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

Abstract

In this carbonaceous material, the volume of pores having a pore diameter of 0.70 nm or less per 1 g of the carbonaceous material as calculated by the QSDFT method on the basis of the nitrogen adsorption isotherm is 0.16 cm3 / g to 0.30 cm3 / g, the amount of iodine adsorption is 750 mg / g to 1340 mg / g, the reactive black 5 value is 6.0 g / L to 30.0 g / L, and the specific surface area is 610 m2 / g to 1400 m2 / g as determined by the BET method on the basis of the 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, volatile organic compounds such as trihalomethanes (represented by chloroform, which is present in trace amounts in tap water) and substances with a musty odor, such as 2-methylisoborneol (2-MIB), are designated as substances to be removed in the Household Products Quality Labelling Law for household water purifiers, with the aim of removing them from tap water.

[0003] To remove such harmful substances, carbonaceous materials are commonly used in household water purifiers. For example, Patent Document 1 describes a carbonaceous material with a benzene adsorption capacity of 25% to 40%, a vitamin B12 adsorption capacity of 13.0 mg / g to 50.0 mg / g, and a mesopore volume of 0.070 cm³ calculated using the Barrett-Joyner-Halenda method based on a nitrogen adsorption isotherm. 3 / g or more and 0.150cm 3 / g or less.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2020 / 218370 Summary of the Invention

[0007] -The technical problem the invention aims to solve-

[0008] However, the pore volume and specific surface area of ​​the carbonaceous material described in Patent Document 1 are designed to remove substances with relatively large molecular sizes, such as 2-MIB, rather than substances with relatively small molecular sizes, such as trihalomethanes, such as chloroform. Therefore, although the filtration capacity for substances such as 2-MIB is high, it is difficult to remove substances with relatively small molecular sizes, such as trihalomethanes, using this carbonaceous material, and it is extremely difficult to remove chloroform, which has an even smaller molecular size among trihalomethanes.

[0009] Furthermore, 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 aims to create a household water purifier capable of removing a wider variety of harmful substances compared to previous models.

[0010] Of the five additional substances targeted for removal, anionic surfactants have a molecular size larger than 2-MIB. Conventional carbonaceous materials used in household water purifiers, such as those in Patent Document 1, were designed with pore volume and specific surface area suitable for removing molecules around 2-MIB size. Therefore, conventional carbonaceous materials have difficulty removing harmful substances with larger molecular sizes, such as anionic surfactants.

[0011] As such, after the revision of the Japanese Industrial Standard JIS Test Method, it is required that carbonaceous materials used in household water purifiers can remove a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, with equivalent performance.

[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 remove a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, with equivalent performance.

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

[0014] To achieve the above objectives, the inventors conducted in-depth research and discovered that carbonaceous materials with pore volume, iodine adsorption capacity, and active black 5 value within specific ranges can remove a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, with equivalent performance. This led to the completion of the present invention.

[0015] The present invention includes the following embodiments.

[0016] [1] A carbonaceous material, whose pore volume with a pore size of less than 0.70 nm is calculated to be 0.16 cm³ per 1 g of carbonaceous material using the QSDFT (Quenched Solid Density Functional Theory) method based on nitrogen adsorption isotherms. 3 / g or more and 0.30cm 3 The adsorption capacity of iodine is above 750 mg / g and below 1340 mg / g, the active black 5 value is above 6.0 g / L and below 30.0 g / L, and the specific surface area calculated by the BET (Brunauer-Emmett-Teller) method based on the N2 adsorption isotherm at -196℃ is 610 m² / g. 2 / g or more and 1400m 2 / g or less.

[0017] [2] Based on the carbonaceous material described in [1], the ratio (A / B) of the pore volume (A) of pores with a diameter of less than 1.00 nm per 1g of carbonaceous material calculated by QSDFT method based on nitrogen adsorption isotherm to the pore volume (B) of mesopores calculated by BJH method based on N2 adsorption isotherm at -196℃ is 3.0 or more and 8.0 or less.

[0018] [3] 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 0.030 cm³. 3 / g or more and 0.140cm 3 / g or less.

[0019] [4] Based on the carbonaceous material described in [1], the specific surface area calculated by the BET method based on the N2 adsorption isotherm at -196℃ is 610 m². 2 / g or more and 1400m 2 / g or less.

[0020] [5] Based on the carbonaceous material described in [1], the filling density measured by the tapping method is above 0.36 g / mL and below 0.60 g / mL.

[0021] [6] Based on any one of [1] to [5], the carbonaceous material is used in water to remove at least chloroform and anionic surfactants.

[0022] [7] A method for manufacturing a carbonaceous material, wherein the carbonaceous material is any one of [1] to [5], and the manufacturing method comprises: a carbonization step of carbonizing raw materials to obtain a carbide, and an activation step of activating the carbide to obtain an activated material.

[0023] [8] Based on the manufacturing method described in [7], the manufacturing method further includes a cleaning step for cleaning the activated material.

[0024] [9] Based on the manufacturing method described in [7], the raw material is coconut shell.

[0025]

[10] An adsorption filter comprising any one of [1] to [5] carbonaceous material.

[0026]

[11] A water purifier filter element, the water purifier filter element comprising any one of [1] to [5] carbonaceous material.

[0027]

[12] A water purifier comprising any one of [1] to [5] carbonaceous material.

[0028]

[13] A water purification device, the water purification device comprising any one of [1] to [5] carbonaceous materials.

[0029] -The effects of the invention-

[0030] 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 are provided, which can remove a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, with equivalent performance. Attached Figure Description

[0031] 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.

[0032] Figure 2 This is a schematic cross-sectional view used to illustrate a rotary kiln. Detailed Implementation

[0033] 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.

[0034] [Carbon-based materials]

[0035] Regarding the carbonaceous material of this embodiment, the pore volume with a pore size of 0.70 nm or less, calculated by the QSDFT method based on the nitrogen adsorption isotherm, is 0.16 cm³ per 1g of carbonaceous material. 3 / g or more and 0.30cm 3 / g or less, iodine adsorption capacity is above 750mg / g and below 1340mg / g, and Active Black 5 value is above 6.0g / L and below 67.0g / L.

[0036] Carbonaceous materials, by possessing certain characteristics, can remove a wide range of harmful substances with equivalent performance, from relatively small molecules like chloroform to relatively large molecules like anionic surfactants. In other words, the pore volume of carbonaceous materials with a pore size of less than 0.70 nm is within a specific range, thus enabling them to exhibit high adsorption performance for relatively small molecules like chloroform. Furthermore, the pore size of carbonaceous materials is controlled to be suitable for relatively large molecules like anionic surfactants, thus also enabling them to exhibit high adsorption performance.

[0037] Carbonaceous materials can appropriately adsorb chloroform and anionic surfactants.

[0038] It should be noted that with the revision of Japanese Industrial Standard JIS in 2019, volatile organic compounds other than chloroform (bromodichloromethane, dibromochloromethane, bromoform, cis-1,2-dichloroethylene and trans-1,2-dichloroethylene, tetrachloroethylene, trichloroethylene, and benzene) can be replaced by chloroform in the test methods in Appendix A of Japanese Industrial Standard JIS S3201:2019. Therefore, it can be said that if the removal performance for chloroform can be met, then the removal of other volatile organic compounds can also be achieved. In other words, carbonaceous materials can appropriately adsorb chloroform and one or more of these volatile organic compounds.

[0039] In addition, examples of anionic surfactants include alkyl sulfonates such as sodium dodecylbenzenesulfonate. Carbonaceous materials can appropriately adsorb one or more of these anionic surfactants.

[0040] In carbonaceous materials, the pore volume (cm³) of pores with a diameter of less than 0.70 nm per 1 g of carbonaceous material is calculated using the QSDFT method based on nitrogen adsorption isotherms. 3 / g (hereinafter also referred to as "pore volume with a pore size of less than 0.70 nm") is 0.16 cm³. 3 / g or more and 0.30cm 3 / g or less. By ensuring that the pore volume with a pore size of 0.70 nm or less is within the above-mentioned range, the carbonaceous material exhibits high removal performance, primarily for chloroform and other similar substances. This is achieved by setting the pore volume of the carbonaceous material with a pore size of 0.70 nm or less to 0.16 cm³. 3 With a volume of over / g, the effective pore volume for removing relatively small molecules like chloroform is sufficient, significantly improving the adsorption performance for chloroform. Furthermore, by achieving a pore volume of 0.30 cm³ for pores with a diameter of 0.70 nm or less... 3 With a volume of less than 1 g, the amount of pores suitable for substances with molecular sizes smaller than chloroform decreases, while the amount suitable for chloroform increases. Therefore, the adsorption performance for chloroform and the like is significantly improved.

[0041] 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." Micropores are smaller than mesopores and are primarily effective for adsorbing relatively small molecules such as chloroform. Mesopores, on the other hand, are effective for adsorbing relatively large molecules such as anionic surfactants.

[0042] In this specification, pore volumes with pore sizes of 0.70 nm or less, or 1.00 nm or less, are calculated using the QSDFT (Quenched Solids Density Functional Method). The QSDFT method is an analytical method for analyzing the pore size of geometrically and chemically irregular microporous / mesoporous carbon, capable of calculating pore size distributions from approximately 0.5 nm to approximately 40 nm. The QSDFT method explicitly considers the effects of surface roughness and inhomogeneity of the pores; therefore, it significantly improves the accuracy of pore size distribution analysis. For specific measurement and calculation methods of pore volumes with pore sizes of 0.70 nm or less, or 1.00 nm or less, please refer to the examples.

[0043] The preferred pore volume for pore sizes below 0.70 nm is 0.18 cm³. 3 / g or more and 0.29cm 3 / g or less, more preferably 0.20cm 3 / g or more and 0.28cm 3 Below / g, further preferably 0.22cm 3 / g or more and 0.27cm 3 / g or less. When the pore volume range with a pore size of 0.70 nm or less is within the above range, it is likely that a carbonaceous material can be obtained that maintains the removal performance for anionic surfactants, etc., while having higher adsorption performance for chloroform, etc.

[0044] The iodine adsorption capacity of carbonaceous materials is above 750 mg / g and below 1340 mg / g.

[0045] Iodine adsorption capacity is an indicator of the surface area of ​​the pores in carbonaceous materials that can physically adsorb substances with relatively small molecular sizes, such as chloroform, and anionic surfactants with relatively large molecular sizes. By keeping the iodine adsorption capacity of carbonaceous materials within the aforementioned range, the materials can maintain high removal performance for chloroform while also exhibiting high removal performance for anionic surfactants. By setting the iodine adsorption capacity to 750 mg / g or higher, the pore volume of the carbonaceous material becomes sufficiently large, significantly improving the adsorption performance for chloroform and anionic surfactants. By setting the iodine adsorption capacity to 1340 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 chloroform and anionic surfactants.

[0046] 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.

[0047] From the viewpoint of having higher removal performance for chloroform and anionic surfactants, the iodine adsorption capacity is preferably 900 mg / g or more and 1330 mg / g or less, more preferably 1000 mg / g or more and 1310 mg / g or less.

[0048] The reactive black 5 value for carbonaceous materials is above 6.0 g / L and below 67.0 g / L. Reactive black 5 is a dye represented by the following formula (1), and is also known as CI reactive black 5.

[0049] [Chemical Formula 1]

[0050]

[0051] 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 chloroform and the like, while exhibiting particularly high adsorption performance for anionic surfactants. By keeping the Reactive Black 5 value above 6.0 g / L, the cumulative pore volume of the larger pores in the carbonaceous material does not become excessively large, and the carbonaceous material can also maintain relatively small pores that are effective for chloroform and the like. Therefore, it is possible to maintain high removal performance for chloroform and the like, which have relatively small molecular sizes, while also exhibiting high removal performance for anionic surfactants and the like, which have relatively large molecular sizes. By keeping the Reactive Black 5 value below 67.0 g / L, the amount of pores in the carbonaceous material suitable for adsorbing anionic surfactants and the like, which have relatively large molecular sizes, increases. Therefore, the adsorption performance for anionic surfactants and the like is significantly improved.

[0052] 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.

[0053] The active black 5-value is preferably 6.3 g / L or higher and 50.0 g / L or lower, more preferably 6.5 g / L or higher and 40.0 g / L or lower, even more preferably 7.0 g / L or higher and 30.0 g / L or lower, and even more preferably 7.2 g / L or higher and 27.0 g / L or lower. By keeping the active black 5-value within the above range, it is preferable to obtain a carbonaceous material that maintains its removal performance for chloroform and the like while exhibiting higher adsorption performance for anionic surfactants and the like.

[0054] In carbonaceous materials, the ratio (A / B, hereinafter also referred to as "pore volume with a pore size of 1.0 nm or less") calculated per 1g of carbonaceous material by the QSDFT method based on nitrogen adsorption isotherms to the mesopore volume (B) calculated by the BJH method based on N2 adsorption isotherms at -196°C is preferably 3.0 or more and 8.0 or less, more preferably 3.5 or more and 7.5 or less, and even more preferably 4.0 or more and 7.0 or less.

[0055] Pore ​​volume with a pore size of 1.00 nm or less is an indicator of smaller pores, primarily effective for substances like chloroform with relatively small molecular sizes. Conversely, mesopore volume is an indicator of larger pores, primarily effective for substances like anionic surfactants with relatively large molecular sizes. Therefore, the mesopore ratio is an indicator of the performance balance for removing substances like chloroform and anionic surfactants.

[0056] When the mesoporous ratio is within the above-mentioned range, a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, can be removed with equivalent performance. By setting the mesoporous ratio to 3.0 or higher, the proportion of larger pores that are effective for removing anionic surfactants is sufficiently large, tending to result in high adsorption performance for anionic surfactants. By setting the mesoporous ratio to 8.0 or lower, the proportion of smaller pores that are effective for removing chloroform is sufficiently large, tending to result in high adsorption performance for chloroform. For specific methods of measuring and calculating the mesoporous ratio, please refer to the examples.

[0057] In carbonaceous materials, the preferred pore volume of mesopores, determined by the BJH method based on the N2 adsorption isotherm at -196℃, is 0.030 cm³. 3 / g or more and 0.140cm 3 / g or less, more preferably 0.035cm 3 / g or more and 0.100cm 3 Below / g, more preferably 0.040cm 3 / g or more and 0.090cm 3 / g or less.

[0058] By making the pore volume of the mesopore 0.030 cm³ 3 With a volume of 0.140 cm³ / g or more, carbonaceous materials can retain a relatively large number of pores that are effective against anionic surfactants. 3 The pore volume is below / g, thus preventing the pores of the carbonaceous material from becoming excessively large, and allowing the carbonaceous material to retain a relatively large number of pores effective for adsorbing chloroform and other substances. Therefore, when the pore volume of the mesopores is within the above range, it tends to achieve a higher level of removal performance for chloroform and other substances, as well as for anionic surfactants and other substances. For specific methods of measuring and calculating the pore volume of the mesopores, please refer to the examples.

[0059] In carbonaceous materials, the preferred 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 610 m². 2 / g or more and 1400m 2 / g or less, preferably 800m 2 / g or more and 1300m 2 / g or less, more preferably 900m 2 / g or more and 1300m 2 / g or less.

[0060] BET specific surface area is an indicator of the degree of activation of carbonaceous materials. By maintaining the BET specific surface area within the aforementioned range, carbonaceous materials tend to achieve high removal performance for anionic surfactants while maintaining removal performance for substances such as chloroform. A BET specific surface area of ​​610 m² is achieved. 2 With a specific surface area of ​​1400 m² / g or more, carbonaceous materials possess sufficient surface area to facilitate physical adsorption, thus tending to exhibit high adsorption performance for chloroform and similar substances. This is achieved by setting the BET specific surface area to 1400 m² / g. 2 With a surface area below / g, the porosity of carbonaceous materials does not become excessively large, and carbonaceous materials tend to have more pores effective for adsorbing anionic surfactants, etc. For specific methods of measuring and calculating the BET specific surface area, please refer to the examples.

[0061] In carbonaceous materials, the packing density (hereinafter also simply referred to as "packing density") measured by the tapping method is preferably 0.36 g / mL or more and 0.60 g / mL or less, more preferably 0.40 g / mL or more and 0.58 g / mL or less, and even more preferably 0.44 g / mL or more and 0.55 g / mL or less. By keeping the packing density within the above range, carbonaceous materials tend to achieve a higher level of adsorption performance for a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size. By keeping the packing density at 0.36 g / mL or more, the pores of the carbonaceous material do not become too large, and the carbonaceous material can retain more pores that are effective for chloroform and anionic surfactants. Therefore, carbonaceous materials tend to have high adsorption performance for chloroform and anionic surfactants. By keeping the packing density at 0.60 g / mL or less, sufficient pores that facilitate physical adsorption tend to exist. Therefore, carbonaceous materials tend to exhibit higher adsorption performance for substances such as chloroform and anionic surfactants. For specific methods of measuring and calculating packing density, please refer to the examples.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] Activated carbon is the preferred carbonaceous material.

[0067] [Manufacturing methods for carbonaceous materials]

[0068] The carbonaceous material of this embodiment can be obtained by known manufacturing methods.

[0069] 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 generally easier to manufacture materials with a pore volume of 0.16 cm³ per 1g of carbonaceous material, calculated using the QSDFT method based on nitrogen adsorption isotherms, where the pore size is less than 0.70 nm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0070] 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.

[0071] (Carbonization process)

[0072] The manufacturing method of carbonaceous materials includes a carbonization process that carbonizes raw materials to obtain carbides.

[0073] 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.

[0074] The raw material is preferably a natural product, more preferably coconut shell. Using such a raw material, it is easier to produce a pore volume of 0.16 cm³ per 1g of carbonaceous material, calculated using the QSDFT method based on nitrogen adsorption isotherms, where the pore size is less than 0.70 nm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0075] The raw materials may also contain additives, etc., as needed. In addition, additives, etc., may be added to the carbides as needed.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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 a pore volume of 0.16 cm³ per 1g of carbonaceous material, calculated using the QSDFT method based on nitrogen adsorption isotherms, where the pore size is less than 0.70 nm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less, are permitted. In the manufacturing method of carbonaceous materials, after pulverizing the carbide into powder, additives may be added to the powdered carbide as needed, and the mixture may be kneaded using known methods. The resulting mixture may then be shaped using known methods.

[0083] 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.

[0084] In the manufacturing methods of carbonaceous materials, known methods can be used to shape carbides, powdered carbides, mixtures, or powdered mixtures into cylindrical granules. Therefore, it is easier to manufacture carbonaceous materials with a pore volume of 0.16 cm³ per 1g, calculated using the QSDFT method based on nitrogen adsorption isotherms, where the pore size is less than 0.70 nm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0085] 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.

[0086] The carbonization process described above yields carbonized materials.

[0087] 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.

[0088] (Activation process)

[0089] The manufacturing method of carbonaceous materials includes an activation process that activates carbides to obtain activated materials.

[0090] As an activation treatment, known methods can be used.

[0091] 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.

[0092] 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.

[0093] Furthermore, by using a rotary kiln, carbides can be brought into efficient contact with active gases. As a result, it is easier to manufacture carbonaceous materials with higher adsorption performance for chloroform and anionic surfactants.

[0094] 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.

[0095] 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 levels of adsorption performance for a wide range of harmful substances, from relatively small molecules like chloroform to relatively large molecules like anionic surfactants. It should be noted that inert gases such as nitrogen can also be used simultaneously with reactive gases.

[0096] 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.

[0097] 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.

[0098] 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 micropores and mesopores. Therefore, it is preferable to manufacture carbonaceous materials with higher adsorption performance for substances such as chloroform and anionic surfactants.

[0099] 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.

[0100] When using water vapor and oxygen as active gases, the partial pressure of water vapor is more preferably 33.0% by volume or more and 47.0% by volume or less. The partial pressure of oxygen is more preferably 3.0% by volume or more and 7.0% by volume or less. 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 more preferably 46.0% by volume or more and 64.0% by volume or less. By keeping these proportions within the above ranges, it is easier to manufacture a pore volume of 0.16 cm³ per 1g of carbonaceous material with a pore size of 0.70 nm or less, calculated by the QSDFT method based on the nitrogen adsorption isotherm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0101] 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.

[0102] 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 10 minutes or more and 36 hours or less, preferably 30 minutes or more and 24 hours or less, more preferably 60 minutes or more and 12 hours or less, further preferably 100 minutes or more and 360 minutes or less, and even more preferably 120 minutes or more and 300 minutes or less. By keeping the activation time within the above range, it is easier to manufacture a pore volume of 0.16 cm³ per 1g of carbonaceous material with a pore size of 0.70 nm or less, calculated by the QSDFT method based on the nitrogen adsorption isotherm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0103] 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 a pore volume of 0.16 cm³ per 1g of carbonaceous material, calculated using the QSDFT method based on a nitrogen adsorption isotherm, where the pore size is 0.70 nm or less. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] By arranging the stirring blades inside 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.

[0112] 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.

[0113] In this way, by using a rotary kiln as the activation device, it is easier to produce a pore volume of 0.16 cm³ per 1g of carbonaceous material with a pore size of less than 0.70 nm, calculated by QSDFT based on nitrogen adsorption isotherms. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0114] The activated material is obtained through the above activation process.

[0115] 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.

[0116] (Cleaning process)

[0117] The carbonaceous material is preferably obtained through a cleaning process that cleans the activated material obtained in the activation process. Acid washing is more preferred as the cleaning method. This cleaning process tends to make it easier to produce a pore volume of 0.16 cm³ per 1g of carbonaceous material, calculated using the QSDFT method based on the nitrogen adsorption isotherm. 3 / g or more and 0.30cm 3 Carbonaceous materials with an iodine adsorption capacity of 750 mg / g or more and 1340 mg / g or less, and an active black 5 value of 6.0 g / L or more and 67.0 g / L or less.

[0118] Examples of acids used for pickling include: mineral acids such as hydrochloric acid and nitric acid; and organic acids such as formic acid and acetic acid. These acids can be used alone or in combination.

[0119] The acid concentration, pickling temperature, and time should be appropriately adjusted 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 method of drying by heating. Under drying conditions, 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, by using known methods to adjust the particle size through crushing, pulverizing, and grading; by using additional cleaning with, for example, water, organic solvents, acidic aqueous solutions, and alkaline aqueous solutions to improve purity; and by using additional heat treatment to impart durability and adjust the structure, thus 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 substances such as chloroform 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 chloroform and anionic surfactants.

[0131] [Removal methods for chloroform and anionic surfactants, etc.]

[0132] Methods for removing chloroform and anionic surfactants include a removal step of using a carbonaceous material to remove chloroform and anionic surfactants. Chloroform and anionic surfactants are removed, for example, by adsorption onto the carbonaceous material. In addition to using the carbonaceous material described in this embodiment, the removal method may also include steps identical to those in known methods for removing chloroform and anionic surfactants, adsorption methods, concentration methods, and recovery methods.

[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] Because adsorption filters contain carbonaceous materials, they can adsorb a wide range of harmful substances with equivalent performance, from chloroform, which has a relatively small molecular size, to anionic surfactants, which have a relatively large molecular size. Therefore, by installing an adsorption filter in a water purifier, for example, chloroform and anionic surfactants contained in water can be removed efficiently.

[0136] The adsorption filter preferably contains 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 chloroform 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, 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 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] (Chloroform filtration capacity)

[0146] The chloroform filtration capacity can be measured by referring to the volatile organic compound removal performance test specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019. Specifically, the chloroform concentration of the test water is set to 0.060±0.012 (mg / L), and the water temperature is set to 20℃±3℃. This test water is then passed through a carbonaceous material or adsorption filter. The test raw water and filtered water are analyzed by headspace gas chromatography. The removal rate (%) is calculated based on the concentration of the test raw 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 chloroform filtration capacity measured according to Japanese Industrial Standard JIS S3201:2019 is typically 1 cm³ / s. 3 The carbonaceous material has a volume of 5.0L or more, preferably 6.5L or more, and more preferably 8.0L 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 is 5.0L or more, preferably 8.0L or more, and more preferably 10.0L 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 substances such as chloroform 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 chloroform 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 substances such as chloroform 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 carbonaceous materials with substances such as chloroform and anionic surfactants. 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. Water purifiers include adsorption filters, which enable them to remove a wide range of harmful substances, from relatively small molecules like chloroform to relatively large molecules like anionic surfactants, with equivalent performance. Therefore, water purifiers can be appropriately used in faucet installations and kitchen applications.

[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. For example, the structure of such a water purification filter element can be referenced to 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) Pore volume with a pore size of less than 0.70 nm

[0174] Measurements using BELSORP-MAX N2 adsorption isotherm

[0175] Using a 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.

[0176] Measurement of pore volume

[0177] The pore volume (cm³) of carbonaceous material with a pore size of less than 0.70 nm per 1 g of micropores, calculated by QSDFT method based on nitrogen adsorption isotherms. 3The 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. From this, the pore volume (cm³) for pore sizes below 0.70 nm was calculated. 3 / g).

[0178] (2) Iodine adsorption capacity (iodine adsorption performance)

[0179] The iodine adsorption capacity (mg / g) of carbonaceous materials was measured and calculated.

[0180] Specifically, the iodine adsorption capacity was measured according to Japanese Industrial Standard JIS K1474 (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.

[0181] 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.

[0182] 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).

[0183] 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)

[0184] The amount of iodine adsorbed per 1g of carbonaceous material can be calculated using the following formula (II).

[0185] 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)

[0186] It should be noted that the correction factor for the 0.05 mol / L iodine solution is calculated using equation (III).

[0187] 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)

[0188] 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.

[0189] (3) Active Black 5-value

[0190] The Reactive Black 5 value (g / L) of carbonaceous materials was measured.

[0191] 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.

[0192] 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, diluted 20 times with test solution A, was used as test solution B, and this test solution B was used for the absorbance measurement described below.

[0193] 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.

[0194] 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)").

[0195] 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)

[0196] 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).

[0197] RB5 residue rate (%) = (Absorbance of filtrate at 594 nm / Absorbance of test solution B at 594 nm × 20) × 100 ... (V)

[0198] 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).

[0199] 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)

[0200] It should be noted that 0.05 (L) in formula (VI) is the amount of test solution.

[0201] (4) Mesoporous ratio

[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 volume ( / g) was calculated as follows. Specifically, using the N2 adsorption isotherm value obtained by measuring the N2 adsorption isotherm of BELSORP-MAX for pores with a pore size of 0.70 nm or less, the pore size distribution was calculated using N2at 77K carbon [slit pore / cyl.pore (QSDFT Ads.model)] as the calculation model. Thus, the pore volume (cm³) for pores with a pore size of 1.00 nm or less was calculated. 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 below, 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) Pore volume of mesopores

[0211] 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.

[0212] (6) BET specific surface area

[0213] The specific surface area (m²) of carbonaceous materials was measured using the BET method based on the N₂ adsorption isotherm at -196℃. 2 / g).

[0214] 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.

[0215] (7) Filling density

[0216] The filling density (g / mL) of the carbonaceous material, as measured by the tapping method, was calculated.

[0217] Specifically, the carbonaceous material was first dried in a constant-temperature dryer (Yamato Scientific Co., Ltd. DVS402 (trade name)) at 115°C for 3 hours. Then, it was naturally cooled to room temperature in a dryer using silica gel as a desiccant to obtain the naturally cooled carbonaceous material.

[0218] 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 in 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.

[0219] 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 (VIII).

[0220] Filling density (g / mL) = Mass of carbonaceous material (g) / Volume of sample measured (mL) ... (VIII)

[0221] (8) Chloroform filtration capacity

[0222] Under the test conditions specified in the "Test Method for Household Water Purifiers" of Japanese Industrial Standard JIS S3201:2019, the chloroform filtration capacity (L / cm³) of the carbonaceous material was calculated. 3 ).

[0223] 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.

[0224] (9) Filtration capacity of anionic surfactants

[0225] 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 ).

[0226] 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.

[0227] [Example 1]

[0228] (Carbonization process)

[0229] The shells of coconuts from the Philippines were carbonized at 600°C for about 2 hours to obtain carbonized materials.

[0230] (Activation treatment)

[0231] 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.

[0232] 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.

[0233] (Cleaning and drying processes, etc.)

[0234] 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 1, which is activated carbon, was obtained.

[0235] [Example 2]

[0236] In the activation process, the activation treatment is carried out for 200 minutes, otherwise the same as in Example 1, to obtain pulverized carbonaceous material 2 as activated carbon.

[0237] [Example 3]

[0238] In the activation process, the activation treatment is carried out for 250 minutes, otherwise the same as in Example 1, to obtain pulverized carbonaceous material 3 as activated carbon.

[0239] [Example 4]

[0240] In the activation process, the activation treatment is carried out for 280 minutes, otherwise the same as in Example 1, to obtain pulverized carbonaceous material 4 as activated carbon.

[0241] [Comparative Example 1]

[0242] (Carbonization process)

[0243] The shells of coconuts from the Philippines were carbonized at 600°C for about 2 hours to obtain carbonized materials.

[0244] (Activation treatment)

[0245] 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 1 minute, thereby obtaining the activated product.

[0246] (Cleaning and drying processes, etc.)

[0247] 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, Nishimura Kinzoku Co., Ltd.) but passed through 60 mesh (sieve aperture size: 233 μm, Nishimura Kinzoku 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 5, which is activated carbon, was obtained.

[0248] [Comparative Example 2]

[0249] In the activation process, gases (30.0% by volume of water vapor, 2.5% by volume of oxygen and 67.5% by volume of nitrogen) are introduced into the kiln and activated for 260 minutes. Otherwise, it is the same as in Example 1, and pulverized carbonaceous material 6 as activated carbon is obtained.

[0250] [Comparative Example 3]

[0251] In the activation process, gases (30.0% by volume of water vapor, 2.5% by volume of oxygen and 67.5% by volume of nitrogen) were introduced into the kiln and activated for 390 minutes. Otherwise, it was the same as in Example 1, and pulverized carbonaceous material 7 as activated carbon was obtained.

[0252] [Table 1]

[0253]

[0254] -Industry Applicability-

[0255] The carbonaceous material of this embodiment can be suitably used for various applications of removing, adsorbing, concentrating, and recovering a wide range of harmful substances, from chloroform with relatively small molecular size to anionic surfactants with relatively large molecular size, with equivalent performance.

[0256] This application is based on Japanese Patent Application No. 2023-201659, filed on November 29, 2023, the contents of which are incorporated herein by reference.

[0257] - Explanation of figure labels -

[0258] 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. A carbonaceous material, characterized in that: Based on the nitrogen adsorption isotherm, the QSDFT method calculated the pore volume per 1g of carbonaceous material with a pore size of less than 0.70nm to be 0.16cm³. 3 / g or more and 0.30cm 3 The adsorption capacity of iodine is above 750 mg / g and below 1340 mg / g, the active black 5 value is above 6.0 g / L and below 30.0 g / L, and the specific surface area calculated by the BET method based on the N2 adsorption isotherm at -196℃ is 610 m² / g. 2 / g or more and 1400m 2 / g or less.

2. The carbonaceous material according to claim 1, characterized in that: The ratio (A / B) of the pore volume (A) of carbonaceous material with a pore size of less than 1.00 nm 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 3.0 and less than 8.

0.

3. 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 0.030 cm³. 3 / g or more and 0.140cm 3 / g or less.

4. The carbonaceous material according to claim 1, characterized in that: The filling density, measured by the vibration method, is above 0.36 g / mL and below 0.60 g / mL.

5. The carbonaceous material according to any one of claims 1 to 4, characterized in that: In water, the carbonaceous material is used at least to remove chloroform and anionic surfactants.

6. 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 4. 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.

7. The manufacturing method according to claim 6, characterized in that: The manufacturing method further includes a cleaning step for cleaning the activated material.

8. The manufacturing method according to claim 6, characterized in that: The raw material is coconut shell.

9. An adsorption filter, characterized in that: The adsorption filter comprises the carbonaceous material according to any one of claims 1 to 4.

10. 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 4.

11. A water purifier, characterized in that: The water purifier comprises the carbonaceous material according to any one of claims 1 to 4.

12. A water purification device, characterized in that: The water purification equipment includes the carbonaceous material as described in any one of claims 1 to 4.

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