JP3304375B2 - Method for producing activated carbon-attached fiber sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent adsorptivity and moldability .
The present invention relates to a method for producing an activated carbon- attached fiber sheet.

[0002]

2. Description of the Related Art Activated carbon has conventionally been provided in various forms such as granular, fibrous, and molded bodies. However, since granular activated carbon is difficult to handle and has no form stability, a base material for fixing granular activated carbon is required. However, when fixed to a base material with an adhesive or the like, there is a problem that the surface area on which the granular activated carbon works effectively decreases, and the adsorption performance decreases.

[0003] Although fibrous activated carbon is excellent in form stability, it has a problem that it is difficult to mold it into various shapes due to lack of strength, and it is difficult to mold the activated carbon into a cylindrical shape, a plate shape, a honeycomb shape or the like. However, there is a problem that versatility is required because a mold to be molded is required for each.

[0004]

DISCLOSURE OF THE INVENTION The present invention has excellent adsorption performance and is easy to mold into various shapes, so that it has excellent versatility .
It is an object of the present invention to provide a method for producing an activated carbon- attached fiber sheet.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a firing activation treatment.
Adhesive carbonized resin powder on fiber with excellent heat resistance to withstand
Powdered activated carbon adhered without intervening and fired and activated is an activated carbon-adhered fiber or activated carbon-adhered fiber sheet adhered without interposition of an adhesive, and the powdered activated carbon is obtained by firing-activating phenolic resin powder. If it is a substance, it is excellent in adsorptivity to ammonia, trimethylamine and the like.

Also, a feeder 1 for supplying fibers and the like.
And a plurality of adjacent and oppositely rotating fiber opening cylinders 2 ₁ , 2 ₂ , 2 ₃ with a metallic wire attached to the surface for dispersing and moving the fibers and the like supplied from the feeder 1 while moving the fibers. .. _2n (n is a natural number) and a transfer section 4 in which fibers and the like move between adjacent fiber-opening cylinders, and dispersed and fiber-opened fibers and the like are distributed to the terminal fiber-opening cylinder _2n. The opening cylinder 2 having an opening 5 for discharging.
₁ , 2 ₂ , 2, ₃ ... 2 _n , a conveyor 7 for receiving fibers and the like discharged from the opening cylinder 2 _{n at the} outlet end, and a conveyor 7 positioned below the conveyor 7 In a fiber sheet manufacturing apparatus provided with a suction box 8 for sucking fibers and the like, fibers and a carbonized resin powder are supplied from a feeder 1 to obtain a fiber sheet in which the carbonized resin powder adheres to the fibers substantially uniformly. After that, a firing sheet is activated to obtain a fiber sheet to which powdered activated carbon is adhered substantially uniformly, and if a phenolic resin powder is used as the carbonizable resin powder, it has excellent adsorption properties to ammonia, trimethylamine and the like.

[0007]

The activated carbon-attached fiber of the present invention is resistant to firing activation treatment.
Glue carbonized resin powder on fiber with excellent heat resistance
Since the powdered activated carbon that has been applied without being interposed and fired and activated has been attached without interposing an adhesive, the adsorption performance of the powdered activated carbon does not decrease, and it is processed into various fiber sheets such as woven fabric, knitted fabric, and nonwoven fabric. Therefore, the activated carbon-attached fiber sheet is excellent in versatility since it can be easily formed into various shapes. The powdered activated carbon obtained by activating the phenolic resin by firing is excellent in the adsorptivity to ammonia, trimethylamine and the like.

In the method for producing a fiber sheet with activated carbon of the present invention, a feeder 1 for supplying fibers and the like, and a fiber and the like supplied from the feeder 1 are dispersed and spread while moving, and a metallic wire is attached to the surface. , A plurality of adjacent opening cylinders 2 ₁ , 2 ₂ , 2 _3.
.. 2 _n (n is a natural number) and a transfer section 4 in which fibers move between adjacent opening cylinders, and dispersed and opened fibers are discharged to the terminal opening cylinder 2 _n having an opening 5 which, the open fiber cylinder 2 _{1, 2} 2, 2 _3,
..Housing 3 covering 2 _n and conveyor 7 for receiving fibers and the like discharged from opening cylinder 2 _{n at the} outlet end
And a suction box 8 that is located below the conveyor 7 and sucks released fibers and the like. In the fiber sheet manufacturing apparatus, fibers and carbonizable resin powder are supplied from the feeder 1 and carbonized resin is supplied. This is a method of obtaining a fiber sheet in which the powder is attached to the fibers substantially uniformly, and then performing a firing activation treatment.
₁ , 2 ₂ , 2 ₃ ... 2 _n
The fiber sheet is baked because static electricity is generated by friction with the fiber opening cylinders 2 ₁ , 2 ₂ , 2 ₃ ... 2 _n and the housing 3, and the carbonized resin powder adheres to the fibers almost uniformly due to the static electricity. When the activation treatment is performed, an activated carbon-adhered fiber sheet to which the carbonizable resin powder is almost uniformly adhered is obtained, which is advantageous in the process.

Hereinafter, the activated carbon-attached fiber and the activated carbon-attached fiber sheet of the present invention will be described based on a production method.

The fibers used in the present invention are intended to impart morphological stability to powdered activated carbon (hereinafter referred to as "activated carbon"). To obtain excellent activated carbon. Therefore, it is necessary to use fibers having excellent heat resistance. Usually, since the firing activation treatment is performed at 400 ° C. or higher, glass fibers, silica fibers, alumina fibers, ceramic fibers, silicon carbide fibers, quartz fibers, rock wool, and the like can be used, but are not limited thereto.

[0011] The carbonizable resin powder is electrostatically attached to the fiber having excellent heat resistance. Therefore, the carbonized resin powder is attached to the fiber, and the adhesive is not used. Therefore, there is almost no decrease in the adsorption performance of the activated carbon obtained by firing and activating the carbonized resin powder.

Examples of the carbonizable resin powder include a phenolic resin, an epoxy resin, and a PAN resin. Among these, when a phenolic resin is used,
Excellent adsorption performance for ammonia, trimethylamine, etc. In addition, it is preferable to use a carbonizable resin powder having an average particle size of 5 to 100 μm so that these powders need to be electrostatically adhered to the fibers and are efficiently fired and activated.

The phenolic resin is a resin obtained by a condensation reaction between a phenol and an aldehyde.
Phenols such as phenol, cresol, xylenol, resorcinol, phenolsulfonic acid and aldehydes such as formaldehyde, acetaldehyde and furfural may be used.
Activated carbon obtained by subjecting a phenolic resin disclosed in JP-177701 to calcination activation has excellent adsorption properties to ammonia and trimethylamine.

As a method of electrostatically adhering the carbonized resin powder on the fiber, the carbonized resin powder is discharged from a spinneret, then frictionally charged, or charged with a heat electret or an electro-electret, and then the carbonized resin powder is charged. Examples of the method for attaching the powder include, but are not limited to, these.

As described above, a fiber having carbonized resin powder adhered to the fiber without using an adhesive is obtained. This fiber is activated carbon-attached fiber or activated carbon-attached fiber sheet of the present invention by performing a firing activation treatment in a state of a single fiber or after a single fiber is formed into a fiber sheet such as a knitted, woven or nonwoven fabric.

As a method for directly obtaining a fiber sheet to which carbonized resin powder is attached, a feeder 1 for supplying fibers or the like is used.
And a plurality of adjacent and oppositely rotating fiber opening cylinders 2 ₁ , 2 ₂ , 2 ₃ with a metallic wire attached to the surface for dispersing and moving the fibers and the like supplied from the feeder 1 while moving the fibers. .. _2n (n is a natural number) and a transfer section 4 in which fibers and the like move between adjacent fiber-opening cylinders, and dispersed and fiber-opened fibers and the like are distributed to the terminal fiber-opening cylinder _2n. The opening cylinder 2 having an opening 5 for discharging.
₁ , 2 ₂ , 2, ₃ ... 2 _n , a conveyor 7 for receiving fibers and the like discharged from the opening cylinder 2 _{n at the} outlet end, and a conveyor 7 positioned below the conveyor 7 In a manufacturing apparatus of a fiber sheet provided with a suction box 8 for sucking fibers and the like, there is a method of supplying fibers and carbonizable resin powder from a feeder 1. According to this method, the carbonized resin powder is electrostatically attached to the fiber simultaneously with the opening of the fiber, so that a fiber sheet to which the carbonized resin powder is attached can be easily obtained.

This method will be described in more detail with reference to FIG. 1 which is a sectional view of one embodiment of a fiber sheet manufacturing apparatus having four fiber opening cylinders.

The fibers and the carbonized resin powder are supplied from a feeder 1, and the fibers and the carbonized resin powder are subjected to friction with the opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2, ₄ or the opening cylinder 2 ₁ , 2.
By the collision with the housing 3 by the action of the centrifugal acceleration caused by 2 ₂ , 2 ₃ , 2 ₄ , the fibers are dispersed and opened almost uniformly, and at the same time, the opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2 ₄ or the housing 3 are opened. Electrostatic charges due to friction when colliding with Therefore, the fiber and the carbonized resin powder are electrostatically attracted, and the carbonized resin powder adheres to the fiber surface. The “centrifugal acceleration” means an acceleration component of a centrifugal force F = mrw ² that acts when a fiber or a carbonaceous resin powder having a mass m is conveyed by an opening cylinder having a radius r rotating at an angular velocity w.
That is, it means rw ² .

When the feeder 1 is rotated so that the fibers and the carbonized resin powder can be supplied from below, the fibers and the carbonized resin powder can be supplied without fail. Fibers and carbonizable resin powder supplied from the lower side of the feeder 1, as subjected to centrifugal acceleration by the opening cylinder 2 _1, but the fibers and carbonized resin powder is not reverted,
Opening cylinder 2 ₁ is preferably rotated in the same direction as the feeder 1. It is more preferable that the centrifugal acceleration is smaller than that of the other opening cylinders 2 ₂ , 2 ₃ , and 2 ₄ so as not to damage the supplied fiber.

The supplied fibers and carbonized resin powder from the opening cylinder 2 _1, distributed to the opening cylinder 2 _2, 2 _3, 2 ₄ adjacent counter-rotating to each other, moves while being opened. When moving between the fiber-opening cylinders, the fibers are not combed, but simply move, and the fiber is opened by colliding with the housing 3 by centrifugal acceleration. Incidentally, the collision of the housing 3 is effectively performed by the opening cylinder 2 _1, 2 _2, 2 _3, 2 ₄ surface of the metallic wire.

In addition, even if adjacent opening cylinders 2 ₁ ,
Even if the rotation directions of 2 ₂ , 2 ₃ , 2 ₄ are reversed, if the opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2 ₄ were rotating at a low speed, it would only move the fibers. Therefore, it is preferable to rotate at a high speed because the fiber cannot be opened substantially uniformly.
This high-speed rotation is 2500 times or more per minute, and when considering that a normal cylinder is 300 to 500 times per minute, the number of rotations is an order of magnitude higher by one digit.

The radius of the opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2 ₄ is preferably 50 cm or less for high-speed rotation, and in order to efficiently perform substantially uniform dispersion and opening. Is preferably 5 cm or more. Here, when the centrifugal acceleration acting on the fiber and the carbonized resin powder in the opening cylinder having a radius of 5 cm rotating at 2500 revolutions per minute is calculated, rw ² = 5 × (2500 × 2π / 60) ² = 3.4 ×
10 ⁵ (cm / sec ² ), and when a centrifugal acceleration higher than that is applied, the fiber can be efficiently dispersed and spread.

In addition, all the opening cylinders 2 ₁ , 2 ₂ ,
2 _3, 2 ₄ 3.4 × 10 ⁵ cm / sec ² or more it is not necessary to rotate at a centrifugal acceleration of the opening cylinder 2 _{1, 2} 2, 2 _3, 2 ₄ of at least one of 3.4 × 10 ^{What is} necessary is just to rotate at ⁵ cm / sec ² or more. Generally, the feeder 1 and adjoining the opening cylinder 2 ₁ of centrifugal acceleration and another opening cylinder 2 _2,
2 _3, 2 ₄ to less than gradually or greater, to the other opening cylinder 2 _2, 2 _3, 2 ₄ of the centrifugal acceleration constant.

The opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2 ₄ are surrounded by a housing 3, which is separated by centrifugal acceleration by the opening cylinders 2 ₁ , 2 ₂ , 2 ₃ , 2 ₄ . The fibers collide with the fluttered fibers and the carbonized resin powder to disperse and spread the fibers, generate static electricity, and cause the carbonized resin powder to adhere to the fibers. Therefore, the opening cylinder 2 ₁ other than the opening cylinder 2 ₄ terminal, 2 _2, 2 _3, connects the adjacent opening cylinder, with the exception of the delivery unit 4 to move the carbide resin powder and fibers, It is covered by the housing 3. Meanwhile, since the opening cylinder 2 ₄ termini of fibers carbonized resin powder is adhered to release the air by centrifugal acceleration, and fibers carbonized resin powder is adhered caught by the housing 3, is that the release is prevented An opening 5 wider than the transfer part 4 is formed so as not to be provided.

[0025] Such hydrocarbon resin powder adhered fibers are released from the open portion 5 of the housing 3 to cover the distal opening cylinder 2 _4, the carbonizable resin powder excess relative to the amount of fiber When supplied from the feeder 1, the carbonizable resin powder that cannot adhere to the fibers is dispersed between the fibers. Further, the opening cylinder 2 ₄ termini if rotated to emit toward the fibers carbonized resin powder is deposited from above to below, non-directional fiber sheet is obtained.

[0026] Incidentally, established the air shower apparatus 6 above the portion of emitting fibers carbonized resin powder in the opening cylinder 2 ₄ terminal is attached, the indirectly exert air against release fibers The pressure difference due to the air is generated, and the fiber to which the carbonizable resin powder is attached in a portion close to the air is attracted to the air to form a substantially uniformly dispersed fiber sheet.

[0027] Then, the fibers carbonized resin powder released from the opening cylinder 2 ₄ terminal is attached is subjected to the suction effect of the suction box 8 in the vicinity of the conveyor 7, the recovery when there is a surplus of the carbonized resin powder Then, only the fibers to which the carbonized resin powder adheres are accumulated on the conveyor 7 to form a fiber sheet having a strength that can be handled. afterwards,
This fiber sheet is subjected to a firing activation treatment to become the activated carbon-attached fiber sheet of the present invention.

The firing activation treatment in the present invention may be carried out independently or simultaneously with the firing treatment and the activation treatment, and is not particularly limited. When performed alone, the baking treatment is performed at a temperature of 400 in a non-oxidizing atmosphere.
C. or more, more preferably a method of carbonizing the carbonizable resin powder by heat of 500 ° C. or more, and the activation treatment includes heating at 400 ° C. or more in an atmosphere of an oxidizing gas such as steam, carbon dioxide, oxygen, or air. Can be exemplified. On the other hand, if performed simultaneously, water vapor, carbon dioxide,
A method in which heat of 400 ° C. or more is applied in an oxidizing gas atmosphere such as oxygen or air can be exemplified.

The activated carbon-adhered fiber or activated carbon-adhered fiber sheet obtained as described above is efficiently and uniformly carbonized, activated and adsorbed because the carbonizable resin powder is fired and activated in a powder state. Activated carbon with excellent performance.
Activated carbon also applies carbonized resin powder electrostatically to fibers.
Since it is adhered to the fibers by applying and firing-activated treatment , there is no problem of a decrease in adsorption performance due to the adhesive, and the obtained activated carbon-attached fiber or activated carbon-attached fiber sheet is easily molded into various shapes. Therefore, it is excellent in versatility. Further, when a phenolic resin powder, particularly a phenolic resin disclosed in JP-A-57-1770011, is used as the carbonizable resin powder, an activated carbon-adhered fiber or an activated carbon-adhered fiber having excellent adsorptivity to ammonia, trimethylamine, etc. A sheet is obtained.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.

[0031]

【Example】

(Example) Glass fiber (fiber diameter 13 μm, fiber length 10 m)
m) 10 g and phenol resin powder (Bellpearl S-89)
0, Kanebo Ltd., an average particle diameter of 20 [mu] m) 10 g, was fed from the feeder 1 of the production apparatus as shown in FIG. 1, dispersed by the opening cylinder 2 _{1, 2} 2, 2 _3, 2 _4, opening after adhering, receiving the fiber phenolic resin powder is adhered released from the opening cylinder 2 ₄ ends at a conveyor 7,
A fiber sheet was formed. The manufacturing apparatus on Figure 1, the feeder 1 and, this rotates the opening cylinder 2 ₁ adjacent in the same direction as the clock, or less adjacent cylinders 2 _2, 2 _3,
2 ₄ sequentially, rotated in opposite directions. Any of the opening cylinder 2 _{1, 2} 2, 2 _3, 2 ₄ of radius is 5 cm, is rotated per minute 3600 times. The pressure of the air shower was set at 1 kgf / cm ² .

The firing activation treatment of the fiber sheet thus formed is carried out in an electric furnace at room temperature for 3 hours in an air atmosphere.
The temperature is raised to 300 ° C at a rate of 300 ° C / min.
Hold for hours. Thereafter, the temperature was raised to 500 ° C. at a rate of 5 ° C./min, and then naturally cooled to room temperature to obtain an activated carbon-attached fiber sheet. In addition, about the activated carbon which adheres, I
When R (diffuse reflection method) measurement was performed,
At around 700 cm ^-1, absorptions considered to be a hydroxyl group and a carboxyl group were shown.

(Comparative Examples 1-2) 10 g of the phenol resin powder used in the examples was cured at 150 ° C for 1 hour,
It was molded into a plate of 0 × 100 × 1 mm. Then, a firing activation treatment was performed in the same manner as in the example to obtain an activated carbon plate-like body (Comparative Example 1). Thereafter, the activated carbon plate was ground in a mortar to obtain a powder, and an activated carbon powder was obtained (Comparative Example 2).

(Measurement of Deodorization for Ammonia) Into a 2 liter Erlenmeyer flask, the samples (0.2 g) of Examples and Comparative Examples 1 and 2 were placed. After that, ammonia was added to make the initial concentration 800 ppm, and the concentration every hour was measured with a detector tube (manufactured by Gastech Co., Ltd.). On the other hand, the concentration was measured using an Erlenmeyer flask charged with the same amount of ammonia alone as a blank, and the deodorization rate for the blank was determined.
The result is shown in FIG.

(Measurement of Deodorization of Trimethylamine) The deodorization rate was determined in the same manner as the measurement of deodorization of ammonia, except that the initial concentration of trimethylamine was 30 ppm. The result is shown in FIG.

(Other Deodorization Measurements) Deodorization rates of hexane, isopropylamine, trimethylamine and hydrogen sulfide were determined in the same manner as in the case of ammonia, but none of the samples was adsorbed.

From the above deodorization measurement, it is considered that the activated carbon-attached fiber sheet of the example is excellent in the adsorption property to ammonia and trimethylamine because the phenol resin powder is fired and activated in a powder state.

(Regeneration Test) Into a 2-liter Erlenmeyer flask, a sample (0.2 g) of the example was placed. Thereafter, 8 μl of aqueous ammonia is added. After one hour, a detector tube (manufactured by Gastech Co., Ltd., for ammonia, No. 3M)
Is used to measure the concentration of ammonia, and 8 μl of aqueous ammonia is added. One hour later, the ammonia concentration is measured, and 8 μl of aqueous ammonia is added. This operation is repeated until after 4 hours. After that, the sample is
After drying at 3 ° C. for 3 hours for regeneration, the same operation is repeated. As shown in FIG. 4, the results show that the performance hardly decreases before and after the reproduction and can be used repeatedly. The deodorization rate is determined by the following equation. The following concentrations are ppm.

[0039]

[0040]

The activated carbon-attached fiber of the present invention is subjected to a firing activation treatment.
Carbonized resin powder on fiber with excellent heat resistance
The powdered activated carbon that has been attached and fired and activated without adhering to the adhesive is bonded without using an adhesive, so the adsorption performance does not decrease and it can be processed into various fiber sheets such as woven fabric, knitted fabric, and nonwoven fabric. Since it can be formed, it is excellent in form stability, and the obtained activated carbon-attached fiber sheet is easy to be processed into various shapes, so that it is excellent in versatility.

The powdered activated carbon obtained by activating the phenolic resin by firing is excellent in the adsorptivity to ammonia and trimethylamine.

In the method for producing the activated carbon-attached fiber sheet according to the present invention, the fibers and the carbonizable resin powder are dispersed and opened almost uniformly by the opening cylinder, and are charged with static electricity by friction with the opening cylinder and the housing. Since the firing activation treatment is performed after the carbonizable resin powder adheres to the fiber electrostatically, a substantially uniform activated carbon-attached fiber sheet that is simple in process and has no unevenness in the adhesion of the carbonizable resin powder can be obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of a fiber sheet manufacturing apparatus of the present invention.

FIG. 2 is a graph showing the deodorization rate of activated carbon-attached fiber sheets of Examples and Comparative Examples 1 and 2 against ammonia.

FIG. 3 is a graph showing the deodorization rate of activated carbon-attached fiber sheets of Examples and Comparative Examples 1 and 2 with respect to trimethylamine.

FIG. 4 is a graph showing the deodorization rate for ammonia before and after regenerating the activated carbon-attached fiber sheet of the example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Feeder 2 ₁ Spreading cylinder 2 ₂ Spreading cylinder 2 ₃ Spreading cylinder 2 ₄ Spreading cylinder 3 Housing 4 Delivery part 5 Opening part 6 Air shower device 7 Conveyor 8 Suction box

Claims (2)

(57) [Claims] 1. A feeder 1 for supplying fibers and the like, and a fiber and the like supplied from the feeder 1 are dispersed and moved while being spread, and a metallic wire is attached to a surface thereof.
A plurality of adjacent opening cylinders 2 ₁ rotating in opposite directions,
2 ₂ , 2 ₃ ... 2 _n (n is a natural number), and a transfer section 4 in which fibers and the like move between adjacent opening cylinders.
And the end opening cylinder 2 _n of the dispersion had an opening 5 that emits like opening fibers, the open fiber cylinder 2 _1,
2 ₂ , 2 ₃ ... 2 _n , a conveyor 7 for receiving fibers and the like released from the opening cylinder 2 _n at the outlet end, and a released fiber and the like located below the conveyor 7. In the apparatus for manufacturing a fiber sheet provided with a suction box 8 for sucking the fiber, the fiber and the carbonized resin powder are supplied from the feeder 1 to obtain a fiber sheet in which the carbonized resin powder adheres to the fiber substantially uniformly. A method for producing an activated carbon-attached fiber sheet, comprising performing a firing activation treatment. 2. Activated carbon-attached fibers obtained by obtaining a fiber sheet in which carbonizable resin powder is adhered to a fiber having excellent heat resistance that can withstand a firing activation treatment without using an adhesive, and then performing a firing activation treatment. Sheet manufacturing method.