JP2019136627A - Granular activated carbon manufacturing method and filtration cartridge manufacturing method - Google Patents

Abstract

To provide a manufacturing method which allows easy adjustment of the size of obtained granular activated carbon.SOLUTION: A granular activated carbon manufacturing method includes: a molding step S2 of molding into a granular shape a suspension 100 containing 11-43 pts. wt. of cellulose nanofibers 102 based on 100 pts. wt. of a liquid dispersion medium 101; and an activation step S3 of obtaining granular activated carbon 120 by heating and activating the granular suspension 110. A manufacturing method of a filtration cartridge (20) in which the granular activated carbon 120 is accommodated in an accommodation portion (33) having an inflow portion (32) and an outflow portion 75 for a fluid (W) includes the molding step S2, the activation step S3, and an accommodation step S4 of accommodating the granular activated carbon 120 in the accommodation portion (33).SELECTED DRAWING: Figure 5

Description

  The present invention relates to a technique for producing granular activated carbon and a filtration cartridge.

  Patent Document 1 discloses a water purification cartridge in which activated carbon, an ion removing member, and a hollow fiber membrane are stored at different positions. Activated carbon removes trace components such as free residual chlorine and organic substances contained in tap water. The ion removing member removes metal ions contained in tap water. The hollow fiber membrane removes turbid components such as iron rust contained in tap water.

  When using a large activated carbon such as coconut shell activated carbon as the activated carbon for the water purification cartridge, it is necessary to pulverize the original activated carbon. When activated carbon is pulverized, activated carbon in which particles of a wide range from large particles to small particles are mixed is obtained. When this activated carbon is accommodated in the accommodating portion of the water purification cartridge, small particles in the activated carbon accumulate on the upper surface of the filtration layer or enter into the gaps between the large particles.

JP 2008-194596 A

  When small particles in the activated carbon accumulate on the upper surface of the filtration layer, clogging is likely to occur when water is passed through the water purification cartridge, and as a result, water does not flow easily. Further, when small particles enter the gaps between the large particles, the gaps are blocked, and the water flow resistance inside the filtration layer becomes non-uniform. Since it is difficult for water to flow in a portion having a high water flow resistance inside the filtration layer, the contact efficiency between the activated carbon and the water decreases, and the water purification performance decreases accordingly. In order to improve the water purification performance, it is necessary to separately classify the activated carbon.

In addition, the above problems also exist in filtration cartridges other than the water purification cartridge, such as filtration cartridges for air purifiers.
This invention discloses the manufacturing method which makes it easy to adjust the magnitude | size of the granular activated carbon obtained.

The method for producing granular activated carbon of the present invention comprises a molding step of molding a suspension containing 11 to 43 parts by weight of cellulose nanofibers into 100 parts by weight of a liquid dispersion medium,
And an activation step of obtaining granular activated carbon by heating and activating the granular suspension.

Further, the present invention is a method for manufacturing a filtration cartridge in which granular activated carbon is accommodated in an accommodating portion having a fluid inflow portion and an outflow portion,
A molding step of molding a suspension containing 11 to 43 parts by weight of cellulose nanofibers into 100 parts by weight of the liquid dispersion medium;
An activation step of obtaining the granular activated carbon by heating and heating the granular suspension;
A housing step of housing the granular activated carbon in the housing portion.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which makes it easy to adjust the magnitude | size of the granular activated carbon obtained can be provided.

The figure which shows typically the example of the system kitchen incorporating the water faucet with a water purification function. (A) is a perspective view showing an example of a water discharge head with a water purification cartridge attached thereto, and (b) is a perspective view showing an example of a water discharge section with a water purification cartridge attached thereto. The longitudinal cross-sectional view which shows the example of a water purification cartridge. The disassembled perspective view which shows the example of a water purification cartridge. The flowchart which shows typically the example of the manufacturing method of the filtration cartridge containing the manufacturing method of granular activated carbon. (A)-(e) is a figure which shows typically the example of the apparatus which shape | molds suspension into a granule. The figure which shows typically the example of the apparatus which rounds granular suspension. The graph which shows the equilibrium adsorption achievement rate of chloroform with respect to contact time.

  Embodiments of the present invention will be described below. Of course, the following embodiments are merely examples of the present invention, and all the features shown in the embodiments are not necessarily essential to the means for solving the invention.

(1) Summary of technology included in the present invention:
First, the outline | summary of the technique included in this invention is demonstrated with reference to the example shown by FIGS. In addition, the figure of this application is a figure which shows an example typically, The expansion ratio of each direction shown by these figures may differ, and each figure may not match. Of course, each element of the present technology is not limited to the specific example indicated by the reference numeral.
In the present application, the numerical range “Min to Max” means a minimum value Min or more and a maximum value Max or less. The composition ratio represented by the chemical formula indicates the stoichiometric ratio, and the substance represented by the chemical formula includes those that deviate from the stoichiometric ratio.

[Aspect 1]
The manufacturing method of the granular activated carbon which concerns on 1 aspect of this technique WHEREIN: Molding process S2 which shape | molds the suspension liquid 100 containing 11-43 weight part cellulose nanofiber 102 with respect to 100 weight part liquid dispersion medium 101, And the activation process S3 which obtains the granular activated carbon 120 by heating and activating the said granular suspension 110 is included.

  The suspension 100 containing 11 to 43 parts by weight of the cellulose nanofibers 102 with respect to 100 parts by weight of the liquid dispersion medium 101 has fluidity due to the liquid dispersion medium 101 and high viscosity due to the cellulose nanofibers 102. Have. For this reason, the suspension 100 can be easily formed into a granular shape. When the formed granular suspension 110 is heated and activated, granular activated carbon 120 is obtained. Since the object to be molded in the molding step S2 is the highly viscous suspension 100 having fluidity, it is easy to adjust the size of the granular suspension 110. Here, if the granular suspension 110 obtained in the molding step S2 is made larger, the granular activated carbon 120 tends to be larger, and if the granular suspension 110 obtained in the molding step S2 is made smaller, the obtained granular activated carbon 120 tends to be larger. The activated carbon 120 tends to be small. That is, since the size of the granular activated carbon 120 obtained is adjusted by adjusting the size of the granular suspension 110, this embodiment provides a manufacturing method that makes it easy to adjust the size of the obtained granular activated carbon. be able to.

Here, the “granular” is not limited to a perfect sphere, but an oval, oblate, elliptical columnar shape including a cylindrical shape, a cylindrical shape including a cylindrical shape, an elliptical pyramid shape including a conical shape, a rectangular parallelepiped shape including a cubic shape, A tetrahedral shape, a polygonal column shape, a polygonal pyramid shape, a shape obtained by deforming these shapes, and the like are included. That is, the above-mentioned various shapes are included in the shape of the granular suspension and granular activated carbon.
Suspension means a dispersion system in which solid particles as a dispersoid are dispersed in a liquid dispersion medium, and may be in the form of a wet powder. When the suspension medium, ie the dispersion medium, is a liquid, this medium is a liquid dispersion medium. The suspension of aspect 1 may contain one or more additives such as a binder as long as the effects of the present technology are not impaired.
In the activation step, granular activated carbon may be obtained by performing infusibilization treatment for heating and carbonizing the granular suspension, and performing activation treatment for heating and activating the obtained granular carbide. This case is also included in the activation step of aspect 1.
Note that the above-mentioned supplementary notes are also applied to the following aspects.

[Aspect 2]
As illustrated in FIGS. 6A to 6E, in the molding step S2, means for aligning the suspension 100 into particles having a predetermined size (for example, granulators 210, 220, 230, 240, 250). ) To form the suspension 100 into a granular shape. When the size of the obtained granular suspension 110 is uniform, the size of the granular activated carbon 120 obtained is uniform, and the amount of granular activated carbon filled per unit volume is increased. For example, when the granular activated carbon 120 is filled in a housing portion (for example, the inner side 33 of the outer nonwoven fabric) of the filtration cartridge (for example, the water purification cartridge 20), the filling amount of the granular activated carbon 120 can be increased. The filtration using granular activated carbon requires gaps between the granular activated carbons. To make the resistance uniform when the fluid passes through the aggregate of granular activated carbons, the gaps between the granular activated carbons should be as uniform as possible. Is good. As the sizes of the granular activated carbons become uniform, the gaps between the granular activated carbons are made uniform, so that the resistance when the fluid passes through the aggregate of the granular activated carbons is made uniform. Therefore, this aspect can provide a method for producing granular activated carbon that improves purification performance.
Here, the means for aligning the suspension into particles of a predetermined size includes means for extruding the suspension in a line from the die and cutting it at equal intervals, forming the suspension into a plate shape, vertically and horizontally, etc. Means for cutting at intervals, various granulators, etc. are included. This appendix also applies to the following aspects.

[Aspect 3]
As illustrated in FIG. 7, the forming step S2 may include a step of rounding the granular suspension 110 (for example, a rounding step S22). When the granular suspension 110 has a rounded shape, the resulting granular activated carbon 120 has a rounded shape. For this reason, the amount of granular activated carbon per unit volume can be increased. For example, when the granular activated carbon 120 is filled in the accommodating portion (33) of the filtration cartridge (20), the filling amount of the granular activated carbon 120 can be increased. In addition, that a granular activated carbon becomes a rounded shape means that a granular activated carbon approaches the shape of a true sphere. The closer the granular activated carbon is to the shape of a true sphere, the more uniform the gaps between the granular activated carbons, and thus the resistance when the fluid passes through the aggregate of granular activated carbons is made uniform. Therefore, this aspect can also provide a method for producing granular activated carbon that improves purification performance.
Here, rounding the granular suspension is a process in which at least a part of a corner of the granular suspension is rounded or at least a part of a portion having a small radius of curvature has a larger radius of curvature. Well, it is not limited to making the granular suspension spherical.
The step of rounding the granular suspension includes a step of rolling and rolling the granular suspension, a step of rolling the granular suspension by wind, and the like. This appendix also applies to the following aspects.

[Aspect 4]
By the way, the manufacturing method of the filtration cartridge (for example, water purification cartridge 20) which concerns on 1 aspect of this technique is the formation process S2, the activation process S3, and the inflow part (for example, the outer surface 32 of an outer nonwoven fabric) of the fluid (for example, water W). And the accommodating process S4 which accommodates the said granular activated carbon 120 in the accommodating part (for example, the inner side 33 of an outer side nonwoven fabric) which has the outflow part 75 is included. Since the size of the granular activated carbon 120 to be obtained is adjusted by adjusting the size of the granular suspension 110 as in the case of the first aspect, this embodiment is a filter cartridge that makes it easy to adjust the size of the obtained granular activated carbon. A manufacturing method can be provided.

(2) Specific example of a water purifier having a filtration cartridge containing granular activated carbon:
First, with reference to the example shown in FIGS. 1-4, the example of the water purifier which has the filtration cartridge which accommodated the granular activated carbon obtained according to the aspect mentioned above is demonstrated.

  FIG. 1 schematically illustrates a system kitchen SY1 incorporating a faucet 1 with a water purification function (an example of a water purifier). The water purifier in this example is a so-called spout-in water purifier, and exhibits a water purifying function by a water purifying cartridge 20 (an example of a filtration cartridge) containing granular activated carbon obtained by the manufacturing method of this specific example. The detail of the manufacturing method of granular activated carbon is mentioned later. Note that the description of the positional relationship of each unit is merely an example. Therefore, change the left / right direction to the up / down direction or the front / rear direction, change the up / down direction to the left / right direction or the front / rear direction, change the front / rear direction to the left / right direction or the up / down direction, or change the rotation direction to the reverse direction. It is also included in the present technology. Further, the same direction, position, etc. are not limited to exact matching, but include deviation from exact matching due to an error.

  In the system kitchen SY1 shown in FIG. 1, a cabinet 802, a concave sink 803, a faucet 1, and the like are incorporated in a horizontally extending counter 801. The faucet 1 includes a faucet body 2 that is attached vertically through a sink 803 disposed on the lower surface of the counter 801, and a water discharge head (an example of a water purifier body) 10 that can be attached to and detached from the faucet body 2. And an opening lever 3 that can be tilted with respect to the faucet body 2. In addition, the water purifier main body of this specific example means the water discharge head 10 excluding the water purification cartridge 20. The water discharge head 10 is connected to a hose 19 (an example of a water inlet) that is passed through the faucet body 2. The hose 19 supplies tap water from a water supply pipe (not shown) to the water discharge head 10 when the opening lever 3 is open. When the water discharge head 10 is removed from the faucet body 2, the hose 19 is pulled out from the faucet body 2. When the water discharge head 10 is attached to the faucet body 2, the hose 19 is drawn into the faucet body 2. The tap opening lever 3 is configured to supply tap water to the water discharge head 10 via the hose 19 when in the open position (for example, a position above the tilting range), and to be in the closed position (for example, a position below the tilting range). The supply of tap water to the water discharge head 10 is stopped when

  FIG. 2A illustrates the water discharge head 10 to which the water purification cartridge 20 is attached as a partial cross-sectional view. FIG. 2B illustrates a water discharge portion to which the water purification cartridge 20 is attached. A water discharge head 10 shown in FIG. 2 has a water discharge part 11 on the tip side, that is, a downstream side in the water flow direction D1, and a grip part 18 that is attached to and detached from the faucet body 2, and is a replacement part. A water purification cartridge 20 is incorporated. Inside the water discharge head 10, the outside of the water purification cartridge 20 is a tap water passage 10a through which tap water flows. The water discharger 11 is provided with a connection port 12 with the water purification cartridge 20 and a switching lever 15 that can be switched between discharging purified water from the connection port 12 or discharging tap water from the tap water passage 10a. . The switching lever 15 stops the tap water when it is on the purified water side (for example, one end side of the rotation range) and discharges the purified water from the water outlet 13 of the water discharger 11 and is on the tap water side (for example, the other end side of the rotation range). Water purification is stopped and tap water is discharged from the water outlet 13 of the water discharger 11.

As shown in FIG. 2, a male screw 11 a is formed on the outer periphery of the end portion on the upstream side of the water discharge portion 11, and a female screw 18 a is formed on the inner periphery of the end portion on the downstream side of the grip portion 18. The gripping part 18 can be attached to the water discharging part 11 by screwing both the screws 11a, 18a, and the gripping part 18 can be removed from the water discharging part 11 by removing the female screw 18a from the male screw 11a.
Of course, the water discharge head to which the water purification cartridge can be attached is not limited to the water discharge head 10 shown in FIGS. 1 and 2, and various configurations are possible.

  FIG. 3 illustrates a longitudinal section passing through the central axis AX1 of the replaceable water purification cartridge 20. FIG. 4 illustrates the water purification cartridge 20 in an exploded manner. The water purification cartridge 20 includes a hollow fiber membrane case 70 having an adsorbent portion 30 in which an adsorbent AH1 containing granular activated carbon is accommodated, and an accommodating portion 71 of a hollow fiber membrane bundle BH1 in which a plurality of hollow fiber membranes H1 are bundled. Yes. The adsorbent part 30 is disposed on the upstream side in the flow direction D1, and the hollow fiber membrane case 70 is disposed on the downstream side in the flow direction D1. The tap water W (an example of fluid) that has flowed into the water purification cartridge 20 enters the adsorbent portion 30 and the hollow fiber membrane bundle housing portion 71 of the hollow fiber membrane case 70 in this order, and is purified.

  The hollow fiber membrane bundle housing portion 71 is inserted and attached to the water discharge portion 11 in the flow-down direction D1. At this time, the outflow portion 75 of the hollow fiber membrane bundle housing portion 71 is inserted into the connection port 12 of the water discharge portion 11. The water purification cartridge 20 is fixed to the water discharger 11 with the adsorbent part 30 and the outer fitting part 80 of the hollow fiber membrane case 70 coming out of the water discharger 11. The water purification cartridge 20 is removed by drawing it out of the water discharger 11 in the direction opposite to the flow-down direction D1 (extending direction D2). Accordingly, the water purification cartridge 20 can be attached to and detached from the water discharge head 10.

  The adsorbent part 30 has a cylindrical outer nonwoven fabric 31, an outer cap 38, a cylindrical inner nonwoven fabric 41, an inner cap 48, and an inner fitting member 50, and contains an adsorbent AH1 containing activated carbon. Activated carbon removes trace components such as free residual chlorine and organic matter contained in raw water. Although details will be described later, granular activated carbon derived from cellulose nanofiber is used as the activated carbon.

  The adsorbent AH1 may include an ion exchanger or the like as long as the effects of the present technology are not impaired. As the ion exchanger, an inorganic ion exchanger such as zeolite (zeolite), an ion exchange resin such as a cation exchange resin or an anion exchange resin, a chelate compound such as a chelate resin, a combination thereof, or the like can be used. Zeolite and cation exchange resin adsorb metal ions by a cation exchange function. The chelate compound selectively adsorbs a specific metal ion through a chelate bond. That is, zeolite, a cation exchange resin, and a chelate compound function as a metal treating agent. Moreover, the ion exchanger of shapes, such as a granular form, a fiber form, and a powder form, can be used for an ion exchanger.

  The outer nonwoven fabric 31 is formed in a cylindrical shape, and water can flow in the inner and outer directions, that is, in the radial direction centered on the virtual axis AX1 passing through the center of the water purification cartridge 20. Of course, the outer nonwoven fabric 31 is not limited to a cylindrical shape. The downstream end portion 31 b of the outer nonwoven fabric 31 is inserted into and fixed to the outer fitting portion 80 of the hollow fiber membrane case 70. The adsorbent AH1 is accommodated in the inner side 33 of the outer nonwoven fabric 31 inserted into the outer fitting portion 80 (an example of the accommodating portion). An outer cap 38 is inserted into the upstream end 31 a of the outer nonwoven fabric 31, is bent inward, and is welded to the outer surface 38 a of the outer cap 38. Thereby, the opening 31o of the edge part 31a of the outer side nonwoven fabric 31 is obstruct | occluded. In addition, you may join the edge part 31a of the outer side nonwoven fabric 31, and the outer cap 38 with an adhesive etc. instead of welding.

  The inner nonwoven fabric 41 is formed in a cylindrical shape thinner than the outer nonwoven fabric 31, and water can flow inward and outward. The downstream end portion 41 b of the inner nonwoven fabric 41 is inserted into and fixed to the communication port 74 of the hollow fiber membrane case 70. The inner cap 48 is fitted into the upstream end 41 a of the inner nonwoven fabric 41. Thereby, the opening 41o of the edge part 41a of the inner side nonwoven fabric 41 is obstruct | occluded. Adsorbent AH1 is present outside the inner nonwoven fabric 41. The inner side 43 of the inner side nonwoven fabric 41 is connected to the hollow fiber membrane bundle accommodating part 71 via the connection port 74, and becomes a passage of water from which the substance to be adsorbed has been removed.

  The nonwoven fabrics 31 and 41 can be made of thermoplastic resin (synthetic resin) fibers such as polyolefin fibers, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, and combinations thereof.

The inner fitting member 50 is a sealing member formed in an annular shape and has flexibility. As shown in FIG. 3, the inner fitting member 50 is inserted into the inner side 33 of the outer nonwoven fabric 31, and holds the end portion 31 b on the downstream side of the outer nonwoven fabric 31 with the outer fitting portion 80 of the hollow fiber membrane case 70. . Thereby, the downstream end portion 30 b of the adsorbent portion 30 is held by the outer fitting portion 80 of the hollow fiber membrane case 70. As the material of the internal fitting member 50, acrylonitrile butadiene styrene copolymer (ABS) resin, acrylonitrile styrene copolymer (AS) resin, polyolefin resin, thermoplastic elastomer, a combination thereof, or the like can be used.
The fixing means between the outer fitting portion 80 and the adsorbent portion 30 is not limited to the seal member, and may be an adhesive or the like.

The hollow fiber membrane case 70 is formed with a hollow fiber membrane bundle housing portion 71 in which the hollow fiber membrane bundle BH1 is accommodated in an internal space 70c and an outer fitting portion 80 of the end portion 30b of the adsorbent portion 30. The hollow fiber membrane bundle BH1 removes fine turbidity of about 0.1 μm or more, iron rust and general bacteria from the water to be treated. For example, when a hollow fiber membrane bundle BH1 in which a plurality of hollow fiber membranes H1 bent in a U-shape are bundled is inserted into the internal space 70c of the hollow fiber membrane case 70 from the closed end BH1a, and the open end BH1b is fixed with a potting agent. A hollow fiber membrane case 70 in which the hollow fiber membrane bundle BH1 is accommodated is formed. The hollow fiber membrane bundle housing portion 71 is formed with a communication port 74 that faces the closed end BH1a of the hollow fiber membrane bundle BH1. The open end BH1b fixed to the accommodating portion 71 in the hollow fiber membrane bundle BH1 is a water outflow portion 75. The outer fitting portion 80 extends from the hollow fiber membrane bundle housing portion 71 to the adsorbent portion 30 side (extending direction D2), and the downstream end portion 31b of the outer nonwoven fabric 31 is inserted.
For the hollow fiber membrane case 70 and the caps 38 and 48, a thermoplastic resin (synthetic resin) such as ABS resin, AS resin, polyolefin, or a combination thereof can be used.

Next, with reference to FIGS. 1-3, the flow of the water W (example of fluid) of the water discharge head 10 to which the water purification cartridge 20 was attached is demonstrated.
When the switching lever 15 is on the purified water side, the tap water W from the hose 19 shown in FIG. 1 enters the inner side 33 from the outer side 32 (example of the inflow portion) of the outer nonwoven fabric 31 as shown by the arrows in FIG. The adsorbent AH1 removes the substance to be adsorbed (for example, trace components such as free residual chlorine and organic substances). The water inside the outer nonwoven fabric 33 enters the inner 43 of the inner nonwoven fabric 41 and enters the internal space 70 c of the hollow fiber membrane bundle housing portion 71 through the communication port 74. The water in the internal space 70c moves from the closed end BH1a to the open end BH1b in the hollow fiber membrane bundle BH1, and fine turbidity of about 0.1 μm or more, iron rust, and general bacteria are removed. The purified water from the open end BH 1 b, that is, the outflow part 75 is discharged from the water discharge part 11. When the switching lever 15 is on the tap water side, the tap water from the hose 19 flows in the flow direction D <b> 1 outside the water purification cartridge 20 in the water discharge head 10 and is discharged from the water discharge unit 11.

  When removing the used water purification cartridge 20 from the water discharging head 10, first, the gripping portion 18 is turned in a direction to release the screwing of the screws 11 a and 18 a, and the gripping portion 18 is removed from the water discharging portion 11. At this time, as shown in FIG. 2 (b), the adsorbent part 30 and the external fitting part 80 in the water purification cartridge 20 come out from the water discharge part 11. Next, what is necessary is just to grasp the outer fitting part 80 and to draw out the water purification cartridge 20 from the water discharge part 11 in the direction (extending direction D2) opposite to the flow-down direction D1. When the new water purification cartridge 20 is attached to the water discharge head 10, the outer fitting portion 80 may be grasped and the water purification cartridge 20 may be pushed into the water discharge portion 11 from the outflow portion 75 in the flow-down direction D1. As shown in FIG. 2A, when the outflow portion 75 is inserted into the connection port 12 of the water discharge portion 11, the water purification cartridge 20 is attached to the water discharge portion 11.

(3) Specific example of a method for producing a filtration cartridge including a method for producing granular activated carbon:
FIG. 5 schematically shows an example of a method for producing a filtration cartridge including a method for producing granular activated carbon derived from cellulose nanofiber (hereinafter also referred to as CNF). The method for producing granular activated carbon shown in FIG. 5 includes a suspension preparation step S1, a forming step S2, and an activation step S3. The manufacturing method of the water purification cartridge 20 shown in FIG. 5 (an example of a filtration cartridge) includes the above-described steps S1 to S3 and a housing step S4. In the suspension preparation step S1, a suspension 100 containing 11 to 43 parts by weight of CNF 102 is prepared for 100 parts by weight of the liquid dispersion medium 101. In the forming step S2, the suspension 100 is formed into a granular shape. In the activation step S3, granular activated carbon 120 is obtained by heating and activating the granular suspension 110. In the housing step S4, the granular activated carbon 120 is housed inside the outer nonwoven fabric 31 (an example of a housing portion).

If the CNF suspension 100 is prepared, the suspension preparation step S1 may be omitted. The molding step S2 may include a preliminary molding step S21 and a rounding step S22. The activation step S3 may include an infusibilization step S31 and a main activation step S32.
In the following description, “granular suspension” is also referred to as “granular suspension”.

(3-1) Example of suspension preparation step S1:
As the liquid dispersion medium 101, water, alcohol such as methanol or ethanol, an alcohol aqueous solution, a polar organic solvent, or the like can be used. CNF is composed of polysaccharide cellulose having a large number of hydroxyl groups on the surface, which are highly polar functional groups, and exhibits extremely high hydrophilicity. Accordingly, water having a large polarity is particularly preferable as a liquid dispersion medium because CNF can be easily dispersed.

  As CNF102, nanofibers obtained by defibrating plant fibers such as pulp, microfibrillated cellulose derived from bacteria, and the like can be used. Of course, you may use a commercial item for CNF. CNF may also be chemically modified cellulose nanofibers such as carboxymethylcellulose nanofibers. For CNF, for example, a cellulose fiber having a fiber diameter (diameter) of 3 to 400 nm and a fiber length of 50 nm to 50 μm can be used.

  CNF102 can be manufactured by wet-grinding the cellulose raw material which is a material containing a cellulose, for example. Wet pulverization means pulverization performed in the presence of a liquid dispersion medium (preferably water). Woody materials, herbaceous materials, seaweed materials, bacterial materials, animal materials, and the like can be used as the cellulose raw material. Woody materials include coniferous materials and hardwood materials, and include wood chips, wood powder, crushed wood, crushed wood, wood pulp, combinations thereof, and the like. Bamboo etc. may be contained in the woody material. Herbaceous materials include hemp, bagasse, rice straw, rice straw, straw, cotton, herbaceous pulp, combinations thereof, and the like. As the cellulose raw material, wood chips generated at furniture factories and construction sites, pulverized waste materials, pulverized waste materials such as furniture and building materials, etc. can be used, and may be pulped. It does not have to be converted.

  For example, as disclosed in JP-A-2015-86377, for example, as disclosed in JP-A-2015-86377, an apparatus for wet-grinding a cellulose raw material includes a ball mill, a bead mill, a rod mill, a disk mill, a ring mill, a high-pressure homogenizer, a shear mixer, a kneader, a planetary rotary mixer, One or more selected from a jet mill, an attrition mill, and a high-speed mixer can be used. These machines can apply a shearing force to the cellulose raw material to fibrillate the cellulose raw material. Ball mills, bead mills, rod mills, disk mills, and the like are mills that use a processing medium. The strong mechanical energy from the treatment medium fibrillates (beats) the cellulose raw material swollen with water and sufficiently fibrillates it.

The suspension 100, which is a dispersion system in which the CNF 102 is dispersed in the liquid dispersion medium 101 as a dispersoid, has fluidity due to the presence of the liquid dispersion medium, but exhibits high viscosity due to the thin fibers of CNF. In the suspension 100, the weight ratio of the CNF 102 to the liquid dispersion medium 101 is 11 to 43 parts by weight (preferably 14 to 30 parts by weight) of CNF with respect to 100 parts by weight of the liquid dispersion medium 101. The reason why CNF is set to 11 parts by weight or more is to maintain the shape of the granular suspension 110 by increasing the viscosity of the suspension 100 to such an extent that it can be molded. When CNF is 14 parts by weight or more, the viscosity of the suspension 100 is further increased, and the shape retention of the granular suspension 110 is further improved. The reason why the CNF is set to 43 parts by weight or less is to increase the fluidity of the suspension 100 to a formable level and form the suspension 100 into a granular shape. When CNF is 30 parts by weight or less, the fluidity of the suspension 100 is further improved, and the moldability of the suspension 100 is further improved.
For the same reason, the water content of the suspension 100 not containing the additive 103 is preferably 70 to 90% by weight, and more preferably 77 to 87% by weight. The blending ratio of CNF102 in the suspension 100 is preferably 10 to 30% by weight, and more preferably 13 to 23% by weight.

The suspension 100 may include one or more additives 103 that are not included in the liquid dispersion medium 101 and the CNF 102 as long as the effects of the present technology are not impaired. As the additive 103, a binder such as a thermoplastic binder, a thermosetting binder, an inorganic binder, a water-soluble binder, or a natural organic binder, an antibacterial agent, an antiseptic, a fungicide, a colorant, a filler, or the like may be used. it can. The additive 103 is not limited to hydrophilicity (including water solubility), and may be hydrophobic.
Thermoplastic binders include polyolefin resins such as polyethylene (PE) resin and polypropylene (PP) resin, polyester resins such as polyethylene terephthalate resin, thermoplastic elastomers, resins made hydrophilic to these resins, and additives such as modifiers. A resin to which an agent is added, a mixture of these resins, and the like can be used. Specific examples of the hydrophilic thermoplastic binder include polyolefin aqueous dispersion (Chemical (registered trademark)) manufactured by Mitsui Chemicals, Inc. Specific examples of the hydrophobic thermoplastic binder include polyethylene powder manufactured by Mitsui Chemicals, Inc. (Miperon (registered trademark), polyethylene powder manufactured by Asahi Kasei Chemicals Corporation (Sunfine (registered trademark)), and the like.

As the inorganic binder, p-alumina (Al ₂ O ₃ .nH ₂ O), phosphoric acid binder, silicon binder, titanium binder, and the like can be used. Clay-like minerals such as layered silicate minerals such as bentonite (main component is montmorillonite) can also be used as the inorganic binder.
The water-soluble binder includes carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) resin, polyacrylamide (PAM) resin, aluminum phosphate binder, and the like in addition to the above-described p-alumina.

Natural organic binders include molasses such as sugarcane molasses, sugar beet molasses and refined molasses molasses, lignin sulfonates such as calcium lignin sulfonate and calcium lignin sulfonate / sodium mixed salt, alpha starch such as corn starch and tapioca starch, konjac Includes flying powder, sodium alginate, and the like.
The compounding amount of the additive 103 can be, for example, about 0.1 to 60 parts by weight with respect to 100 parts by weight of the liquid dispersion medium.

In addition, when the blending ratio of CNF with respect to 100 parts by weight of the liquid dispersion medium is less than 11 parts by weight for wet pulverization of the cellulose raw material, a treatment for removing a part of the liquid dispersion medium from the original suspension is performed. Thus, the mixing ratio of CNF to 100 parts by weight of the liquid dispersion medium may be 11 to 43 parts by weight. For the process of removing the liquid dispersion medium from the original suspension, the absorbent material absorbs a part of the liquid dispersion medium of the original suspension, and the liquid dispersion medium of the original suspension is partially evaporated. A process of removing the filtrate by partially filtering the original suspension, a process of removing a part of the liquid dispersion medium by centrifuging the original suspension, etc. it can. As the absorbent material, a water absorbent sheet such as a water absorbent paper, a water absorbent polymer, or the like can be used.
The above is the suspension preparation step S1 for preparing a suspension containing 11 to 43 parts by weight of CNF with respect to 100 parts by weight of the liquid dispersion medium.

(3-2) Specific example of forming step S2:
In the forming step S2, the highly viscous suspension 100 is formed into a granular shape. The method of forming the suspension 100 into a granular form includes a method of repeatedly cutting the suspension 100 while extruding it linearly from a die, a method of forming the suspension 100 into a plate shape and cutting it vertically and horizontally, a suspension A method of granulating 100 can be employed.

  6 (a) to 6 (e) schematically show granulators 210, 220, 230, 240, and 250 as examples of apparatuses for forming a suspension into granules. These granulators 210, 220, 230, 240 and 250 are examples of means for aligning the suspension to a predetermined particle size, that is, a particle having a predetermined size.

  In the extrusion granulator 210 shown in FIG. 6A, two rolls 213 and 214 are arranged in a cylindrical rotary die 211 having a plurality of through holes 212, and a cutter 215 is provided on the outer peripheral surface of the rotary die 211. The blade edge is matched. Each through-hole 212 has a circular cross section. The rotating die 211 rotates at a constant speed in a direction facing the cutting edge of the cutter 215 (counterclockwise in FIG. 6A). The lower roll 213 rotates at the same speed in the same direction (counterclockwise in FIG. 6A) according to the rotation of the rotary die 211. The suspension 100 in the rotary die 211 is pushed into the through hole 212 by the rotation of the rotary die 211 and the roll 213, and is pushed out from the through hole 212 in a linear shape. The extruded suspension 100 is cut at substantially equal intervals by the cutter 215 every rotation of the rotary die 211 to become a substantially cylindrical granular suspension 110. Therefore, the obtained granular suspension 110 is almost aligned in a predetermined size.

  In the extrusion granulator 220 shown in FIG. 6B, a roll 223 is disposed on a disk-shaped rotating die 221 having a plurality of through holes 222, and the cutting edge of the cutter 225 is aligned with the lower surface of the rotating die 221. ing. Each through-hole 222 has a circular cross section. The rotary die 221 rotates at a constant speed in a direction facing the cutting edge of the cutter 225 (the front side is the right direction in FIG. 6B). The roll 223 rotates at a constant speed in accordance with the rotation of the rotary die 221 (counterclockwise in FIG. 6B). The suspension 100 on the rotary die 221 is pushed into the through hole 222 by the rotation of the rotary die 221 and the roll 223 and is pushed out from the through hole 222 in a linear shape. The extruded suspension 100 is cut at substantially equal intervals by the cutter 225 every rotation of the rotary die 221 to become a substantially cylindrical granular suspension 110. Therefore, the obtained granular suspension 110 is almost aligned in a predetermined size.

  Furthermore, a pelletizer that cuts the strand extruded from the through-hole of the die with a rotary blade can also be used as a means for aligning particles of a predetermined size. For example, the pelletizer extrudes suspension 100 in a barrel from a plurality of through-holes of a die attached to the tip of a cylindrical barrel by rotating a screw, and linear suspension is performed by a cutter that rotates on the front of the die. The suspension 100 is cut. If each through-hole is circular in cross section, the granular suspension 110 is cylindrical. If the screw rotates at an equal speed and the cutter rotates at an equal speed, the linear suspension 100 extruded from the through-hole of the die is cut at equal intervals, and the particles are arranged in a predetermined size. A suspension 110 is obtained.

  A granulator 230 shown in FIG. 6C includes a plate molding machine (not shown) for forming the suspension 100 into a plate shape, and a cutter for cutting the plate suspension 100 vertically and horizontally at equal intervals. 235. A compression molding machine, an injection molding machine, etc. can be used for a plate-shaped molding machine. In the cutter 235, the blades 235a facing in the vertical direction are arranged at equal intervals in the horizontal direction, and the blades 235b facing in the horizontal direction are arranged at equal intervals in the vertical direction. When the cutter 235 is moved in the thickness direction of the suspension 100 (downward in FIG. 6C) with respect to the plate-like suspension 100, the plate-like suspension 100 is cut at equal intervals vertically and horizontally. Thus, the granular suspension 110 has a rectangular parallelepiped shape (cubic shape in FIG. 6C). Therefore, the obtained granular suspension 110 is arranged in a predetermined size.

  The compression granulator 240 shown in FIG. 6D is a tableting granulator that compresses the suspension 100 supplied to the cavity 242 in the cylinder 241 by moving the piston 243. The granulator 240 closes the cavity 242 by moving the piston 243 to compress the suspension 100, and further opens the cavity 242 by moving the piston 243 in the opposite direction to discharge the granular suspension 110. . The resulting granular suspension 110 has a constant shape that matches the shape of the closed cavity 242, and is aligned in a predetermined size.

  A compression granulator 250 shown in FIG. 6 (e) is a briquetting granulator that compresses a material into a fixed shape by rolls 251 and 252 that rotate in opposite directions. The rolls 251 and 252 have the same shape, and each roll 251 and 252 has a plurality of concave portions for shaping the suspension 100. In FIG. 6E, the left roll 251 rotates clockwise at a constant speed, the right roll 252 rotates counterclockwise at a constant speed, and the rotation speeds of the rolls 251 and 252 are the same. The granulator 250 forms a cavity 253 by the concave portion of the roll 251 and the concave portion of the roll 252, sends the suspension 100 supplied onto the rolls 251 and 252 to the cavity 253, and compresses it into a certain shape. The paper is discharged below the rolls 251 and 252. The obtained granular suspension 110 has a fixed shape matched to the shape of the cavity 253 and is arranged in a predetermined size.

Note that since the viscosity of the suspension is high, the granular suspension 110 may adhere to the cutters 215 and 225 shown in FIGS. 6 (a) and 6 (b). Therefore, the granulators 210 and 220 may be provided with a blower that applies air to the cutters 215 and 225. The granular suspension 110 adhering to the cutters 215 and 225 can be dropped from the cutters 215 and 225 by blowing air to the cutters 215 and 225 by the blower. Thereby, it is suppressed that granular suspension 110 adheres to cutters 215 and 225, and maintenance nature of granulators 210 and 220 improves.
Further, in the granulators 210 and 220, air cutters may be provided that blow the air directly onto the suspension 100 instead of the cutters 215 and 225 to cut the suspension 100. The granular suspension 110 can be dropped from the rotating dies 211 and 221 by directly blowing air onto the suspension 100 pushed out through the through holes 212 and 222 of the rotating dies 211 and 221 to a predetermined length.
Furthermore, in all the granulating apparatuses described above, when the granular suspensions adhere to each other, the granular suspension 110 is dispersed by, for example, blowing air from a blower on the aggregate of the granular suspensions 110, that is, separately. You may perform the process to do.

Further, the molding step S2 may include a preforming step S21 for preforming the highly viscous suspension 100 by the above-described granulator, and a rounding step S22 for rounding the preformed granular suspension 110.
FIG. 7 schematically shows a rolling granulator 260 as an example of means for rounding the preformed granular suspension. A granular suspension 110 </ b> A shown on the left side of FIG. 7 indicates a granular suspension formed from the suspension 100 by a granulator 210, 220, 230, 240, 250, or the like. The granular suspension 110B shown on the right side of FIG. 7 shows the granular suspension rounded from the granular suspension 110A by the rolling granulator 260. The concept of the granular suspension 110 includes granular suspensions 110A and 110B.

  The granulator 260 shown in FIG. 7 has a rotating pan 261 that is open at the top and tilted from the horizontal plane at an inclination angle θ. The inclination angle θ is 0 ° <θ <90 °, and preferably 30 ° <θ <60 °. The rotational speed of the rotary pan 261 can be set to 10 to 30 rpm, for example. When the granular suspension 110A is put in the rotating rotary pan 261, at least a part of the corner of the granular suspension 110A is rounded, or at least a part of a portion having a small curvature radius becomes a larger curvature radius. . Thereby, the shape of the granular suspension 110B obtained is closer to a sphere than the original granular suspension 110A.

  Further, in the rounding step S22, the granular suspension 110 may be caused to flow and round by means of introducing air from the blower into the container in which the granular suspension 110 is placed.

  In the molding step S2, the mixing ratio of the liquid dispersion medium 101 in the granular suspension 110 may be less than the mixing ratio of the liquid dispersion medium 101 in the original suspension 100. For example, when the liquid dispersion medium 101 is water, a heating machine for heating the rotary pan 261 is provided in the rolling granulator 260 shown in FIG. 7, and when the rotary pan 261 is heated by this heater, the granular suspension 110B The water can be vaporized and removed. Moreover, even if the wind sent from a blower is heated with a heater and applied to the granular suspension 110, the water of the granular suspension 110 can be vaporized and removed.

(3-3) Specific example of activation step S3:
In the activation step S3, granular activated carbon 120 is obtained by heating and activating the granular suspension 110. Activation is a reaction that develops micropores in a material to be activated carbon and turns it into a porous material. In this specific example, gas activation is performed by high-temperature treatment in the presence of gas such as water vapor, carbon dioxide, or air. The activation step S3 includes an infusibilization step S31 for performing an infusibilization treatment for heating and carbonizing the granular suspension 110, and an activation treatment for heating and activating the granular carbide obtained by the infusibilization treatment to thereby activate granular activated carbon. Main activation step S32 for obtaining 120 may be included.

  The infusibilization treatment can be, for example, a treatment of carbonizing the granular suspension 110 at 200 to 700 ° C. in an atmosphere of an inert gas such as nitrogen or argon. Various temperature conditions can be set. For example, the temperature is simply raised from room temperature to a predetermined carbonization end temperature (Tce) at a predetermined temperature increase / decrease rate (ΔTi) and held for a predetermined time to be a predetermined infusibilization end temperature (Tie). May be lowered. Further, the temperature is increased from room temperature to a predetermined carbonization start temperature (Tcs) at a predetermined temperature increase / decrease rate ΔTi, held for a predetermined time, then increased to a carbonization end temperature Tce and held for a predetermined time, and a predetermined infusibilization end temperature is reached. You may lower it to Tie. The temperature increase / decrease rate ΔTi can be, for example, 1 to 20 ° C./min (more preferably 2 to 10 ° C./min). The carbonization start temperature Tcs can be, for example, 200 to 350 ° C. (more preferably 220 to 300 ° C.). The time for maintaining the carbonization start temperature Tcs can be, for example, 0.1 to 10 hours (more preferably 1 to 7 hours). The carbonization end temperature Tce can be set to, for example, 500 to 700 ° C. (more preferably 550 to 650 ° C.). The time for maintaining the carbonization end temperature Tce can be, for example, 0.1 to 5 hours (more preferably 1 to 3 hours). The infusibilization end temperature Tie can be set to 40 to 90 ° C., for example.

  In addition, you may perform the process which makes the compounding ratio of the liquid dispersion medium 101 of the granular suspension 110 smaller than the compounding ratio of the liquid dispersion medium 101 of the original suspension 100 as pre-processing which performs an infusibilization process. For example, when the liquid dispersion medium 101 is water, the rolling granulator 260 shown in FIG. 7 is provided with a heater that heats the rotating pan 261, and the rotating pan 261 is heated to, for example, 100 ° C. or more by this heater. When the granular suspension 110 is placed in the rotating pan 261, the water in the granular suspension 110 can be vaporized and removed. The removal of water from the granular suspension 110 includes natural drying for drying the granular suspension 110 at room temperature, vacuum drying for the granular suspension 110, freeze drying for the granular suspension 110, and granular suspension 110. Alcohol substitution drying in which water is substituted with an alcohol such as ethanol and dried at room temperature, critical point drying in which the granular substance after alcohol substitution is immersed in isoamyl acetate and dried using the critical point of liquefied carbon dioxide gas, and the like may be used.

  The activation treatment after the infusibilization treatment is, for example, a treatment for activating granular carbide at 700 to 1100 ° C., more preferably 800 to 1000 ° C. in an atmosphere of an oxidizing gas such as water vapor or carbon dioxide, to obtain granular activated carbon 120. be able to. Moreover, you may switch from the atmosphere of oxidizing gas to the atmosphere of inert gas, such as nitrogen and argon, during a heating. Various temperature conditions can be set. For example, the temperature is increased from room temperature to a predetermined activation end temperature (Tae) at a predetermined temperature increase / decrease rate (ΔTa), held for a predetermined time, and lowered to a predetermined activation processing end temperature (Tcoe). May be. The temperature increase / decrease rate ΔTa can be, for example, 1 to 20 ° C./min (more preferably 2 to 10 ° C./min). The activation end temperature Tae can be set to, for example, 700 to 1100 ° C. (more preferably 800 to 1000 ° C.). The time for holding the activation end temperature Tae can be, for example, 0.1 to 5 hours (more preferably 1 to 3 hours). The activation treatment end temperature Tcoe can be set to 40 to 90 ° C., for example.

  In addition, although there exists an infusible process, since the activity as activated carbon increases, it is preferable, but an infusible process can be abbreviate | omitted and an activation process can also be performed.

  The granular activated carbon 120 obtained by the activation step S3 has a property of adsorbing and removing a trace component from a fluid such as water or air, like the known activated carbon. When the granular activated carbon 120 is used for a water purification cartridge, trace components such as free residual chlorine and organic matter contained in water can be removed. When the granular activated carbon 120 is used in a filtration cartridge for an air cleaner, trace components such as odor components contained in air (an example of fluid) can be removed.

  The granular activated carbon 120 obtained by the activation step S3 is usually smaller than the granular suspension 110 obtained by the molding step S2, and has a size corresponding to the size of the granular suspension 110. That is, there is a positive correlation between the size of the granular suspension 110 and the size of the granular activated carbon 120. The larger the granular suspension 110, the larger the granular activated carbon 120 tends to be, and the smaller the granular suspension 110 is. The granular activated carbon 120 tends to be smaller. From this, the size of the granular activated carbon 120 obtained can be adjusted by adjusting the size of the granular suspension 110. Therefore, the manufacturing method of this example is easy to adjust the size of the granular activated carbon obtained.

(3-4) Specific example of housing step S4:
The granular activated carbon 120 manufactured by the steps S1 to S3 described above can be used for manufacturing the water purification cartridge 20 shown in FIGS. In the housing step S <b> 4 included in the method for manufacturing the water purification cartridge 20, the granular activated carbon 120 is housed in the inner side 33 of the outer nonwoven fabric 31. Hereinafter, the example of the manufacturing method of the water purification cartridge 20 including accommodation process S4 is demonstrated.

  First, the end 41 b of the inner nonwoven fabric 41 is inserted into the communication port 74 of the hollow fiber membrane case 70, and the inner cap 48 is attached to the upstream end 41 a of the inner nonwoven fabric 41. Thereby, the opening 41o of the edge part 41a of the inner side nonwoven fabric 41 is obstruct | occluded, and the inner side 43 of the inner side nonwoven fabric 41 becomes a channel | path of the water purified with adsorption agent AH1. Next, the end 31 b of the outer nonwoven fabric 31 is inserted inside the outer fitting portion 80 of the hollow fiber membrane case 70. Next, the inner fitting member 50 is put into the inner side 33 of the outer nonwoven fabric 31, and the end portion 31 b of the outer nonwoven fabric 31 is held between the outer fitting portion 80 and the inner fitting member 50. For this reason, although the outer nonwoven fabric 31 and the hollow fiber membrane case 70 are connected even if it does not use an adhesive agent, it is also possible to use a small amount of adhesive agents together.

  Here, the adsorbent AH1 containing the granular activated carbon 120 is accommodated inside the outer nonwoven fabric 31 and outside the inner nonwoven fabric 41. Thereafter, the outer cap 38 is inserted into the upstream end 31 a of the outer nonwoven fabric 31, and the end 31 a of the outer nonwoven fabric 31 is bent inward and welded to the outer surface 38 a of the outer cap 38. Thereby, the opening 31o of the end part 31a of the outer nonwoven fabric 31 is closed, and the outer side of the inner nonwoven fabric 41 and the inner side 33 of the outer nonwoven fabric 31 serve as a storage space for the adsorbent AH1, and the manufacture of the water purification cartridge 20 is completed.

  The adsorbent AH1 may be all granular activated carbon 120, but one or more additives 130 may be included as shown in FIG. 5 as long as the effects of the present technology are not impaired. As the additive 130, the above-described ion exchanger or the like can be used. The compounding quantity of the additive 130 can be about 0.1-60 weight part with respect to 100 weight part granular activated carbon 120, for example.

(4) Effects and effects of the manufacturing method according to the specific example:
The CNF suspension 100 formed in the forming step S2 includes 11 to 43 parts by weight of CNF 102 with respect to 100 parts by weight of the liquid dispersion medium 101, and thus has fluidity due to the liquid dispersion medium 101, and , Having high viscosity due to CNF102. For this reason, the suspension 100 can be easily formed into particles. Since the granular activated carbon 120 has a size corresponding to the size of the granular suspension 110, the size of the granular activated carbon 120 (by adjusting the size of the granular suspension 110, which is easy to adjust the size) ( For example, the particle size) is adjusted. Therefore, this example can provide a production method that makes it easy to adjust the size of the obtained granular activated carbon.

Moreover, when the means for aligning the suspension 100 into particles having a predetermined particle size is used, the particle size of the granular suspension 110 is uniform, and the particle size of the obtained granular activated carbon 120 is uniform. Thereby, the quantity per unit volume of the granular activated carbon 120 accommodated in the inner side 33 of the outer side nonwoven fabric of the water purification cartridge 20 can be increased. In addition, as the granularity of the granular activated carbon 120 becomes uniform, the gaps between the granular activated carbons are made uniform, so that the water flow resistance of the aggregate of the granular activated carbon 120 accommodated in the inner side 33 of the outer nonwoven fabric is made uniform, and the filtration cartridge Improved water purification performance.
Furthermore, if there exists rounding process S22 in shaping | molding process S2, the granular suspension 110 will become a rounded shape, and the granular activated carbon 120 obtained will become a rounded shape. Also by this, the quantity per unit volume of the granular activated carbon 120 accommodated in the inner side 33 of the outer nonwoven fabric of the water purification cartridge 20 can be increased. In addition, since the gap between the granular activated carbons becomes more uniform as the granular activated carbon 120 approaches the true spherical shape, the water flow resistance of the aggregate of the granular activated carbons 120 accommodated in the inner side 33 of the outer nonwoven fabric is made uniform. The water purification performance of the filtration cartridge is improved.

(5) Modification:
Various modifications can be considered for the present invention.
For example, it is preferable that the adsorbent and the hollow fiber membrane bundle arranged in the flow-down direction are the upstream side of the adsorbent and the downstream side of the hollow fiber membrane bundle, but the upstream side of the hollow fiber membrane bundle and the downstream side of the adsorbent. Good. In addition to the hollow fiber membrane case 70, the member having the outflow portion may be a member having an outflow portion without accommodating the hollow fiber membrane bundle. The faucet provided with the water purification cartridge may be provided in a place other than the system kitchen such as a vanity table or a bathroom. The water discharge device may be a water discharge head that discharges only purified water, in addition to a water discharge head that can switch between purified water and tap water. Of course, the filtration cartridge may be a filtration cartridge for an air purifier that removes a substance to be removed from the air.

(6) Example:
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited by the following examples.

[Example 1]
BiNFi-s (registered trademark) cellulose WMa-10010 (10 wt% for standard industrial materials) manufactured by Sugino Machine Co., Ltd. was used as the CNF suspension. The 10 wt% CNF suspension has a water content of 90 wt% and contains 11.1 parts by weight of CNF with respect to 100 parts by weight of water.
The diameter of the granular material dried by extruding the CNF suspension by changing the inner diameter (diameter) of the nozzle for extruding the CNF suspension to 1.0 mm, 1.3 mm, 1.6 mm, and 2.0 mm. The diameter of the granular carbide obtained by subjecting the dried granular suspension to infusibilization treatment and the diameter of the granular activated carbon obtained by subjecting the granular carbide to activation treatment were measured. Infusibilization treatment is performed under an atmosphere of nitrogen gas, a temperature increase / decrease rate ΔTi = 3-4 ° C./min, a carbonization start temperature Tcs = 280 ° C. (5 hours hold), a carbonization end temperature Tce = 600 ° C. (1 hour hold), and The infusibilization end temperature Tie = 50 ° C. The activation treatment is performed in a steam gas atmosphere under the temperature conditions of temperature increase / decrease rate ΔTa = 3 to 4 ° C./min, activation end temperature Tme = 800 ° C. (held for 2 hours), and activation treatment end temperature Tae = 50 ° C. It was.

The test results are shown in Table 1.

As shown in Table 1, it turns out that the diameter of a granular material is so small that a process progresses. The diameter of the obtained granular activated carbon increases as the nozzle inner diameter corresponding to the diameter of the granular suspension increases, and decreases as the nozzle inner diameter decreases. Therefore, it can be seen that there is a positive correlation between the diameter of the granular suspension and the diameter of the granular activated carbon, and the diameter of the granular activated carbon can be adjusted by adjusting the diameter of the granular suspension.

[Example 2]
As the CNF suspension, the 10 wt% CNF suspension used in Example 1 was used. As a water absorbent paper for adjusting the moisture content of the CNF suspension, Nippon Paper Crecia Kim Towel (registered trademark) was used.
In test group 1, a 10 wt% CNF suspension was used as it was. In test groups 2 to 7, water absorption paper was applied to the CNF suspension, and the water contents were 89.1 wt%, 87.5 wt%, 84.4 wt%, 82.1 wt%, 77.3 wt%, and 72, respectively. A CNF suspension adjusted to 2 wt% was used. In each test group, the inner diameter (diameter) of the nozzle for extruding the CNF suspension was 2.3 mm, the CNF suspension was extruded, and the diameter of the granular material dried at room temperature was measured.

The test results are shown in Table 2. Table 2 also shows the blending ratio of CNF obtained from the water content of the CNF suspension in each test section, the blending amount of water and CNF converted to parts by weight.

As shown in Table 2, even if the water content of the CNF suspension was 72.2 to 90.0% by weight, the CNF suspension could be extruded from the nozzle. On the other hand, when the water content of the CNF suspension is 69.0% by weight or less (CNF is 44.9 parts by weight or more with respect to 100 parts by weight of water), the CNF suspension becomes hard, and the CNF suspension Could not be pushed out of the nozzle. Further, when water is added to the CNF suspension to make the water content 91.0% by weight or more (CNF is 9.9 parts by weight or less with respect to 100 parts by weight of water), the fluidity of the CNF suspension is high, The CNF suspension extruded from the nozzle has spread greatly.
In addition, since the diameter of the dried granular suspension becomes larger as the moisture content becomes lower, the moisture content of the CNF suspension can be increased within a range in which the CNF suspension can be extruded and the granularity of the CNF suspension is maintained. The diameter of granular activated carbon can be adjusted also by adjusting.

[Example 3]
As the CNF suspension, the 10 wt% CNF suspension used in Example 1 was used. This CNF suspension is extruded, the resulting CNF suspension is vacuum dried under a temperature environment of 40 ° C., the dried granular material is infusibilized, and the resulting granular carbide is activated. The granular activated carbon of Example 3 was obtained. The conditions for the infusibilization treatment and the activation treatment are the same as those in Example 1.

[Comparative Example 1]
The coconut shell activated carbon GW48 / 100 manufactured by Kuraray Chemical Co., Ltd. was pulverized according to the particle size of the granular activated carbon of Example 3 to obtain the granular activated carbon of Comparative Example 1.

[Evaluation of adsorption rate of granular activated carbon]
As the raw water sample, a 60 ± 15 ppb chloroform aqueous solution was used. Chloroform is an indicator substance for trace components contained in water.
0.1 g of granular activated carbon of Example 3 and Comparative Example 1 was put in each of 9 water sampling bottles, and 100 g of raw water sample was injected into each water sampling bottle. The contents of each water bottle are agitated at 1000 rpm by a rotating device, and the raw water sample is taken at the specified contact time (10 seconds, 20 seconds, 30 seconds, 60 seconds, 2 minutes, 5 minutes, 10 minutes, 30 minutes, 60 minutes). Suctioned off with a syringe and filtered through a 0.8 μm filter, the filtrate was placed in a vial and sealed with a lid. The chloroform concentration of the filtrate injected into each vial was measured by gas chromatography.

The test results are shown in FIG. FIG. 8 shows the equilibrium adsorption achievement rate of chloroform with respect to the contact time (unit: second) in Example 3 and Comparative Example 1. The equilibrium adsorption achievement rates when the contact time is 30 minutes and 60 minutes are not shown in the graph shown in FIG. 8, but are 0.98 and 1.00 in the case of Comparative Example 1, respectively. In either case, it is 1.00. When the equilibrium adsorption achievement rate is 0.00, it indicates that no chloroform has been removed from the raw water sample, and when the equilibrium adsorption achievement rate is 1.00, chloroform is removed from the raw water sample at the highest rate. Indicates that As shown in FIG. 8, the equilibrium adsorption achievement rate of Example 3 using granular activated carbon derived from CNF was obtained by using granular activated carbon obtained by pulverizing coconut shell activated carbon in any contact time of 10 seconds to 10 minutes. The equilibrium adsorption achievement rate of Comparative Example 1 was higher. This means that the granular activated carbon of Example 3 adsorbs faster than the granular activated carbon of Comparative Example 1.
Therefore, it was confirmed that the granular activated carbon obtained by the production method of the present technology using CNF has high purification performance as activated carbon.

(7) Conclusion:
As described above, according to the present invention, techniques such as a manufacturing method that makes it easy to adjust the size of the obtained granular activated carbon can be provided according to various aspects. Needless to say, the above-described basic functions and effects can be obtained even with the technology consisting only of the constituent elements according to the independent claims.
In addition, the configurations disclosed in the above-described examples are mutually replaced or the combination is changed, the known technology and the configurations disclosed in the above-described examples are mutually replaced or the combinations are changed. The configuration described above can also be implemented. The present invention includes these configurations and the like.

1 ... faucet (example of water purifier), 2 ... faucet body,
10 ... Water discharge head (example of water purifier body), 10a ... Tap water passage,
DESCRIPTION OF SYMBOLS 11 ... Water discharging part, 12 ... Connection port, 13 ... Water outlet, 15 ... Switching lever,
18 ... gripping part, 19 ... hose (example of water inlet),
20 ... water purification cartridge (example of filtration cartridge),
30 ... Adsorbent part, 30b ... End part,
31 ... outer nonwoven fabric, 31a, 31b ... end, 31o ... opening,
32 ... Outer side surface (example of inflow part), 33 ... Inner side (example of accommodating part),
38 ... outer cap, 38a ... outer surface,
41 ... inner nonwoven fabric, 41a, 41b ... end, 41o ... opening, 43 ... inside,
48 ... Inner cap,
50. Internal fitting member,
70 ... hollow fiber membrane case, 70c ... internal space, 71 ... hollow fiber membrane bundle housing part, 74 ... communication port,
75 ... Outflow part, 80 ... Outer fitting part,
100 ... suspension,
101 ... Liquid dispersion medium, 102 ... Cellulose nanofiber, 103 ... Additive,
110, 110A, 110B ... granular suspension, 120 ... granular activated carbon, 130 ... additive,
210, 220, 230, 240, 250, 260 ... granulator,
211: Rotating die, 212: Through hole, 213, 214 ... Roll, 215 ... Cutter,
221 ... Rotating die, 222 ... through hole, 223 ... roll, 225 ... cutter,
235 ... cutter, 235a, 235b ... blade,
241 ... Cylinder, 242 ... Cavity, 243 ... Piston,
251,252 ... roll, 253 ... cavity,
261 ... rotating pan,
AH1 ... adsorbent, AX1 ... shaft,
BH1 ... hollow fiber membrane bundle, BH1a ... closed end, BH1b ... open end,
D1 ... Flowing direction, D2 ... Extension direction,
H1 hollow fiber membrane,
S1 ... Suspension preparation step, S2 ... Molding step, S3 ... Activation step, S4 ... Storage step,
S21 ... Preliminary molding step, S22 ... Rounding step, S31 ... Infusibilization step, S32 ... Main activation step,
SY1 ... System kitchen, W ... Water (example of fluid).

Claims (4)

A molding step of molding a suspension containing 11 to 43 parts by weight of cellulose nanofibers into 100 parts by weight of the liquid dispersion medium;
A method for producing granular activated carbon, comprising: an activation step of obtaining granular activated carbon by heating and heating the granular suspension.   The method for producing granular activated carbon according to claim 1, wherein, in the forming step, the suspension is formed into particles by means for aligning the suspension into particles having a predetermined size.   The said shaping | molding process is a manufacturing method of the granular activated carbon of Claim 1 or Claim 2 including the process of rounding the said granular suspension. A method of manufacturing a filtration cartridge in which granular activated carbon is accommodated in an accommodating portion having an inflow portion and an outflow portion of a fluid,
A molding step of molding a suspension containing 11 to 43 parts by weight of cellulose nanofibers into 100 parts by weight of the liquid dispersion medium;
An activation step of obtaining the granular activated carbon by heating and heating the granular suspension;
A housing step of housing the granular activated carbon in the housing section.