JP3528685B2 - Activated carbon and water purifier equipped with it - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to activated carbon having excellent adsorption properties for organic chlorine compounds, which are harmful components in water, particularly trihalomethanes, in water purification treatment, and a water purifier equipped with the activated carbon.

[0002]

2. Description of the Related Art Tap water used for drinking needs to contain residual chlorine added for the purpose of sterilization in a certain concentration or more. It is prescribed. However, chlorine added for the purpose of sterilization has an oxidative action of inorganic substances and an oxidative decomposition action of organic substances in addition to the bactericidal action, and humic substances, which are a kind of natural organic substances contained in raw water of tap water, etc. It is oxidized and decomposed to produce trihalomethanes which are carcinogens. On the other hand, the water quality of raw water used for tap water, etc. has been deteriorating in recent years due to the spread of pollution, and the humic substances contained in the raw water have been increasing along with this, and are generated by the oxidative decomposition of humic substances. The concentration of trihalomethanes is also increasing.

Therefore, as a means for removing trihalomethanes, various purification treatments with activated carbon having an adsorbing action have been studied. Generally, in the conventional activated carbon for water treatment, activated carbon having a large surface area with good properties such as iodine adsorption performance and methylene blue adsorption performance has been used in order to increase the adsorption capacity per unit volume of the object to be removed. In addition to the surface area, various activated carbons having a large number of pores with a pore diameter of 10 Å or less have been studied for the adsorption and removal of.

For example, Japanese Patent Laid-Open No. 9-110409 uses activated carbon based on a phenol resin as a base material in order to remove organochlorine compounds, and in particular, it occupies a pore volume having a pore diameter of 100 Å or less. Disclosed is activated carbon in which the proportion of pore diameters 6 to 8Å is 65 vol% or more.

These have large equilibrium adsorption amount, which is the static adsorption force of trihalomethanes, and the adsorption capacity was 3 mg or more per 1 g of activated carbon. In addition, activated carbon for water treatment is
It is also desirable that the hydrophilicity is high, and most of them are activated by steam as gas activation, but in addition, chemically activated carbon obtained by activation treatment with alkali hydroxide is also used. Activated carbon has various shapes, and in addition to powder, crushed, spherical, granular, and fibrous shapes, shaped cylinders, discs, granules, spheres, etc. are manufactured and used.

[0006]

However, in the above-mentioned conventional activated carbon gas-activated by water vapor, when water to be treated is passed, an adsorption zone for adsorbing trihalomethane is formed,
Since it is a dynamic adsorption that is adsorbed in the adsorption zone, the adsorption capacity per unit weight of activated carbon is lower than the equilibrium adsorption amount which is static adsorption, and there was a problem that the adsorption performance of activated carbon was not fully exhibited. .

[0007] Further, activated carbon made from coconut husk has a large surface area and has a wide range of adsorption properties for many substances contained in water. However, in the adsorption purification treatment of trihalomethanes, trihalomethane is activated by conventional gas activation or the like. If the pore diameter D that contributes to the adsorption of the group is adjusted so as to form a large number of pores in the range of 6 to 8Å, the pores having a pore diameter of 10 Å or more will be extremely reduced, and the malodorous components and coloring components, etc. There is also a problem of deteriorating the adsorption property.

Activated carbon made from a phenolic resin has a large adsorption capacity at the time of equilibrium adsorption when it forms pores having a pore diameter D of 6 to 8Å that selectively contributes to the adsorption of trihalomethanes. Since the diffusion speed of the molecule becomes very slow, there is a problem that the equilibrium arrival speed is slow when the trihalomethanes are removed from the passing water and the adsorption is not sufficient.

The present invention solves the above-mentioned conventional problems by providing an activated carbon having a large adsorption capacity for trihalomethanes from passing water and excellent adsorption characteristics for malodorous components and coloring components, and trihalomethanes and others. It is an object of the present invention to provide a water purifier that is equipped with activated carbon excellent in the adsorption property of the component (3) and can purify tap water with a simple structure.

[0010]

In order to solve the above problems, the activated carbon of the present invention has a parameter dV / dlogR.
In the pore diameter distribution represented by (V: pore volume, R: pore radius), dV / dlogR value is (a) pore diameter D is 10
The dV / dlogR value is 0.03 ~ in the range of Å- 40Å
At least one peak value in the range of 0.2,
(B) dV / dlog when the pore diameter D is in the range of 6Å to 9Å
R values and a least one or more peak values in the range of 1.0 to 7.0, a large number of pore diameter D on the inner surface of the large diameter pores of diameter D is 10 Å ～50A is 6Å A small-diameter pore of ~ 9Å is formed to absorb trihalomethane when passing water.
The adsorption capacity is 118 to 220 ppb · ton , which makes it possible to obtain activated carbon having a large adsorption capacity for trihalomethanes from passing water and excellent adsorption characteristics for malodorous components, coloring components, etc. Can be obtained.

Further, the water purifier of the present invention is provided with the activated carbon of the present invention as a water purifying material, which makes it possible to adsorb trihalomethanes and other harmful components from tap water. The advantageous effect that the device can be made compact is obtained.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention provides a parameter dV / dlogR (V: pore volume (cc
/ G), R: in a pore size distribution in terms of pore radius (Å)), dV / dlogR value is (a) a pore diameter D 10 Å
The dV / dlogR value is 0.03 to 0.
2 and at least one peak value in the range of 2, and (b) at least one peak value in the range of pore diameter D of 6Å to 9Å and dV / dlogR value of 1.0 to 7.0. the provided a number of pore diameter D on the inner surface of the large diameter pores are formed small diameter pores 6A～9A, adsorption capacity of water passing through the trihalomethanes pore diameter D is 10 Å ～50A
Is 118 to 220 ppb · ton, and as a result, the pore diameter D having a high static adsorption property of trihalomethane represented by chloroform (molecular diameter 5 Å) is 6 Å
Since there are many pores in the range of up to 9Å, the intermolecular force works strongly and the adsorption capacity of trihalomethane can be increased. Also, the pore diameter D is many pores in the range of 10 Å ～50A,
These pores serve as introduction holes for trihalomethane into pores having a pore diameter D of 6Å to 9Å, the dynamic adsorption characteristics are improved, and the adsorption capacity is further increased. Therefore, turbidity components, residual chlorine, chromaticity components, Excellent in other adsorption characteristics such as odorous components. Na
The adsorption capacity at the time of water flow is shown in paragraph 0035 below.
It is measured by the described method.

[0013] Here, when the dV / dlogR value in the range pore diameter D is 10 Å ～40A is greater than 0.2, a pore diameter D is low dV / dlogR value in the range of 6A～9A, trihalomethane The adsorption capacity of TiO2 tends to decrease, and conversely dV / d when the pore diameter D is in the range of 6Å to 9Å
When the logR value is larger than 7.0, the pore diameter D becomes 10
The dV / dlogR value in the range of Å to 40Å is small, and when it is smaller than 1.0, the static adsorption force tends to be low and the adsorption capacity of trihalomethane tends to be low, which is not preferable.

The invention according to claim 2 of the present invention is the activated carbon according to claim 1, wherein the pore diameter D is 20Å to 50.
In the range of Å, the dV / dlogR value does not become less than 0.03, whereby the adsorptive power becomes high, and the adsorptive removal capacity for various components other than trihalomethane can be enhanced.

The invention according to claim 3 of the present invention is that in claim 1 or 2, the raw material of the activated carbon is fruit shells, whereby the fruit shells which are industrial wastes are used. With this, activated carbon can be obtained at low cost, and since the amount of metallic impurities is less than that of mineral-based raw materials such as coal, the structure can be adjusted safely and easily.

The invention according to claim 4 of the present invention is that in the activated carbon according to claim 1 or 2, the raw material of the activated carbon is coconut husk, whereby coconut husk which is an industrial waste is converted. By using the raw material, the raw material can be obtained at low cost, and since the amount of metal impurities is smaller than that of the mineral raw material such as coal, the structure can be safely and easily adjusted. Furthermore, since it is stably supplied from Southeast Asia, activated carbon can be stably manufactured at low cost.

Here, coconut husks as the main material are used, and coconut husks and a mixture of coconut husks from several different production areas, as well as a mixture of cellulosic materials (eg wood chips and rice husks) and starches (eg rice, wheat, millet, rice bran) , Corn, potatoes), a mixture of organic or inorganic binders may be used.

The invention according to claim 5 of the present invention is that in claim 1 or 2, the raw material of the activated carbon is a thermosetting synthetic resin, whereby the activated carbon is cured during carbonization and activation treatment. Activated carbonization allows diversification of materials.

According to a sixth aspect of the present invention, in the fifth aspect, the raw material of the activated carbon is a phenolic synthetic resin, whereby the raw material contains few metal impurities, is safe, and has a structure. Designing the pore distribution by adjustment can be performed particularly easily.

Here, in addition to the phenol resin which is the main raw material, a synthetic resin (acrylonitrile resin, melanin resin, polyvinyl alcohol resin) that can serve as a carbon source, cellulosic material (for example, wood chips and rice husks), and starchy material (for example, rice, Wheat, millet, bran, corn, potatoes), other organic substances,
Alternatively, a mixture of inorganic binders can be used. As a result, the adsorption rate of activated carbon can be increased in the method for purifying trihalomethanes in water, which forms an adsorption zone, and the treated water passes through the adsorption zone, and therefore the adsorption capacity for trihalomethanes can be improved. You can

[0021] A water purifier according to claim 7 of the present invention comprises the activated carbon according to any one of claims 1 to 6 as a water purifying material. In the purification of trihalomethanes in water in which water to be treated passes through the adsorption zone, the adsorption capacity per unit weight of activated carbon is lower than the equilibrium adsorption amount, and the adsorption performance of activated carbon is not sufficiently exerted. In order to solve the problem, by designing the activated carbon within the range of the peak of the pore size distribution, the adsorption capacity can be greatly improved as compared with the conventional technique.

The activated carbon of the present invention (Embodiment 1), the pore diameter D is the parameter dV / dlogR at 10 Å ～40A least one or more peak values in the range of 0.03 to 0.2, a pore diameter D is 6Å ~ 9Å
And has a peak value of at least one in the range of dV / dlogR of 1.0 to 7.0 and a pore diameter D of 10Å to 5
On the inner surface of the large diameter hole in the range of 0Å, the diameter D
Is formed with a small-diameter hole in the range of 6Å to 9Å, which is manufactured by carbonization and activation as follows. First, carbonization treatment is performed by heating a raw material of activated carbon, such as phenol resin or coconut husk, to 400 to 700 ° C. in an inert atmosphere, for example, with nitrogen or argon gas. The heating at this time is 0.5 to 1.
400 ° C to 700 over 5 hours, preferably about 1 hour
C., for example, to 600.degree. C., after which this temperature (carbonization temperature), for example, 600.degree. Then, the activated carbon of the present invention further activates the carbide thus obtained. This activation treatment is performed while passing water vapor, oxygen, carbon dioxide, a gas containing two or more kinds of these gases, or nitrogen or argon gas further containing these gases through 800
It is carried out by heating to ℃ to 1000 ℃. The heating at this time is performed for 0.5 to 1.5 hours, preferably about 1 hour, from the start of heating to 800 ° C. to 1000 ° C., for example, 900 ° C., and then the activation temperature, for example, 900 ° C. It is maintained for 5 to 1.5 hours, preferably about 1 hour, and then naturally cooled.

Next, the pores formed by the above process will be described in more detail. At the time of carbonization, the pores of activated carbon are formed by first vaporizing water and light hydrocarbons from the raw material and at the same time distilling liquid tar, thereby forming a large number of pores having a pore diameter D of 100 Å or more. Then, upon activation, pores having a D of 6 to 9 Å are quickly formed on the inner surface of the pores having a D of 100 Å or more as the temperature rises. With the formation of pores with D of 6 to 9Å, D is 6
Since the activation temperature is high at the edge part that connects pores of ~ 9 Å to pores of 100 Å or more, the activated carbon itself expands due to heat and surface functional groups such as phenol groups contained in the activated carbon are removed by heat. It collapses when released. That is, the edge portion has a strong influence of heat due to activation, the temperature rises faster than the surroundings, and the activation gas such as water vapor reacts with carbon earlier than other portions, and gas such as H ₂ O, CO, and CO ₂ is gasified. As a result, the edge portion around the entrance of the pore having D of 6 to 9 Å is greatly engraved. When the temperature is 800 ° C. or lower, the amount of heat supplied is not sufficient and gasification does not occur, so that the cut-out of the edge portion becomes small. Therefore, at most, it will be a hollow hole with a diameter of 10 Å or less.
00 ° C. below D pores of 10 Å ～40A is not so much formed by activation. Therefore, this hollow does not form an introduction hole for adsorbing trihalomethane in a dynamic state, resulting in activated carbon having a poor adsorption force in a dynamic state.

Next, when the temperature is 1000 ° C. or higher,
The cut-out at the edge around the entrance of the pores with D of 6 to 9Å is very large and wide, which results in D of 10 to 40
As dV / dlogR of Å increases, the dV / dlogR value of D of 6 to 9Å relatively decreases. Therefore, since the number of pores having a function of adsorbing trihalomethane of 6 to 9Å is reduced, the activated carbon has a reduced adsorption power in terms of static adsorption exhibiting the original adsorption power.

In the temperature range from 800 to 1000 ° C.,
The higher the temperature, the larger the cut-out at the edge portion, and many cut-out holes having the same pore size with D of 6 to 9Å or more are formed at each activation temperature, and at least D is from 10 to 4
One or more peak values of dV / dlogR will appear in the range of 0Å. And, as the activation temperature is higher, the average size of the hollow becomes larger, and because the ash distribution of the composition of the raw material is also non-uniform, the pores with D of 40 to 50 Å as the temperature approaches 1000 ° C. The probability of formation of D is 4 and D formed at 800 ° C is 4
As a result, the dV / dlogR value is larger than the dV / dlogR value of the pores of 0 to 50Å. This D is 40-50Å
The size of the pores is very large as an introduction hole, and the probability of capturing diffusing trihalomethane increases, and D is 1
0 ~40Å introduction hole action is further up than that of,
The dynamic adsorption force can be greatly improved.

However, since the distribution of the dV / dlogR value slightly changes depending on the material used as the raw material of the activated carbon, the type of gas used for the carbonization treatment and the activation treatment, the carbonization temperature, and the activation temperature,
The above-mentioned carbonization treatment, activation treatment gas, carbonization temperature, activation temperature, etc. should be appropriately changed.

(Embodiment 2) Next, a water purifier provided with the activated carbon of the present invention will be described, but the present invention is not limited to this.

FIG. 5 is a schematic view of the essential parts of a water purifier equipped with the activated carbon of the present invention. In FIG. 5, 1 is a discharge pipe for discharging purified water that has passed through activated carbon, 2 is a water purifier body, 3 is a hollow fiber membrane, 4 is activated carbon of any one of Examples 1 to 3 described later, and 5 is hollow fiber. A water purification cartridge containing the membrane 3 and activated carbon 4, 6 is a water guiding tube for introducing tap water into the water purifier body 2, 7 is a water switch, and 8 is a faucet.

The water passage of the water purifier provided with the activated carbon of the present invention will be described. First, tap water supplied from the faucet 8 is introduced into the water purifier body 2 through the water guide tube 6 via the water switch 7. At this time, the water switch 7 can select whether to pass the tap water through the water purifier main body 2 or to discharge the tap water outside without passing through the water purifier main body 2 by a built-in switch. Further, when tap water is introduced into the water purifier main body 2, water is passed through the activated carbon 4 arranged in the lower portion of the water purification cartridge 5 to adsorb turbid substances having a small particle size and harmful substances such as trihalomethane in water. After that, the hollow fiber membrane 3 removes suspended particles having a large particle diameter, and the water is discharged through the discharge pipe 1 to be mainly used as drinking water.

As described above, the water purifier of the second embodiment is
Since it is formed by using activated carbon having excellent adsorption characteristics, a large amount of water purification capacity can be obtained with a small amount of activated carbon, and the entire water purifier can be made compact.

[0031]

Embodiments of the present invention will be described below with reference to FIGS.

(Example 1) Using a phenol resin as a raw material,
As the carbonization treatment, in an inert atmosphere, for example, under nitrogen, the temperature was raised to 500 ° C. in 1 hour from the start of heating, kept for 3 hours, and then naturally cooled. The carbide obtained as described above is heated to 900 ° C. for 1 hour from the start of heating as an activation treatment,
After passing through nitrogen containing steam, the mixture was kept for 1 hour and then naturally cooled.

The activated carbon obtained as described above was sieved and various measurements were carried out using a particle size of 60/200 mesh. Specific surface area determined by BET method is 1020 m
It was m ² / g. Parameter dV / which expresses pore size distribution
dlogR is a high-precision fully automatic gas adsorption device BERUSO
It is measured by adsorbing nitrogen with RP28 (manufactured by Nippon Bell Co., Ltd.), and the dV / dlogR value in the range of the pore diameter D (= 2R) of 20Å to 100Å is calculated from the adsorption isotherm of the nitrogen gas by the DH method (Dollimore). -Heal method), dV / dlog in the range of D to -20Å
The R value was analyzed by the MP method (Micropore method) from t-plot of the adsorption isotherm of nitrogen gas. The results are shown in FIGS. 1 (a) and 1 (b). That is, FIG. 1 (a) is a diagram showing the dV / dlogR value of the activated carbon of Example 1 of the present invention, and FIG. 1 (b) is an enlarged view of the relevant part.

As is apparent from FIG. 1 (a), dV / dlogR has one peak having a peak value of 5.8 in the range of the pore diameter D of 6 to 9Å. In FIG. 1B, two peaks of dV / dlogR with peak values of 0.15 and 0.17 in the range of D of 10 to 20 Å, D of 20 to 30
One peak with a peak value of 0.09 in the range of Å, D is 3
In the range of 0 to 40Å, the peak value of dV / dlogR is 0.
It has one peak of 07, D has a range of 10 to 40 Å, and has a total of four peaks with a peak value of dV / dlogR of 0.03 or more. When D is in the range of 6 to 40Å, there are a total of 5 peaks having a peak value of dV / dlogR of 0.03 or more. Further D is 10-5
It can be seen that dV / dlogR does not have a portion less than 0.03 even in the range of 0Å.

The adsorption characteristics of trihalomethane on the activated carbon having the above characteristics were measured by the following method. First, 100 ppb of trihalomethanes was added to tap purified water that had been purified by activated carbon and a 0.2 μm filter in advance, to obtain adjusted raw water. Then, volume capacity 50ml, thickness 20
A cylindrical column of mm was packed with activated carbon having the above-mentioned characteristics, and the above-mentioned adjusted raw water was passed through the activated carbon layer at an SV value of 640. The concentration of trihalomethanes in the effluent that passed through the activated carbon layer was subjected to a concentration pretreatment by the purge and trap method and quantitatively measured by a gas chromatograph-mass spectrometer. At this time, a point at which the concentration of trihalomethanes in the outflow water in water was 20% or more before and after passing through the activated carbon layer was defined as a breakthrough point, and the life of the activated carbon as an adsorbent was defined.
The amount of trihalomethanes adsorbed by activated carbon up to this point was determined to be 220 ppb ton, and it was found that the adsorption capacity of trihalomethanes was remarkably large. The results are shown in (Table 1).

[0036]

[Table 1]

As shown in (Table 1), the activated carbon of Example 1 has a very high adsorption capacity of trihalomethane of 6.3 times when passing water as compared with the activated carbon of Comparative Example 1 described later. there were.

(Example 2) Using a phenol resin as a raw material,
As the carbonization treatment, in an inert atmosphere (under nitrogen), the temperature was raised to 500 ° C. in 1 hour from the start of heating, held for 3 hours, and then naturally cooled. The charcoal-based material obtained as described above was heated to 850 ° C. in 1 hour from the start of heating as an activation treatment, nitrogen containing water vapor was passed through, held for 1 hour, and then naturally cooled. The specific surface area determined by the BET method is 950 mm ² /
It was g.

The activated carbon of Example 2 obtained as above was used with a particle size of 60/150 mesh and d
The V / dlogR value was measured in the same manner as in Example 1 and shown in FIG.
FIG. 2B is an enlarged view of the main part shown in FIG.

As is apparent from FIG. 2A, dV / dlogR has one peak with a peak value of 6.3 in the range of the pore diameter D of 6 to 9Å. In FIG. 2 (b), D is in the range of 10 to 20Å and the peak values of dV / dlogR are four peaks of 0.17, 0.14, 0.15 and 0.11, and D is in the range of 20 to 30Å. There is no peak with a peak value of 0.03 or more, D has one peak with a peak value of 0.1 in the range of 30 to 40Å, and dV / dlogR has a peak value of 0 in the range of D to 10 to 40Å. It has 5 peaks of 0.03 or more in total. When D is in the range of 6 to 40Å, there are a total of 6 peaks having a peak value of dV / dlogR of 0.03 or more. However, D has a part of less than 0.03 in dV / dlogR in the range of 20 to 50Å, which is lower than that of Example 1 as a whole.

The results of measuring the adsorption characteristics of trihalomethane for the activated carbon having the above characteristics by the same method as in Example 1 are shown in (Table 1). As can be seen from (Table 1), the amount of trihalomethanes adsorbed was 118 ppb · ton, and when D was 20 to 50Å, dV / dlogR was 0.
Since it has a portion less than 03, it was found to be lower than in Example 1. However, the adsorption capacity of trihalomethane during water passage was 3.4 times higher than that of the activated carbon of Comparative Example 1 described later.

(Example 3) Using coconut husk as a raw material for activated carbon, and as a carbonization treatment,
5 hours from the start of heating in an inert atmosphere (under nitrogen)
The temperature was raised to 00 ° C., the temperature was maintained for 3 hours, and then naturally cooled. Next, as activation treatment, the temperature was raised to 900 ° C. in 1 hour from the start of heating, nitrogen containing water vapor was passed through and kept for 1 hour, and then naturally cooled. The specific surface area obtained by the BET method is 1
It was 100 mm ² / g.

Of the activated carbon of Example 3 obtained as described above, one having a particle size of 60/150 mesh was used, and the dV / dlogR value was measured in the same manner as in Examples 1 and 2, and FIG. It is shown in FIG.
It is shown in (b).

As is apparent from FIG. 3A, dV / dlogR has one peak having a peak value of 4.3 in the range of the pore diameter D of 6 to 9Å. In FIG. 3 (b), two peaks of dV / dlogR peak values of 0.15 and 0.25 in the range of D of 10 to 20Å, D of 20 to 30
There is no peak with a peak value of 0.03 or more in the range of Å, and D
There is no peak with a peak value of 0.03 or more even in the range of 30 to 40Å. That is, when D is in the range of 10 to 40 Å , d
Peak to peak value of V / dlogR is 0.03 or more
There are only 2 in total, and dV / d in the range of 6-40Å
3 peaks with a logR peak value of 0.03 or more
I only have one. Further, in the range of D of 20 to 50Å, the numerical value is low as a whole, and dV / dlogR is 0.0.
It is 2 or less, and the pore volume is lower than that of Example 2 as a whole.

Activated carbons having the above characteristics were used in Examples 1 and 2.
The results of measuring the adsorption characteristics of trihalomethane by the same method as in (1) are summarized in (Table 1). When the adsorption capacity of the amount of trihalomethanes was determined, it was 120 ppb · ton, which was 3.4 times higher than the activated carbon of Comparative Example 1 described later, but lower than that of Example 1 and D was 10 to 10. The peak value 0.25 of dV / dlogR in the range of 20Å is shown in FIG.
It was present at the position shown in (b) and had an adsorption capacity substantially similar to that of Example 2.

Comparative Example 1 A phenol resin was used as a raw material for activated carbon, and the carbonization treatment was carried out in an inert atmosphere (under nitrogen), the temperature was raised to 500 ° C. in 1 hour from the start of heating, and the mixture was kept for 3 hours and then spontaneously released. Chilled Next, as activation treatment, 90 hours after starting heating
The temperature was raised to 0 ° C., nitrogen containing water vapor was passed through and kept for 1 hour, and then naturally cooled. The specific surface area determined by the BET method was 960 mm ² / g.

Using a particle size of 60/150 mesh, dV / dlogR value was measured by the same method as in Examples 1 to 3 . The results are shown in FIG. 4 (a), and an enlarged view of the relevant parts is shown in FIG. 4 (b).

As is apparent from FIG. 4 (a), dV / dlogR has one peak with a peak value of 5.9 in the range of the pore diameter D of 6 to 9Å. In FIG. 4B, three peaks of dV / dlogR have peak values of 0.23, 0.11, and 0.1 in the range of D of 10 to 20Å, and D is 2
In the range of 0 to 30Å, the peak value of dV / dlogR does not have a peak of 0.03 or more, and in the range of D of 30 to 40Å, the peak value of dV / dlogR is not 0.03 or more, 0.025 was the maximum. D is 10-40
There are 3 peaks with a peak value of 0.03 or more in the range of Å, and a total of 4 dV / dlog in the range of D of 6 to 40 Å.
It has an R peak. However, there is no part where dV / dlogR is 0.03 or more in the range of D to 20 to 50Å,
It was low as a whole as compared with Examples 1 to 3 .

The trihalomethane adsorption capacity of the activated carbon of Comparative Example 1 having the above characteristics was determined and is shown in (Table 1).
As can be seen from (Table 1), the adsorption capacity of trihalomethane is 35 ppb · ton, which is extremely small as compared with Examples 1 to 3 .

[0050]

According to the invention described in claim 1 of the present invention, the pore diameter D having a high static adsorption property is 6Å with respect to trihalomethane represented by chloroform (molecular diameter 5Å).
Since there are many pores in the range of up to 9Å, the intermolecular force works strongly and the adsorption capacity of trihalomethane can be increased.

According to the second aspect of the present invention,
In addition to the effect of the invention described in claim 1, the ability to adsorb and remove various components other than trihalomethane can be further enhanced.

According to the invention of claim 3 of the present invention,
In addition to the effects of the invention described in claims 1 and 2, by using fruit shells which are industrial wastes, activated carbon can be obtained at low cost, and metal impurities are contained more than mineral raw materials such as coal. Since there are few, it is safe and the structure adjustment is easy.

According to the invention of claim 3 of the present invention,
In addition to the effects obtained by the invention according to claim 1 or 2, by using fruit shells which are industrial wastes, activated carbon can be obtained at low cost, and metal is more preferable than mineral-based raw materials such as coal. Since it contains few impurities, it excels in safety, structural adjustment is easy, and design freedom is excellent.

According to the invention of claim 4 of the present invention,
In addition to the effect obtained by the invention described in claim 3, the adsorption property of trihalomethanes is dramatically improved without deteriorating the wide range of purification performance of the coconut husk activated carbon which has been widely used from the past. Can be improved.

According to the invention of claim 5 of the present invention,
In addition to the effect obtained by the invention of claim 1 or 2, it is possible to diversify the material by hardening at the time of carbonization and activation to activate carbonization.

According to the invention of claim 6 of the present invention,
In addition to the effect obtained by the invention described in claim 5, by increasing the adsorption capacity of activated carbon made of a phenol resin having a high adsorption property for trihalomethanes, the running cost of activated carbon having a high material cost is reduced. Can be realized.

According to the invention of claim 7 of the present invention,
Since the amount of activated carbon required for adsorbing trihalomethanes is reduced, the amount of activated carbon required to fill a cartridge used in a water purifier or the like is reduced, so that the cartridge can be downsized and the service life can be extended.

[Brief description of drawings]

FIG. 1 (a) dV / dl of activated carbon of Example 1 of the present invention
Figure showing the ogR value (b) Enlarged view of the main part

FIG. 2 (a) is a diagram showing dV / dlogR values of the activated carbon of Example 2 (b) is an enlarged view of a main part thereof.

FIG. 3 (a) is a diagram showing the dV / dlogR value of the activated carbon of Example 3 (b) is an enlarged view of the relevant part.

FIG. 4 (a) is a diagram showing the dV / dlogR value of the activated carbon of Comparative Example 1 (b) is an enlarged view of the relevant part.

FIG. 5 is a schematic view of a main part of a water purifier equipped with activated carbon according to the present invention.

[Explanation of symbols]

1 discharge pipe 2 Water purifier body 3 hollow fiber membranes 4 activated carbon 5 water purification cartridge 6 water transfer tube 7 water switch 8 faucet

Continuation of front page (56) Reference JP-A-11-157821 (JP, A) JP-A-10-297912 (JP, A) JP-A-9-328308 (JP, A) JP-A-10-279303 (JP , A) JP-A-7-215711 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C01B 31/08-31/14 B01J 20/20 C02F 1/28

Claims (7)

(57) [Claims] 1. In the pore size distribution represented by the parameter dV / dlogR (V: pore volume, R: pore radius), dV
/ DlogR value, (a) a pore diameter D is 10 Å ～40A
In the range of dV / dlogR value of 0.03 to 0.2, at least one peak value, and (b) pore diameter D
Is in the range of 6Å to 9Å and the dV / dlogR value is 1.0 to
Comprising at least one or more peak values, the ranges of 7.0, the small-diameter pores of a number of pore diameter D on the inner surface of the large diameter pores of diameter D is 10 Å ～50A is 6Å~9Å Is formed, and the adsorption capacity of the trihalomethane during water flow is 118
Activated carbon characterized in that it is ~ 220 ppb ton . 2. The activated carbon according to claim 1, wherein the pore diameter D is in the range of 20Å to 50Å and the dV / dlogR value does not become less than 0.03. 3. The activated carbon according to claim 1, wherein the raw material of the activated carbon is fruit shell. 4. The activated carbon according to claim 1, wherein the raw material of the activated carbon is coconut husk. 5. The activated carbon according to claim 1, wherein the raw material of the activated carbon is a thermosetting resin. 6. The activated carbon according to claim 5, wherein the thermosetting resin is a phenol resin. 7. A water purifier comprising the activated carbon according to any one of claims 1 to 6 as a water purification material.