WO1995016638A1 - Water purifying material, process for producing the same, and water purification equipment - Google Patents
Water purifying material, process for producing the same, and water purification equipment Download PDFInfo
- Publication number
- WO1995016638A1 WO1995016638A1 PCT/JP1994/001835 JP9401835W WO9516638A1 WO 1995016638 A1 WO1995016638 A1 WO 1995016638A1 JP 9401835 W JP9401835 W JP 9401835W WO 9516638 A1 WO9516638 A1 WO 9516638A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- activated carbon
- silver
- hot water
- water purification
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
- C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
Definitions
- TECHNICAL FIELD This invention relates to a water purification material, a manufacturing method thereof, and water purification equipment, and more particularly, a water purification material used for purifying domestic water and industrial water, a manufacturing method thereof, and an industrial-scale water purification equipment using the water purification material.
- water purification facilities are facilities for obtaining the water required by various industries such as the food industry, the pharmaceutical industry, and the semiconductor industry, in other words, water from which free chlorine and organic matter have been removed. is provided with an activated carbon filtration tower that adsorbs and removes free chlorine and organic matter in the raw water supplied from the raw water supply channel and sends the treated water to the treated water extraction channel, and injects free chlorine into the raw water supply channel.
- This is an activated carbon water treatment facility equipped with means for injecting free chlorine.
- a water purification material made by impregnating activated carbon with silver is used.
- many water purification materials with various filtering materials have been developed. It has been recognized that the small amount of silver contained in these water purifying materials has the effect of preventing germs from occurring inside the water purifying materials.
- this water purification material has a relatively large amount of silver elution, which has been a problem from a sanitary point of view.
- the antibacterial activity is expressed by the eluted silver ions, the duration of the antibacterial activity is extremely short, and it could not be adopted for industrial scale applications.
- the activated carbon filtration layer in the activated carbon filtration tower becomes the optimum environment for the growth of viable bacteria. As a result, if left as it is, viable bacteria will proliferate in the activated carbon filter layer and mix into the treated water, making it impossible to obtain sterile treated water.
- a first object of the present invention is to develop and provide a water purifying material that has an excellent effect of suppressing bacteria generated inside in addition to general water purifying effects such as removing chlorine smell and musty odor.
- a second object of the present invention is to provide a method for producing such a water purification material.
- a third object of the present invention is to provide a water purification facility that can obtain sterilized treated water from which free chlorine and organic matter are removed while maintaining a good operating rate of the activated carbon filtration tower. at the point.
- the water repellent material of the present invention is characterized in that it consists of silver-bound zeolite or a silver-supported and bound zirconium phosphate compound and active ash power.
- the water purifying material of the present invention is characterized in that, in the above invention, the content of silver bonded to the zeolite or silver supported and bonded to the zirconium phosphate compound is 0.01 to 3.0% of the entire water purifying material. At a certain point as 0 0%.
- the present inventors When silver is used as a water purification material, the present inventors have conventionally used activated carbon as its carrier. By blending the fungicide carried and bound to the activated carbon, it imparts excellent antibacterial properties to the water purification material when tap water is passed under the same conditions as the silver-impregnated activated carbon, and the silver is added to the purified water. It was found that the amount of elution to In addition, zeolite with silver bound or silver supported However, by mixing activated carbon with the bound zirconium phosphate compound, we obtained the result that an excellent water purification effect can be obtained in combination with the adsorption effect of activated carbon. Based on these findings, the present invention was completed.
- the water purification material of the present invention has excellent antibacterial properties, and the amount of silver eluted into purified water is very small.
- the water purifying material of the present invention is most characterized by having excellent antibacterial properties, but it also contains ingredients that impair the taste of water, such as chlorine odors, impurities, malodorous components, and strong odors due to free chlorine. It has a high function of adsorbing and removing .
- the present invention will be described in detail below.
- the water purification material of the present invention must contain silver-bonded zeolite or silver-supported and bonded zirconium phosphate compound.
- zeolites are composed primarily of alkaline-metal or alkaline-earth metal aluminosilicates, each containing one Si02 tetrahedron and one A104 tetrahedron in a methane-type structure. It forms a three-dimensional skeletal structure with large, regular cavities in which atoms are shared.
- zeolite Due to the cyclic structure of oxygen forming the skeleton of zeolite, zeolite has a constant pore size in the range of 310 A, and has adsorptive and molecular sieving properties based on this pore structure. Therefore, silver ionically bonded inside the pores of the zeolite itself has a low ionization tendency, and is therefore not eluted at a dissolved ion concentration similar to that of tap water.
- zeolites with extremely uniform pore diameters have been synthesized by synthetic methods, and other zeolites such as kairiyokulite and fluorite are also produced naturally.
- naturally occurring zeolites can also be used for the base material of the water purification material of the present invention.
- zeolite since zeolite has the composition described above, it is completely harmless from a sanitary point of view.
- Silver ions, copper ions, etc. are known to have antibacterial properties against general bacteria and bacteria, and since they are inorganic, they have antibacterial properties against a wide range of bacteria and fungi, making them suitable for water purification materials. , from a sanitary point of view, these heavy metal ions cannot be directly injected into tap water. However, when these antibacterial metal ions bond with the atoms constituting the pore structure of the zeolite skeleton, they are hardly eluted when tap water is treated, and it is possible to impart high antibacterial properties to the water purification material. can.
- the antibacterial activity of the present invention is basically different from the principle of expecting the antibacterial force of eluted silver ions seen in conventional silver-impregnated activated carbon. They die on contact. Furthermore, since the amount of elution into water is small, it is also preferable when the water purification material is used for a long period of time. This is the most significant feature of the water purification material of the present invention.
- a zirconium phosphate compound also has similar properties to zeolite, and when silver is supported and bound to it, exhibits the same antibacterial properties as when silver is bound to zeolite, so it can be used as the water purification material of the present invention.
- activated carbon was used as a carrier for impregnating silver, but when tap water is passed through to purify water, impregnating silver to the extent that it imparts sufficient antibacterial properties to the water purification material often results in sanitary conditions. It may exceed 50 ppb, which is considered to be the above safety standard. As shown in Table 1, even if the amount of silver impregnated is very small, the amount of elution is quite high, so it is difficult to increase the amount of impregnated silver, the antibacterial property is not necessarily sufficient, and the usable period is also comparable. was short.
- zeolite or zirconium phosphate compounds have a very low elution amount even when silver is bound to the extent that they provide sufficient antibacterial properties. ing.
- the silver ions of zeolite bound with silver or zirconium phosphate compounds bound with silver when in contact with microorganisms, inhibit enzymes in the respiratory system and basic metabolic system of microbial cells, or inhibit mass transfer in cell membranes. exhibit antibacterial properties It is considered to be a thing. Along with this antibacterial effect, it is thought that it also exhibits deodorizing properties by inhibiting the growth of fungi that cause offensive tastes and odors.
- the bacteria that may grow on the water purification material include common bacteria, Escherichia coli, Staphylococcus aureus, etc., but any of these bacteria or other bacteria can be used. It has been confirmed to exhibit strong antibacterial properties.
- the amount of silver bound to zeolite is not particularly limited.
- the content is preferably about 0.5 to several percent in consideration of antibacterial properties when coexisting with activated carbon.
- the water purification material of the present invention must contain activated carbon in addition to silver-bonded zeolite or silver-supported and bonded zirconium phosphate compound.
- the activated carbon used as the base material here usually has a large surface area of several 100 m 2 per gram or more, and can be used in a wide range of carbon materials that exhibit high adsorption properties. Generally, carbonized materials such as coconut shells or wood or coal are used, but any of them may be used. Activation may be performed in an atmosphere of either water vapor or carbon dioxide at elevated temperatures.
- the effect is recognized regardless of whether it is crushed coal, granulated coal or granular coal. It may be convenient to use a sheet-like adsorption layer impregnated with granulated carbon or activated carbon in terms of handling such as pressure loss and replacement.
- Granulated coal is prepared by adding 30 to 60 parts of petroleum pitch or coal as a binder to 100 parts of a carbonaceous material according to a conventional method, and then activating after kneading and molding.
- Activated charcoal as a very unique non-polar adsorbent, exhibits high adsorption properties for almost all dissolved substances in water. It is highly effective in purifying tap water by adsorbing and removing the strong odor caused by free chlorine present in tap water and other components that impair the taste of water.
- the water purification material of the present invention contains either silver-bonded zeolite or a silver-supported and bonded zirconium phosphate compound and activated carbon, and the silver mainly imparts antibacterial properties to the water purification material.
- the adsorbability of activated carbon removes impurities, malodorous components, and strong odors in tap water, and the synergistic effect of both provides a high refining effect and, in particular, imparts antibacterial properties to the water purification material, making it possible to use it for a long time.
- Monodea The mixing ratio of the silver-bonded zeolite or the silver-supported and bonded zirconium phosphate compound and the activated carbon in the water purification material is not particularly limited. Considering the water purification effect, the amount of the above-mentioned antibacterial material is limited to the extent necessary to impart antibacterial properties, and a composition using as much activated carbon as possible is preferable.
- the silver content of the water purification material is not particularly limited, it is preferably 0.01 to 3.00% of the entire water purification material.
- the silver content is 0.01% or less, the antibacterial properties tend to decrease. Also, even at 3.00% or more, almost no improvement in antibacterial properties is observed, and on the contrary, there is a tendency for the silver elution amount to increase.
- the characteristic configuration of the method for producing the water purification material of the present invention is that silver-bound zeolite or silver-supported and bound zirconium phosphate compound is mixed and pulverized with a carbonaceous raw material, and if necessary, a binder and After adding and mixing the admixture, it is made into granulated coal or granular coal, oxidized at 300 ° C or less in an atmosphere containing oxygen, carbonized and carbonized in an inert gas, and then activated.
- a predetermined amount of silver-bound zeolite or a silver-supported and bound zirconium phosphate compound and a carbonaceous raw material are sufficiently mixed, pulverized, and further used as a binder.
- pitch, coal tar, etc. are added, and if necessary, water or heavy oil is added as an admixture, and after mixing with a mixer, granulated coal or granulated coal is obtained.
- Granulated coal or granular coal should be oxidized at 30 CTC or less in an atmosphere containing oxygen.
- the atmosphere containing oxygen is air, a mixed gas of oxygen and nitrogen, a gas containing oxygen in water vapor or carbon dioxide, or the like. Water vapor, carbon dioxide, etc. are inert to the carbonaceous raw material at 300°C or lower.
- Granulated coal or granular coal is oxidized by this process, and oxygen atoms are bound to the carbonaceous surface. Oxidized granulated coal or granular coal should be carbonized and carbonized in inert gas. In order to sufficiently carbonize granulated coal or granular coal, it is necessary to raise the dry distillation temperature to 600°C to 650°C.
- the water purification material of the present invention having excellent antibacterial properties can be obtained.
- the activating atmosphere is water vapor, carbon dioxide, a mixed gas thereof, or the like.
- the activating atmosphere preferably has a high water vapor content and a composition containing carbon dioxide, such as a gas obtained by burning liquefied petroleum gas.
- the water purifying material thus obtained consists only of silver-bonded zeolite or silver-supported and bonded zirconium phosphate compound, and activated carbon.
- the zeolite with silver or the zirconium phosphate compound with silver supported and bound, and the carbonaceous raw material are mixed and pulverized into granulated coal or granulated coal, which is further processed in an oxygen-containing atmosphere.
- the process of oxidizing at 00°C or less, dry-distilling and carbonizing in an inert gas, and then activating is a characteristic process in the manufacturing method of this water purification material.
- the water purifying material of the present invention is limited only to those obtained by the aforementioned manufacturing method. Therefore, according to the present invention, the water purification material of the present invention has antibacterial properties of silver-bound zeolite or a silver-supporting and binding zirconium phosphate compound, and release in tap water due to the adsorptivity of activated carbon. Excellent water purification effect due to the synergistic effect of adsorbing and removing chlorine, impurities, malodorous substances, and musty odors.
- the characteristic configuration of the water purification equipment of the present invention is characterized in that the activated carbon filter in the activated carbon filtration tower
- the water purification material according to the present invention is dispersedly mixed in the overlayer, and activated carbon regeneration means is provided for supplying hot water to the activated carbon filtration layer to regenerate the activated carbon.
- the mixed amount of the water purification material that is, the mixed amount of silver ions is calculated as the amount of activated carbon in the activated carbon filtration layer.
- the amount of silver contained in the activated carbon filtration tank is 0.01 to 3 of the total amount of activated carbon including the activated carbon filled in the activated carbon filtration layer and the activated carbon contained in the water purification material. 0.00% has been found to achieve sterilization of the activated carbon filtration layer.
- activated carbon As a means for sterilizing the activated carbon filtration layer by antibacterial treatment, for example, activated carbon called antibacterial carbon, that is, impregnated with silver compounds and dissolving silver ions in the treated water is antibacterial. It is also conceivable to use activated charcoal that expresses the ability. In this case, the antibacterial activity is expressed by the elution of silver ions into the treated water, that is, the antibacterial carbon loses its antibacterial activity in a period of about one month after silver is consumed during water treatment. In order to maintain the antibacterial activity, it is necessary to perform costly and time-consuming maintenance such as replacing the antibacterial charcoal.
- the activated carbon filter layer antibacterial and sterile by using silver zeolite
- the silver zeolite is fragile and easily microparticulated, it is microparticulated and flows out during water treatment.
- the desired sterilization of the activated carbon filter layer cannot be maintained, and costly and troublesome maintenance such as replenishment of silver zeolite is required.
- silver ion which kills viable bacteria by physical contact with them, is hardly eluted into water, and is contained in the activated carbon filter layer in the form of a water purification material. Since the activated carbon filter layer is made antibacterial by dispersing and mixing, maintenance for maintaining the antibacterial ability is not required, or if necessary, it is very light.
- hot water is used as a heating means.
- a predetermined temperature about 85 ° C
- the hot water circulation step In this case, a small amount of heat input for heat dissipation loss is sufficient, and temperature control is extremely easy.
- FIG. 1(a) shows changes in the raw water treatment period and the number of bacterial colonies in purified water in Comparative Example 6.
- FIG. 1(b) shows changes in the raw water treatment period and the number of bacterial colonies in purified water in Example 9.
- Fig. 2 is a schematic configuration diagram showing the operating state of water treatment.
- Fig. 3 is a schematic configuration diagram showing the state of hot water circulation regeneration operation.
- Fig. 4 is a schematic configuration diagram showing the raw water washing operation state.
- Fig. 5(a) is a graph showing changes in the number of viable bacteria over time in a conventional activated carbon filtration tower.
- FIG. 5(b) is a graph showing changes in the number of viable bacteria over time in the activated carbon filtration tower of the present invention.
- Figure 6 is a graph showing the relationship between filtered water volume and removal rate
- Fig. 7 is a graph showing the relationship between flow rate and silver ion elution amount
- Fig. 8 is a schematic configuration diagram showing the water treatment operation state of another embodiment
- Fig. 9 is a schematic configuration diagram showing a hot water circulation regeneration operation state of another embodiment
- FIG. 10 is a schematic configuration diagram showing the raw water washing operation state of another embodiment.
- Synthetic zeolite bound with 2.2% silver was added to 100 parts of coconut shell charcoal to give the silver content shown in Table 1, and the mixture was well pulverized with an atomizer mill. To this, 30 parts of pitch as a binder, 18 parts of heavy oil and 10 parts of water as admixtures were added and thoroughly mixed with a mixer. Next, after forming into granulated coal with a diameter of 4 mm using a pellet mill, the granulated coal was pulverized and sieved to 7 to 16 mesh with a vibrating sieve to obtain granulated coal with almost uniform particle sizes.
- the silver-bound zeolite content of the sample of Example 6 was the same as that of Example 5, and zeolite with an increased silver-bound amount was used as a raw material. .
- the coal granules were placed in a fluidized bed furnace and heated to 180°C at 165°C while blowing air. heated and oxidized. Furthermore, the air was shut off and the mixture was gradually heated to dry distillation and carbonization at 530°C to 630°C. Dry distillation reduced the filled specific gravity from 0.705 to 0.590. Next, the dry-distilled coal was inserted into an activation furnace, and kerosene combustion gas was blown into it to activate it at 700°C to 950°C to obtain a water purification material.
- Example 1 The silver contents of the water purification materials obtained as described above were 0.002% (Example 1), 0.05% (Example 2) and 0.29% (Example 3), respectively. , 0.8% (Example 4), 1.2% (Example 5) and 3.5% (Example 6).
- activated carbon obtained in the same manner and a sample impregnate with silver were prepared with a silver content of 0.009% (Comparative Example 1) and 0.071% (Comparative Example 1). 2) and non-silver-impregnated activated carbon (Comparative Example 3) were prepared.
- the silver elution amount was measured by a flameless atomic absorption photometer (using a pyrocarbonized graphite tube) based on the Food Additives Test Method.
- the amount of residual free chlorine was determined by measuring the amount of residual free chlorine in tap water immediately after filling a cartridge with 250 g of the sample and running 50 liters of tap water at 2 liters/min.
- the amount of free chlorine in the raw tap water was 1.2 ppm.
- the above-mentioned sample was pulverized, a small amount of latex was used as a binder, and it was evenly attached to a 5 cm square foamed polyurethane sheet.
- the test piece After inoculating the test piece with 1 m 1 of a suspension of Aspergillus niger spores (containing 104 spores Zm 1 ), the specimen was placed at a relative humidity of 90% for 25 minutes. It was left in a constant temperature bath for 24 hours.
- test piece Place the test piece with the surface sprayed with the spore suspension of the sheet down on a fungal agar medium (GP medium), 25, and place it in a constant temperature bath with a relative humidity of 90%. It was left to stand for 20 days, and the state of mycelium growth was observed.
- GP medium fungal agar medium
- the status of mycelium development was evaluated according to the following criteria. Namely
- Evaluation 1 Among the areas inoculated with the spore suspension of the test piece, the area where mycelium was generated is 1 Z 3 or less.
- Evaluation 2 Among the areas inoculated with the spore suspension of the test piece, the area where mycelium was generated is 1 Z 3 or more.
- Evaluation 3 Mycelium was generated at high density on the entire area of the test piece inoculated with the spore suspension. .
- Table 1 shows the results of these tests.
- the silver-impregnated activated carbon of the comparative example has a very low silver content, the silver elution amount is considerably high. The elution amount is also very low.
- the water purifying material of the present invention has remarkably high antibacterial properties. Furthermore, the water purification material of the present invention has excellent water purification functions such as free chlorine removal.
- a water purification material containing the silver-bonded zeolite of the present invention (Example 7) or silver-supported and bonded zirconium phosphate (Example 8), and conventionally used silver-impregnated activated carbon water purification for comparison A laboratory-scale water purification test was conducted using a water purification material (Comparative Example 5) and a water purification material using only activated carbon (Comparative Example 4). As shown in Table 2, the composition of the water purification material is uniform at a ratio of 80% granular coconut shell activated carbon to 20% antibacterial water purification material of the present invention and conventional silver-impregnated activated carbon. Prepared by mixing.
- Table 3 shows the number of bacterial colonies generated in the purified water of Examples 7 and 8 and Comparative Examples 4 and 5.
- the number of bacterial colonies generated was measured by measuring the number of colonies formed in the medium after culturing for 36°48 hours using a standard agar medium.
- Example 7 The water purifying material used in Example 7 as the water purifying material of the present invention (Example 9), and the water purifying material used in Comparative Example 5 as the silver-impregnated activated carbon water purifying material conventionally used for comparison (Comparative Example 6) was packed into an industrial scale activated carbon tower. Tap water was used as raw water, and the water flow was continued for 6 months under the following conditions, and the treatment period and the number of bacterial colonies generated in the purified water were measured. Table 4 shows the composition of the water purification material and the sterilization conditions for the activated carbon tower.
- the activated carbon tower filled with silver-impregnated activated carbon was subjected to heat sterilization by periodically circulating heated water, whereas the water purification material of the present invention was not subjected to the above operation.
- FIGS. 1(a) and (b) The relationship between the water flow period and the number of bacterial colonies generated in the purified water of Comparative Example 6 and Example 9 is shown in FIGS. 1(a) and (b), respectively.
- the viable count of general bacteria in the purified water is measured by opening the sampling cock while the activated carbon tower is in operation, and sampling the purified water after passing through the activated carbon tower. After culturing at 6°C for 48 hours, the number of colonies formed in the medium was counted. ho 1]
- the activated carbon tower filled with silver-impregnated activated carbon which has been conventionally used as a water purification material, has been subjected to frequent heat sterilization, but the number of colonies is Force reaching 2 to 20 colonies/m 1 Almost no colonies were detected during the treatment period in the purified water of the activated carbon tower filled with the water purification material of the present invention.
- the eluted Ag ions varied between 0.5 and 3 ppb.
- the antibacterial activity of the water purification material of the present invention is significantly higher than that of conventional silver-impregnated activated carbon, and that there is a remarkable effect especially when used for a long period of time in a large-scale industrial water purification apparatus. .
- this water purification facility is an activated carbon filtration tower that adsorbs and removes free chlorine and organic matter in raw water a supplied from raw water supply channel 1 and sends treated water b to treated water extraction channel 2.
- 3 is provided, free chlorine injection means for injecting free chlorine into the raw water supply channel 1, and activated carbon regeneration means are provided.
- the raw water supply channel 1 is provided with a raw water storage tank 4 and a water pump 5 for taking out the raw water a from the raw water storage tank 4 and sending it to the activated carbon filtration tower 3 .
- An activated carbon trap filter 6 for removing activated carbon in the treated water is installed in the treated water extraction path 2 .
- the activated carbon filtration tower 3 has an activated carbon filtration layer 3B filled with granular activated carbon in the tower 3A. It is configured to be installed in a filtering state, and is of a type in which the raw water a is pressurized and passed through the activated carbon filtration layer 3B.
- the activated carbon filter layer 3B is formed by filling the tower 3A with activated carbon, and granular water purification materials are dispersedly mixed in the activated carbon filter layer 3B.
- This water clearing material has the antibacterial properties shown in the examples of the water purifying material and its manufacturing method.
- this water purification material contains zeolite (hereinafter referred to as silver zeolite) in which silver ions are bonded to ion exchange groups by an ion exchange reaction and activated carbon as components. It is something to do. More specifically, silver zeolite and a carbonaceous raw material are mixed and pulverized, a binder and, if necessary, an admixture are added and mixed, then granulated into granules, and the granules are placed in an oxygen-containing atmosphere. It is produced by oxidizing at 300 ° C or less at , dry-distilling and carbonizing in an inert gas, and then activating in a high-temperature activation atmosphere.
- Carbonaceous raw materials include coconut shells, wood and coal, binders include petroleum pitch and coal tar, and admixtures include water and heavy oil.
- the oxygen-containing atmosphere includes air or a mixed gas of oxygen and nitrogen, and a gas containing oxygen in water vapor or carbon dioxide.
- the inert gas is a gas that is inert to the carbonaceous raw material in the dry distillation temperature range of 600 ° C to 650 ° C that can sufficiently carbonize the granules. , nitrogen gas containing a small amount of carbon dioxide, or the like.
- the activating atmosphere is water vapor, carbon dioxide, or a mixed gas atmosphere of both.
- the antibacterial water purification material is activated carbon and antibacterial water purification material filled in the activated carbon filtration tower 3 so that the amount of silver contained in the activated carbon filtration tank 3B constitutes the activated carbon filtration layer 3B. It is mixed so that it becomes 0.01 to 3.00% of the total amount of activated carbon including the activated carbon contained in the material.
- the reason why the amount of silver is set in the range of 0.01 to 3.00% is that if the amount is less than 0.01%, the desired antibacterial activity cannot be exhibited, and if the amount is more than 3.00%, the antibacterial effect This is because it is uneconomical because no improvement in performance can be seen.
- the free chlorine injection means includes a storage tank 7 for storing hypochlorous acid hooda c, and sodium hypochlorite c taken out from the storage tank 7 and supplied to the upstream side of the raw water storage tank 4 in the raw water supply channel 1. c Then, the raw water a into which the sodium hypochlorite c is injected is retained in the raw water storage tank 4 for a predetermined time, so that the sodium hypochlorite c injected for sterilization is added to the raw water a. It is configured so that a side reaction of reacting organic matter with sodium hypochlorite c occurs and part of the organic matter changes to an organochlorine compound.
- the retention time in the raw water storage tank 4 is set to a sufficient time for the organic substances in the raw water a to react with the sodium hypochlorite c to partly transform into organochlorine compounds.
- the supply pump 8 sets the concentration of free chlorine (C 12 ) at the tower inlet 3a of the activated carbon filtration tower 3 to a set value (a value necessary to prevent the growth of viable bacteria in the raw water supply channel 1, It is generally 0.3 ppm.)
- Sodium hypochlorite c is supplied so as to maintain it above.
- the activated carbon regeneration means is means for supplying warm water to the activated carbon filter layer 3B to regenerate the activated carbon, that is, means for recovering the adsorption capacity of the activated carbon.
- the activated carbon regeneration means includes a heat exchanger 10 that heats water by exchanging heat with steam from the boiler 9, and hot water heated by this heat exchanger 10 is supplied to the raw water supply path 1 at the tower inlet 3a.
- a drainage channel 17 is provided and configured to connect the upstream part to the drainage part 16 .
- the activated carbon regeneration means includes flow path switching means, a temperature sensor 20 for detecting the hot water temperature in the hot water outward path 11, and the hot water temperature is set to the set temperature T h based on the detection result of the temperature sensor 20.
- a temperature regulating valve 21 for automatically regulating the amount of steam supplied to the heat exchanger 10 and operating means for switching the operating state are provided.
- the channel switching means is connected to the hot water return channel 13 of the treated water extraction channel 2.
- a first on-off valve V1 is installed at a point downstream of the point, a second on-off valve V2 is installed on the inlet side of the warm water return path 13, and a third on-off valve V3 is installed in the drainage path 17.
- a fourth on-off valve V4 is installed at a location upstream of the activated carbon trap filter 6 in the treated water extraction channel 2 and downstream of the connection with the drainage channel 17. It is
- the operation state switching operation means operates the boiler 9, the circulation pump 12 as the circulation means, and the flow path switching means to switch between an operation stop state, a hot water circulation regeneration operation state, and a raw water washing operation state, which enable water treatment. It is a means for switching the operating state of the activated carbon regeneration means to three states.
- the boiler 9 and the circulation pump 12 are operated, the second on-off valve V2 and the fourth on-off valve V4 are opened, By closing 1 and the third on-off valve V3, the hot water heated by the heat exchanger 10 is passed through the hot water outbound path 11, the raw water supply path 1 downstream portion, the tower inlet 3a, the activated carbon filter layer 3B, and the tower outlet. 3b, fourth on-off valve V4, activated carbon trap filter 6, second on-off valve V2, circulation pump 12, warm water return path 13, heat exchanger 10, and circulate in order to pass through, It is a state in which the adsorption capacity of activated carbon is recovered (regenerated) by heating. That is, it is a state in which the organochlorine compound adsorbed on the surface of the activated carbon of the activated carbon filter layer 3B is eluted.
- the water pump 5 is operated, the circulation pump 12 and the boiler 9 are stopped, the third on-off valve V3 is opened, and the fourth on-off valve V3 is opened.
- the valve V4 By closing the valve V4, the raw water a is passed through the raw water supply channel 1, the tower inlet 3a, the activated carbon filter layer 3B, the tower outlet 3b, the upstream part of the treated water extraction channel 2 and the third 3 It is a state in which the on-off valve V3 and the drainage channel 17 are passed through in the order listed and discharged to the drainage part 16. That is, the activated carbon filter layer 3B is washed with the raw water a.
- the adjustment of the hot water temperature by the temperature control valve 21 is performed in the hot water circulation regeneration operation state.
- the set temperature T h at that time is a temperature at which the low-boiling organochlorine compounds adsorbed on the activated carbon can be eluted, and is 80°C or higher, preferably 100°C.
- the desired water treatment using the activated carbon filtration tower 3B that is, the activated carbon Stop the water treatment by supplying the raw water a to the filtration tower 3, and switch to the hot water circulation regeneration operation state.
- the time when the organic chlorine compound reaches saturation varies depending on the size of the activated carbon filter layer 3B (the amount of activated carbon), the amount of treated water, the amount of organic matter contained in the raw water, and the like. It takes about 20 to 30 days when the coconut shell granular activated carbon used for treatment is used, the amount thereof is about 2,000 liters, and the raw water supply rate is 20 m3/h.
- the operation state is switched to the raw water cleaning operation state. That is, the predetermined time is a time necessary and sufficient for elution of free chlorine compounds. Specifically, when the set temperature Th is 90°C, it takes about 30 to 60 minutes after the hot water temperature rises to 90°C with the start of operation. 3> After continuing the raw water washing operation state for the set time, switch to the operation stop state. The setting time is approximately 5-10 minutes.
- the water treatment with the activated carbon regeneration means stopped is performed in the following manner .
- Sodium hypochlorite c is injected into the raw water a, and the raw water a into which the sodium hypochlorite c is injected is retained in the raw water storage tank 4 for a set time.
- the organic substances in water a and hypochlorous acid fouda c are reacted to convert the organic substances into organochlorine compounds with low boiling points.
- the organic matter in the raw water a is adsorbed to the activated carbon as an organic chlorine compound, and as a result, it is eluted from the activated carbon by heating the hot water with the activated carbon regeneration means, and the activated carbon can be regenerated.
- the specifications of the activated carbon filtration tower used are as follows.
- the activated carbon filtration layer of the activated carbon filtration tower with the above specifications 400 liters of granular antibacterial water purification material composed of silver zeolite and activated carbon was uniformly dispersed in 1,600 liters of granular coconut shell activated carbon for water treatment.
- the antibacterial water purifying material is produced by the method described in the above examples using a carbonaceous raw material as a coconut shell, and contains approximately 20% silver zeolite.
- the antibacterial water purification material used is granulated so that it can be uniformly dispersed only by normal backwashing of the activated carbon filter layer.
- Table 5 shows the performance and particle size distribution of the antibacterial water purification material and the granular coconut shell activated carbon for water treatment. The performance and particle size distribution of activated carbon were determined by test methods based on JIS standard K1474 and the like.
- filtration treatment is performed in a state where heat sterilization is performed two to three times a week, and in the activated carbon filtration tower of the present invention, hot water of 90 ° C.
- Filtration treatment was carried out in a state in which the activated carbon was thermally regenerated by split circulation, and the viable cell count of general bacteria in the treated water (filtered water) was periodically investigated.
- the number of viable bacteria was investigated by opening the sampling cock while the activated carbon filtration tower was in operation (water treatment), allowing about 10 liters of water to flow, sampling, and culturing at 36°C for 48 hours using a standard agar medium. After that, the number of colonies formed in the medium was measured.
- FIG. 5(b) shows the relationship when using the conventional activated carbon filtration tower is shown in FIG.
- Table 6 shows the average number of viable bacteria in each month for one year. ND in Table 6 indicates not detected.
- the activated carbon filtration tower of the present invention can almost certainly sterilize treated water, and is extremely superior in terms of sterilizing treated water compared to conventional activated carbon filtration towers.
- Heat regeneration was performed by circulating hot water at a temperature of 90-95°C at a flow rate (SV) of 4-3 for 40 minutes through the activated carbon filter bed.
- the maximum concentration of chloroform in the raw water was 0.139 ppm, the minimum concentration was 0.040 ppm, and the average concentration was 0.096 ppm.
- activated carbon can be regenerated by periodically circulating and supplying warm water to the activated carbon filter layer.
- Silver zeolite in other words, confirms the ability to maintain the antibacterial activity of the antibacterial material.
- Raw water was supplied to the activated carbon filtration layer of the activated carbon filtration tower of the present invention, and the relationship between the treatment (filtration) flow rate and the elution amount of silver ions was examined. The results are shown in FIG.
- the activated carbon regeneration means is operated about once or twice a month to regenerate the activated carbon. It was found that the ability to sterilize water and remove organic matter was always obtained in a stable state.
- the activated carbon regeneration means may be configured as follows.
- a heat exchanger 10 similar to that of the embodiment is provided, and hot water heated by the heat exchanger 10 is introduced into the treated water outlet 2 near the tower outlet 3b.
- the outward hot water path 11a for supplying, the outward hot water path 11a, part of the raw water supply path 1, part of the treated water extraction path 2, and the heat exchanger 10 and the activated carbon filtration tower 3 Water is taken out from the treated water take-out channel 2 at a location downstream of the activated carbon trap filter 6 so as to form a circulation channel that circulates the water at , and the taken-out water is supplied to the heat exchanger 10 as water to be heated.
- Drainage channel 17a that connects the hot water supply channel 16a to the drainage part 16a, and a portion of the treated water extraction channel 2 downstream of the connection to the hot water outward channel 11a is connected to the raw water supply channel 1.
- a communication passage 22 is provided, and a passage switching means and an operation mode switching operation means are provided.
- the flow path switching means includes a first on-off valve V1a installed at a location downstream of a connection location with the hot water return channel 13a in the treated water extraction channel 2, and on the inlet side of the hot water return channel 13a.
- a second on-off valve V2a is installed in the drain passage 17a.
- a fifth on-off valve V5a is installed at a location between the connection point to the warm water outgoing path 11a and the connection point to the communication path 22 in the treated water extraction path 2, and the communication path 22 is connected to the It consists of 6 on-off valves V6a.
- the operation state switching operation means operates the boiler 9, the circulation pump 12a, and the channel switching means to switch between an operation stop state, a hot water circulation regeneration operation state, and a raw water washing operation state, which enable water treatment. It is a means for switching the operating state of the activated carbon regeneration means according to the state.
- the water supply pump 5 is operated, the circulation pump 12a and the boiler 9 are stopped, and the third on-off valve V3 is opened, while the remaining Raw water supply channel 1 - Tower inlet 3 a Activated carbon filter layer 3 B Tower outlet 3 b Treated water extraction channel 2 upstream part Third on-off valve V 3 a Drainage It is in a state of being discharged to the drainage section 16 by passing through the passage 17a and its order of description. In other words, the activated carbon filter layer 3B is washed with the raw water a.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU80040/94A AU8004094A (en) | 1993-12-13 | 1994-10-31 | Water purifying material, process for producing the same, and water purification equipment |
EP94931192A EP0684210A4 (en) | 1993-12-13 | 1994-10-31 | WATER PURIFICATION MATERIAL, PROCESS FOR PRODUCING SUCH MATERIAL, AND WATER PURIFICATION INSTALLATION. |
KR1019950703381A KR960700965A (ko) | 1993-12-13 | 1994-10-31 | 정수재 및 그 제법과 정수설비(water purifying material, process for producing the same, and water purification equipment) |
FI953786A FI953786A (fi) | 1993-12-13 | 1995-08-09 | Vedenpuhdistusaine ja sen valmistusmenetelmä ja vedenpuhdistusjärjestelmä |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP34236193 | 1993-12-13 | ||
JP5/342361 | 1993-12-13 | ||
JP6/214473 | 1994-09-08 | ||
JP6214473A JPH07222983A (ja) | 1993-12-13 | 1994-09-08 | 浄水材及びそれの製法並びに浄水設備 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995016638A1 true WO1995016638A1 (en) | 1995-06-22 |
Family
ID=26520335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1994/001835 WO1995016638A1 (en) | 1993-12-13 | 1994-10-31 | Water purifying material, process for producing the same, and water purification equipment |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0684210A4 (ja) |
JP (1) | JPH07222983A (ja) |
KR (1) | KR960700965A (ja) |
AU (1) | AU8004094A (ja) |
CA (1) | CA2155870A1 (ja) |
FI (1) | FI953786A (ja) |
TW (1) | TW327627B (ja) |
WO (1) | WO1995016638A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003953A1 (en) * | 1998-07-17 | 2000-01-27 | Worldwide Water Technologies Pty Ltd | Water treatment apparatus and components |
US7402239B2 (en) | 2001-01-09 | 2008-07-22 | Ionics Perpetual, Inc. | Water purification apparatus and method of using the same |
US8758626B2 (en) | 2009-12-07 | 2014-06-24 | Fresenius Medical Care Holdings, Inc. | Water purification cartridge using zirconium ion-exchange sorbents |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5772896A (en) * | 1996-04-05 | 1998-06-30 | Fountainhead Technologies | Self-regulating water purification composition |
US6254894B1 (en) | 1996-04-05 | 2001-07-03 | Zodiac Pool Care, Inc. | Silver self-regulating water purification compositions and methods |
AU6670098A (en) * | 1997-02-21 | 1998-09-09 | Engelhard Corporation | Composite material based on zeolite and active carbon, preparation and use thereof in water treatment |
WO1998036830A1 (en) * | 1997-02-21 | 1998-08-27 | Engelhard Corporation | Composite material based on zeolite and active carbon, preparation and use thereof in water treatment |
KR20010003976A (ko) * | 1999-06-23 | 2001-01-15 | 황규하 | 음용수의 방취 항균 정수제의 조성물 |
JP2001062290A (ja) * | 1999-08-27 | 2001-03-13 | Nippon Chem Ind Co Ltd | 有機ハロゲン化合物除去処理材およびその処理方法 |
SE0100371L (sv) * | 2001-02-07 | 2002-08-08 | Bmt Bio Mineral Technologies A | Filteravdelning och förfarande för rening av avloppsvatten innehållande oorganiska-, organiska föroreningar och/eller patogener |
KR100460318B1 (ko) * | 2002-08-27 | 2004-12-08 | 수석토건설(주) | 항균 정화가 가능한 수질 개선장치 |
US20070199890A1 (en) * | 2006-02-27 | 2007-08-30 | Agion Technologies, Inc. | Antimicrobial activated carbon and use thereof |
JP5252385B2 (ja) * | 2007-08-16 | 2013-07-31 | 株式会社メイプル・リンク | 浄水装置 |
KR101471861B1 (ko) * | 2008-04-22 | 2014-12-11 | 코웨이 주식회사 | 정수기용 항균성 포스트 카본 블록 및 정수기 |
CN102145188B (zh) * | 2011-02-14 | 2014-02-19 | 天润绿业(北京)环保技术有限公司 | 一种除臭吸附剂 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63239205A (ja) * | 1986-10-15 | 1988-10-05 | Kanebo Ltd | 抗菌ならびに防カビおよびcod低下機能を有するゼオライト‐活性炭複合体およびその製造方法 |
JPH01278408A (ja) * | 1988-04-28 | 1989-11-08 | Matsushita Electric Ind Co Ltd | 防菌性活性炭 |
JPH02273588A (ja) * | 1989-04-13 | 1990-11-08 | Ube Ind Ltd | 浄水用カートリッジの洗浄方法及びその装置 |
JPH0422410A (ja) * | 1990-05-17 | 1992-01-27 | Takuma Co Ltd | 濾材 |
JPH04243591A (ja) * | 1991-01-25 | 1992-08-31 | Kitz Corp | 浄水器の自動再生殺菌装置 |
JPH04247233A (ja) * | 1991-02-04 | 1992-09-03 | Osaka Gas Co Ltd | 成形吸着体 |
JPH04285005A (ja) * | 1991-03-12 | 1992-10-09 | Kuraray Co Ltd | 繊維状活性炭の再生方法 |
-
1994
- 1994-09-08 JP JP6214473A patent/JPH07222983A/ja active Pending
- 1994-10-19 TW TW083109691A patent/TW327627B/zh active
- 1994-10-31 AU AU80040/94A patent/AU8004094A/en not_active Abandoned
- 1994-10-31 KR KR1019950703381A patent/KR960700965A/ko active IP Right Grant
- 1994-10-31 EP EP94931192A patent/EP0684210A4/en not_active Withdrawn
- 1994-10-31 CA CA002155870A patent/CA2155870A1/en not_active Abandoned
- 1994-10-31 WO PCT/JP1994/001835 patent/WO1995016638A1/ja not_active Application Discontinuation
-
1995
- 1995-08-09 FI FI953786A patent/FI953786A/fi not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63239205A (ja) * | 1986-10-15 | 1988-10-05 | Kanebo Ltd | 抗菌ならびに防カビおよびcod低下機能を有するゼオライト‐活性炭複合体およびその製造方法 |
JPH01278408A (ja) * | 1988-04-28 | 1989-11-08 | Matsushita Electric Ind Co Ltd | 防菌性活性炭 |
JPH02273588A (ja) * | 1989-04-13 | 1990-11-08 | Ube Ind Ltd | 浄水用カートリッジの洗浄方法及びその装置 |
JPH0422410A (ja) * | 1990-05-17 | 1992-01-27 | Takuma Co Ltd | 濾材 |
JPH04243591A (ja) * | 1991-01-25 | 1992-08-31 | Kitz Corp | 浄水器の自動再生殺菌装置 |
JPH04247233A (ja) * | 1991-02-04 | 1992-09-03 | Osaka Gas Co Ltd | 成形吸着体 |
JPH04285005A (ja) * | 1991-03-12 | 1992-10-09 | Kuraray Co Ltd | 繊維状活性炭の再生方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0684210A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000003953A1 (en) * | 1998-07-17 | 2000-01-27 | Worldwide Water Technologies Pty Ltd | Water treatment apparatus and components |
US7402239B2 (en) | 2001-01-09 | 2008-07-22 | Ionics Perpetual, Inc. | Water purification apparatus and method of using the same |
US8758626B2 (en) | 2009-12-07 | 2014-06-24 | Fresenius Medical Care Holdings, Inc. | Water purification cartridge using zirconium ion-exchange sorbents |
Also Published As
Publication number | Publication date |
---|---|
FI953786A (fi) | 1995-10-04 |
EP0684210A4 (en) | 1996-11-06 |
FI953786A0 (fi) | 1995-08-09 |
JPH07222983A (ja) | 1995-08-22 |
EP0684210A1 (en) | 1995-11-29 |
AU8004094A (en) | 1995-07-03 |
CA2155870A1 (en) | 1995-06-22 |
KR960700965A (ko) | 1996-02-24 |
TW327627B (en) | 1998-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5443735A (en) | Method and device for inhibiting bacterial growth on sorbent media | |
Rengaraj et al. | Agricultural solid waste for the removal of organics: adsorption of phenol from water and wastewater by palm seed coat activated carbon | |
US20200398254A1 (en) | Chloramine and chlorine removal material and methods for making the same | |
WO1995016638A1 (en) | Water purifying material, process for producing the same, and water purification equipment | |
US6180016B1 (en) | Microbiological water filtering | |
US5346876A (en) | Air purifying agent and a process for producing same | |
US10093555B2 (en) | Counter current filter apparatus for treatment or purification of water | |
JP5424543B2 (ja) | バイオガス生成システム | |
EP3131669B1 (de) | Verwendung eines partikulären adsorptionsmaterials zur verlängerung der einsatz- und/oder standzeit einer adsorptiven filtereinheit | |
US6004522A (en) | Solid filtration media incorporating elevated levels of permanganate and water | |
CN108744729B (zh) | 一种石墨烯改性活性炭复合滤芯及其制备方法和应用 | |
Jendia et al. | Removal of nitrate from groundwater by eggshell biowaste | |
CN101513999B (zh) | 活性炭及改性方法和在含内分泌干扰物水处理的应用 | |
JPS641197B2 (ja) | ||
EP2286886B1 (en) | pH stable activated carbon | |
KR100436981B1 (ko) | 수처리장치 | |
CN110624408A (zh) | 一种空气净化剂及其制备方法 | |
Sajid | Industrial Applications of Activated Carbon | |
CN113200594B (zh) | 一种多功能复合净水滤芯及其制备方法与应用 | |
JP3828133B2 (ja) | 浄水器用浄化材およびこれを用いた上水浄化方法並びに浄水器 | |
JP2009078219A (ja) | 浄水器用カートリッジ | |
JPH0686972A (ja) | 浄水器 | |
Ncibi et al. | Recent patents on activated carbon production and applications | |
JP2560179Y2 (ja) | 浄水器 | |
NL1032645C2 (nl) | Op kool gebaseerde geactiveerde kool met langzaam afgevend fosfaat en werkwijze voor het filtreren van water. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA FI KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1994931192 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 953786 Country of ref document: FI |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2155870 Country of ref document: CA |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1994931192 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 1995 492122 Country of ref document: US Date of ref document: 19951130 Kind code of ref document: A |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1994931192 Country of ref document: EP |