (mL) × Correction factor of 0.1 mol / L sodium thiosulfate solution × 12.69 / 10··· (I)

[0179] The amount of iodine adsorbed per 1g of carbonaceous material can be calculated using the following formula (II).

[0180] Iodine adsorption capacity per 1g of carbonaceous material = (correction factor of 10 × 0.05 mol / L iodine solution - volume of 0.1 mol / L sodium thiosulfate solution used for titration (mL) × correction factor of 0.1 mol / L sodium thiosulfate solution) × 12.69 × 5 / mass of carbonaceous material (g) ··· (II)

[0181] It should be noted that the correction factor for the 0.05 mol / L iodine solution is calculated using equation (III).

[0182] The correction factor for 0.05 mol / L iodine solution = (volume of 0.1 mol / L sodium thiosulfate solution used for titration (mL) × correction factor for 0.1 mol / L sodium thiosulfate solution) / 10···(III)

[0183] Based on the Freundlich adsorption isotherm, an adsorption isotherm was constructed with the iodine residual concentration on the horizontal axis and the iodine adsorption amount per 1g of carbonaceous material on the vertical axis. The iodine adsorption amount per 1g of carbonaceous material (mg / g) when the iodine residual concentration is 2.5g / L was calculated. This iodine adsorption amount was taken as the iodine adsorption performance.

[0184] (2) Active Black 5-value

[0185] The Reactive Black 5 value (g / L) of carbonaceous materials was measured.

[0186] Specifically, firstly, the carbonaceous material is pulverized to approximately 10.0 μm or less, representing 50% of the cumulative particle size (D50) based on a volumetric criterion, and then dried for 3 hours in a constant-temperature dryer (Yamato Scientific Co., Ltd., DVS402 (trade name)) at 115°C. Then, it is naturally cooled to room temperature in a dryer using silica gel as a desiccant to obtain the naturally cooled carbonaceous material.

[0187] On the other hand, test solution A, containing phosphate buffer and Reactive Black 5 (manufactured by Sigma-Aldrich Co. LLC), was prepared as follows: 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 phosphate buffer (pH: 7.0). Then, Reactive Black 5 was added to 1 L of the obtained phosphate buffer at a concentration of approximately 0.5 g to 1.2 g to prepare test solution A. It should be noted that the amount of Reactive Black 5 was adjusted as follows: The amount of Reactive Black 5 added to 1 L of phosphate buffer was appropriately adjusted so that the absorbance of the solution after diluting test solution A 20 times with distilled water was in the range of 1.18 to 1.23. The absorbance was measured at a wavelength of 594 nm using a glass cuvette with a 10 mm optical path length and a UV-Vis spectrophotometer (Hitachi High-Tech Corporation U-2910 double-beam spectrophotometer). It should be noted that the solution obtained above, after diluting test solution A 20 times, was used as test solution B, and this test solution B was used for the absorbance measurement described below.

[0188] Next, in a stoppered 100mL Erlenmeyer flask, take an arbitrary mass (the amount calculated by the following formula (V) such that the residual percentage of Reactive Black 5 in the filtrate is approximately 10%) of the naturally cooled carbonaceous material described above, and add this carbonaceous material to 50mL of the above-prepared test solution A. Using a shaking thermostat (TAITEC CORPORATION MM-10 water bath shaker, trade name), shake at 150 times / minute for 5 hours in a 40°C water bath to obtain a mixture. Then, filter the mixture using a membrane filter (Advantec Toyo Kaisha, Ltd. DISMIC 25HP045AN, trade name), thereby obtaining the filtrate.

[0189] Using a 10 mm glass cuvette, the absorbance of the obtained test solution B and filtrate was measured at a wavelength of 594 nm using a UV-Vis spectrophotometer (Hitachi High-Tech Corporation U-2910 double-beam spectrophotometer). Using these absorbances, the adsorption amount of Reactive Black 5 per 1 g of carbonaceous material was calculated using the following formula (IV) (hereinafter referred to as "RB5 adsorption amount per 1 g of carbonaceous material ( / g)").

[0190] The RB5 adsorption capacity per 1g of carbonaceous material ( / g) = (Absorbance of test solution B at 594nm wavelength × 20 - Absorbance of filtrate at 594nm wavelength) / Mass of carbonaceous material (g) ... (IV)

[0191] In addition, the residual rate of Reactive Black 5 contained in the filtrate (hereinafter referred to as "RB5 residual rate (%)") is calculated by the following formula (V).

[0192] RB5 residue rate (%) = (Absorbance of filtrate at 594 nm / Absorbance of test solution B at 594 nm × 20) × 100 ... (V)

[0193] Next, a power function approximation curve was constructed with the RB5 residual rate (%) as the horizontal axis and the RB5 adsorption amount per 1g of carbonaceous material ( / g) as the vertical axis. Using its power function approximation, the adsorption amount of Reactive Black 5 at a residual rate of 1% was calculated (hereinafter referred to as "RB5 adsorption amount ( / g) at a residual rate of 1%)", and the Reactive Black 5 value (g / L) was calculated using equation (VI).

[0194] Reactive Black 5 value (g / L) = (Absorbance of test solution B at 594nm wavelength × 20 × 0.99 / Adsorption amount of RB5 at 1% RB5 residue ( / g)) / 0.05 (L) ... (VI)

[0195] It should be noted that 0.05 (L) in formula (VI) is the amount of test solution.

[0196] (3) BET specific surface area

[0197] The specific surface area (m²) of carbonaceous materials was measured using the BET method based on the N₂ adsorption isotherm at -196℃. 2 / g).

[0198] Specifically, the BET specific surface area (m²) is calculated as follows. 2 / g). Specifically, firstly, using a specific surface area / pore size distribution measuring device (BELSORP (registered trademark) – miniII (trade name) manufactured by MicrotracBEL Corp.), the carbonaceous material was heated at 250°C for 3 hours under reduced pressure (vacuum degree: below 0.1 kPa), and the nitrogen adsorption isotherm of the carbonaceous material at -196°C was measured. Using the obtained nitrogen adsorption isotherm, through BET analysis, a straight line was obtained in the region where the relative pressure P / P0 = 0.01 or higher and 0.10 or lower using a multi-point method based on the obtained curve. The BET specific surface area was then calculated from this straight line.

[0199] (4) Mesoporous ratio

[0200] Measurements using BELSORP-MAX N2 adsorption isotherm

[0201] Using a specific surface area / pore distribution measuring device (BELSORP (registered trademark) - MAX (trade name) manufactured by MicrotracBEL Corp.), the N2 adsorption isotherm was measured at 77K after heating the carbonaceous material at 300°C for 3 hours under vacuum conditions.

[0202] Measurement of pore volume with a pore size of less than 1.00 nm

[0203] The pore volume (cm³) of carbonaceous material with a pore size of less than 1.00 nm per 1 g of micropores, calculated by QSDFT method based on nitrogen adsorption isotherms. 3 The pore size distribution ( / g) was calculated as follows. Specifically, using the N2 adsorption isotherm value obtained through the above-mentioned "N2 adsorption isotherm measurement using BELSORP-MAX", the pore size distribution was calculated using N2 at 77K carbon [slit pore / cyl.pore (QSDFT Ads.model)] as the calculation model, thereby calculating the pore volume (cm³) for pore sizes below 1.00 nm. 3 / g).

[0204] Measurement of pore volume of mesopores

[0205] The pore volume (cm³) of mesopores in carbonaceous materials was measured using the BJH method based on the N₂ adsorption isotherm at -196℃. 3 / g). Specifically, using the nitrogen adsorption isotherm used in the BET specific surface area measurement described above, a curve was obtained by BJH analysis in the region where the relative pressure P / P0 = 0.385 or higher and 0.99 or lower. Based on the obtained curve, the cumulative pore volume relative to each pore size was calculated, and the cumulative pore volume up to 2.0 nm was subtracted from the cumulative pore volume up to 50.0 nm, thereby calculating the pore volume of mesopores with a pore size of 2.0 nm or higher and 50.0 nm or lower.

[0206] Calculation of mesoporous ratio

[0207] The mesoporous ratio of carbonaceous materials was calculated.

[0208] Specifically, the mesoporous ratio (A / B) of carbonaceous materials is the pore volume (cm³) using pore sizes of 1.00 nm or less. 3 / g)(A) and the pore volume of mesopores (cm³) 3 / g)(B) is calculated by the following formula (VII).

[0209] The mesoporous ratio (A / B) of carbonaceous materials = pore volume of pores with a diameter of less than 1.00 nm (A) / pore volume of mesopores (B) ... (VII)

[0210] (5) The proportion of mesopores

[0211] BJH specific surface area

[0212] The specific surface area (m²) of carbonaceous materials was measured using the BJH method based on the N₂ adsorption isotherm at -196℃. 2 / g). It should be noted that the BJH specific surface area is the specific surface area obtained by measuring the pore volume and pore size of carbonaceous materials using the BJH method.

[0213] Specifically, using the nitrogen adsorption isotherm used in the BET specific surface area calculation described above, curves were obtained through BJH analysis in the region where the relative pressure P / P0 = 0.385 or higher and 0.99 or lower. Based on the obtained curves, the pore volume of the mesopores was calculated for each pore size in the range of 2.0 nm or higher and 50.0 nm or lower, and the specific surface area was calculated using these values ​​and the following equation (VIII). The specific surface areas of each pore size were then summed to calculate the BJH specific surface area of ​​the carbonaceous material.

[0214] Ap = 2 × Vp / (rp × 10) 7 ) × 0.0001···(VIII)

[0215] It should be noted that in equation (VIII), Ap represents the specific surface area (m²) at a certain aperture. 2 / g), Vp represents the pore volume (cm³) at a certain pore size. 3 / g), rp represents its pore size (nm).

[0216] Calculation of the proportion of mesopores

[0217] The proportion (%) of mesoporous materials in carbonaceous materials was calculated.

[0218] Specifically, the proportion (%) of mesoporous materials in carbonaceous materials is determined using the BET specific surface area (m²) calculated above. 2 / g) and BJH specific surface area (m²) 2 / g) is calculated using the following formula (IX).

[0219] The proportion of mesoporous surfaces = BJH specific surface area / BET specific surface area × 100... (IX)

[0220] (6) Pore volume of mesopores

[0221] The pore volume (cm³) of mesopores in carbonaceous materials was determined by the BJH method based on the N₂ adsorption isotherm at -196℃. 3 / g) is measured and calculated by "mesopore volume measurement" in the above mesopore ratio.

[0222] (7) Total pore volume

[0223] The total pore volume (cm³) of carbonaceous materials was measured using the BJH method based on the N₂ adsorption isotherm at -196℃. 3 / g). Specifically, using the nitrogen adsorption isotherm used in the calculation of the BET specific surface area described above, a curve was obtained by BJH analysis in the region where the relative pressure P / P0 = 0.385 or higher and 0.99 or lower. Based on the obtained curve, the cumulative pore volume of pore sizes of 1.2 nm or higher and 97.4 nm or lower was calculated, and this value was taken as the total pore volume of the carbonaceous material.

[0224] (8) Filling density

[0225] The filling density (g / mL) of the carbonaceous material, as measured by the tapping method, was calculated.

[0226] Specifically, the carbonaceous material was first dried for 3 hours in a constant-temperature dryer (Yamato Scientific Co., Ltd. DVS402 (trade name)) at 115°C. Then, it was naturally cooled to room temperature in a dryer using silica gel as a desiccant to obtain the naturally cooled carbonaceous material.

[0227] Weigh out 5.0g of the naturally cooled carbonaceous material and divide it into approximately three equal parts. Place one part (about 1 / 3 of the amount) of the carbonaceous material into a 150mL graduated cylinder (inner diameter: 31mm, TSUTSUI RIKAGAKU KIKAI CO., LTD.). Stopper the graduated cylinder with a rubber stopper and place it on an automatic compaction device (TSUTSUI RIKAGAKU KIKAI CO., LTD. Powder Loss Measuring Machine TPM-3A (trade name)). Compact the cylinder for 1 minute at an amplitude of 45mm and a frequency of 35-36 times / minute. After compaction, add the remaining portion (about 1 / 3 of the amount) of the previously divided carbonaceous material to the graduated cylinder and stopper it again. Compact the cylinder for 1 minute under the same conditions. Then, add the remaining portion (about 1 / 3 of the amount) of the previously divided carbonaceous material to the graduated cylinder and stopper it again. Compact the cylinder for 30 minutes under the same conditions.

[0228] After compaction, remove the rubber stopper and use a scraper to level the upper surface of the sample inside the graduated cylinder. Visually determine the sample volume (mL) according to the graduations on the graduated cylinder. Using the measured sample volume, calculate the filling density obtained by the compaction method using the following formula (X).

[0229] Filling density (g / mL) = Mass of carbonaceous material (g) / Volume of sample measured (mL) ... (X)

[0230] (9) Free residual chlorine filtration capacity

[0231] Under the test conditions specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019, the free residual chlorine filtration capacity (L / cm³) of carbonaceous materials was calculated. 3 ).

[0232] It should be noted that the filtration capacity test was conducted by filling a 50cm section of a flowing water column (self-designed and machined, inner diameter φ50mm, height 60mm) made of DURACON (registered trademark) (polyoxymethylene) with water. 3 The carbonaceous material was used for filtration at a flow rate of 3.0 L / min.

[0233] (10) Filtration capacity of anionic surfactants

[0234] Under the test conditions specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019, the filtration capacity of carbonaceous materials using anionic surfactants was calculated (L / cm²). 3 ).

[0235] It should be noted that the filtration capacity test was conducted by filling a 50cm section of a flowing water column (self-designed and machined, inner diameter φ50mm, height 60mm) made of DURACON (registered trademark) (polyoxymethylene) with water. 3 The carbonaceous material was used for filtration at a flow rate of 3.0 L / min.

[0236] [Example 1]

[0237] (Carbonization process)

[0238] The shells of coconuts from the Philippines were carbonized at 600°C for about 2 hours to obtain carbonized materials.

[0239] (Activation treatment)

[0240] The resulting carbides were placed in a volume of 1 m³ relative to the rotary kiln. 3 Approximately 0.06 times the amount was added to a container heated to 900°C, such as... Figure 1 and Figure 2 The illustration shows a rotary kiln equipped with stirring blades inside. Then, while rotating the kiln at a speed of 3.0 rpm, gas (30.0% by volume of water vapor, 2.5% by volume of oxygen, and 67.5% by volume of nitrogen) is introduced into the kiln for activation treatment for 260 minutes, thereby obtaining the activated product.

[0241] It should be noted that in the rotary kiln used, six stirring blades are arranged around the central axis of the tube at 60° intervals. In addition, the height of the stirring blades is more than 15% and less than 25% of the inner radius of the tube, and the thickness of the stirring blades is more than 40% and less than 80% of the thickness of the tube.

[0242] (Cleaning and drying processes, etc.)

[0243] The activated material was thoroughly washed with water and dried to obtain a dried material. The dried material was then pulverized and sieved using a metal mesh sieve as specified in Japanese Industrial Standard JIS Z8801-1:2019. The particle size was adjusted so that it did not pass through 140 mesh (sieve aperture size: 106 μm, Tokyo Screen Co., Ltd.) and passed through 60 mesh (sieve aperture size: 233 μm, Tokyo Screen Co., Ltd.) to make the particle size (50% particle size in the cumulative distribution based on volume, D50) 210 μm. Thus, pulverized carbonaceous material 1 as activated carbon was obtained.

[0244] [Example 2]

[0245] In the activation process, the activation treatment is carried out for 390 minutes, otherwise the same as in Example 1, to obtain pulverized carbonaceous material 2 as activated carbon.

[0246] [Example 3]

[0247] In the activation process, the activation treatment is carried out for 420 minutes, otherwise the same as in Example 1, to obtain pulverized carbonaceous material 3 as activated carbon.

[0248] [Comparative Example 1]

[0249] (Carbonization process)

[0250] The shells of coconuts from the Philippines were carbonized at 600°C for about 2 hours to obtain carbonized materials.

[0251] (Activation treatment)

[0252] The resulting carbides were placed in a volume of 1 m³ relative to the rotary kiln. 3 Approximately 0.06 times the amount was added to a container heated to 900°C, such as... Figure 1 and Figure 2 The rotary kiln shown is equipped with stirring blades inside. Then, while the kiln is rotated at a speed of 3.0 rpm, gas (40.0% by volume of water vapor, 5.0% by volume of oxygen, and 55.0% by volume of nitrogen) is introduced into the kiln for activation treatment for 130 minutes, thereby obtaining the activated product.

[0253] It should be noted that in the rotary kiln used, six stirring blades are arranged around the central axis of the tube at 60° intervals. In addition, the height of the stirring blades is more than 15% and less than 25% of the inner radius of the tube, and the thickness of the stirring blades is more than 40% and less than 80% of the thickness of the tube.

[0254] (Cleaning and drying processes, etc.)

[0255] The activated material was thoroughly washed with water and dried to obtain a dried material. The dried material was then pulverized and sieved using a standard metal mesh as specified in Japanese Industrial Standard JIS Z8801-1:2019. The particle size was adjusted so that it did not pass through 140 mesh (sieve aperture size: 106 μm, Tokyo Screen Co., Ltd.) and passed through 60 mesh (sieve aperture size: 233 μm, Tokyo Screen Co., Ltd.) to make the particle size (50% particle size in the cumulative distribution based on volume, D50) 210 μm. Thus, pulverized carbonaceous material 4 as activated carbon was obtained.

[0256] [Comparative Example 2]

[0257] In the activation process, the activation treatment was carried out for 200 minutes. Otherwise, it was the same as Comparative Example 1, and pulverized carbonaceous material 5 as activated carbon was obtained.

[0258] [Comparative Example 3]

[0259] In the activation process, the activation treatment was carried out for 250 minutes. Otherwise, it was the same as Comparative Example 1, and pulverized carbonaceous material 6 as activated carbon was obtained.

[0260] [Comparative Example 4]

[0261] In the activation process, the activation treatment was carried out for 280 minutes. Otherwise, it was the same as Comparative Example 1, and pulverized carbonaceous material 7 as activated carbon was obtained.

[0262] [Comparative Example 5]

[0263] (Carbonization process)

[0264] Coconut shells from the Philippines were carbonized at 600°C for about 2 hours to obtain carbide 1.

[0265] The obtained carbide 1 was pulverized to an average particle size of 20 μm or more and 80 μm or less to obtain a pulverized product. Then, 1000 g of the pulverized product, a calcium chloride aqueous solution obtained by dissolving 25 g of calcium chloride (reagent grade, manufactured by FUJIFILM Wako Pure Chemical Corporation) in 57 g of water, 250 g of hard pitch (softening point: 110℃, manufactured by JFE Chemical Corporation PK-Mflake (trade name)), 80 g of creosote oil (manufactured by JFE Chemical Corporation creosote oil (Naphtalin B (trade name)), 15 g of lignin (manufactured by Nippon Paper Industries Co., Ltd. SANX (registered trademark) M (trade name)), and 73 g of water were added to a mixer (manufactured by Universe Co., Ltd., high-speed mixer DH-5 (trade name)) and mixed for 25 minutes to obtain a mixture. The resulting mixture was then fed into an extrusion granulator with an aperture of 4.0 mm (a disc granulator manufactured by Fuji Paudal Co., Ltd., trade name) and extruded to obtain granules. The granules were then carbonized at 650°C for approximately 30 minutes to obtain carbide 2.

[0266] (Activation treatment)

[0267] The resulting carbide 2 was placed in a volume of 1 m³ relative to the rotary kiln. 3 Approximately 0.06 times the amount was added to a container heated to 900°C, such as... Figure 1 and Figure 2The rotary kiln shown is equipped with stirring blades inside. Then, while the kiln is rotated at a speed of 3.0 rpm, gas (40.0% by volume of water vapor, 5.0% by volume of oxygen, and 55.0% by volume of nitrogen) is introduced into the kiln for activation treatment for 150 minutes, thereby obtaining the activated product.

[0268] It should be noted that in the rotary kiln used, six stirring blades are arranged around the central axis of the tube at 60° intervals. In addition, the height of the stirring blades is more than 15% and less than 25% of the inner radius of the tube, and the thickness of the stirring blades is more than 40% and less than 80% of the thickness of the tube.

[0269] (Cleaning and drying processes, etc.)

[0270] The activated material was washed with dilute hydrochloric acid, then thoroughly washed with water to remove residual hydrochloric acid and dried to obtain a dried material. The dried material was then pulverized and sieved using a standard metal mesh as specified in Japanese Industrial Standard JIS Z8801-1:2019. The particle size was adjusted so that it did not pass through 140 mesh (sieve aperture size: 106 μm, TokyoScreen Co., Ltd.) but passed through 60 mesh (sieve aperture size: 233 μm, Tokyo Screen Co., Ltd.) to achieve a particle size (50% particle size in the cumulative distribution based on volume, D50) of 210 μm. Thus, pulverized carbonaceous material 8, which is activated carbon, was obtained.

[0271] [Table 1]

[0272]

[0273] -Industry Applicability-

[0274] The carbonaceous material of this embodiment can be appropriately used for various applications of removing, adsorbing, concentrating, and recovering free residual chlorine and anionic surfactants with relatively large molecular sizes that can be decomposed on the surface of carbonaceous materials.

[0275] This application is based on Japanese Patent Application No. 2023-201658, filed on November 29, 2023, the contents of which are incorporated herein by reference.

[0276] - Explanation of figure labels -

[0277] A, B, C, D, E, F… stirring blades, 1… tube body, 2… direction of flow of active gas, 3… direction of rotation of tube body, 4… direction of fall of carbide, 5… carbide.

Claims

1. A carbonaceous material, characterized in that: The carbonaceous material has an iodine adsorption capacity of ≥1300 mg / g and ≤1800 mg / g, an active black 5 value of ≥1.0 g / L and ≤6.0 g / L, and a specific surface area of ​​1100 m² / g calculated by the BET method based on the N₂ adsorption isotherm at -196 °C. 2 / g or more and 1700m 2 / g or less.

2. The carbonaceous material according to claim 1, characterized in that: The ratio (A / B) of the pore volume (A) below 1.00 nm per 1g of carbonaceous material calculated by QSDFT based on nitrogen adsorption isotherms to the pore volume (B) of mesopores calculated by BJH based on N2 adsorption isotherms at -196℃ is greater than 1.0 and less than 4.

0.

3. The carbonaceous material according to claim 1, characterized in that: The proportion of mesoporous structures is above 4.8% and below 15.0%.

4. The carbonaceous material according to claim 1, characterized in that: The mesopore volume, determined by the BJH method based on the N2 adsorption isotherm at -196℃, is 0.06 cm³. 3 / g or more and 0.30cm 3 / g or less.

5. The carbonaceous material according to claim 1, characterized in that: The total pore volume, determined by the BJH method based on the N2 adsorption isotherm at -196℃, is 0.25 cm³. 3 / g or more and 1.00cm 3 / g or less.

6. The carbonaceous material according to claim 1, characterized in that: The filling density, measured by the vibration method, is above 0.30 g / mL and below 0.50 g / mL.

7. The carbonaceous material according to any one of claims 1 to 6, characterized in that: In water, the carbonaceous material is used at least to remove free residual chlorine and anionic surfactants.

8. A method for manufacturing a carbonaceous material, characterized in that: The carbonaceous material is the carbonaceous material according to any one of claims 1 to 6. The manufacturing method includes: a carbonization step of carbonizing raw materials to obtain a carbide, and an activation step of activating the carbide to obtain an activated product.

9. The manufacturing method according to claim 8, characterized in that: The manufacturing method further includes a cleaning step for cleaning the activated material.

10. The manufacturing method according to claim 8, characterized in that: The raw material is coconut shell.

11. An adsorption filter, characterized in that: The adsorption filter comprises the carbonaceous material according to any one of claims 1 to 6.

12. A water purifier filter element, characterized in that: The water purifier filter element comprises the carbonaceous material as described in any one of claims 1 to 6.

13. A water purifier, characterized in that: The water purifier comprises the carbonaceous material according to any one of claims 1 to 6.

14. A water purification device, characterized in that: The water purification equipment includes the carbonaceous material as described in any one of claims 1 to 6.

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