JP4856610B2 - Method for producing molded article for water purification - Google Patents

Description

  The present invention relates to a water purification molded article for purifying water by contacting with water and a method for producing the same.

  For purifying the water by bringing it into contact with water, a number of methods using carbon materials such as activated carbon and charcoal in combination with other materials and members therefor are known. (For example, refer to Patent Documents 1 and 2) These purify water by adsorbing impurities in sewage to activated carbon or charcoal, and the adsorption sites of activated carbon and charcoal are saturated with adsorbed substances such as impurities. If this happens, the ability to purify is lost, and frequent replacement is often required.

On the other hand, a method is disclosed in which activated carbon or charcoal is used as a carrier for bacteria such as aerobic bacteria that consume organic matter. (For example, refer to Patent Document 3) This method uses the fact that bacteria naturally inhabiting in sewage adhere to the carrier naturally, and the bacteria grow as organic nutrients in the sewage and become sludge. There is a problem that the purification ability is lowered.
JP 2000-233189 A JP 2007-831 A Japanese Patent Application Laid-Open No. 2000-176489

  An object of the present invention is to provide a molded body for water purification that exhibits excellent water purification performance over a long period of time by contact with water, and a method for producing the same.

  The gist of the present invention is a composite containing carbon powder, bacteria that consume harmful substances in water, and an adhesive, wherein the particles of the carbon powder are connected via the adhesive and are porous. The object is to be a water purification molded body formed with a body.

  The bacterium may be a bacterium that is in a dormant state due to drying.

The bacteria may be a Empedobact e r bacterium SIID2926-1b strain (FERM AP- 10360).

  The adhesive may be a cement-based adhesive.

  The charcoal powder may include charcoal-derived charcoal powder obtained by carbonizing and firing a southern ocean material.

  The charcoal powder may include charcoal-derived charcoal powder obtained by carbonizing and firing wood having an air-dry specific gravity of 0.5 or less.

  The charcoal powder may include charcoal-derived charcoal powder obtained by carbonizing and firing wood at 450 ° C. or higher and lower than 800 ° C.

In addition, the gist of the present invention is that
Preparing a mixture containing charcoal powder, bacteria that consumes harmful substances in water, and an adhesive;
It is a method for producing a water purification molded article including a step of solidifying the mixture to obtain a molded article by curing the adhesive.

Further, the gist of the present invention is that the adhesive contains cement and a coagulant for cement,
It is in the manufacturing method of the said molded object for water purification which solidifies the said cement by standing the said mixture and obtains a molded object.

  In the method for producing a molded body for water purification, the cement coagulant may include an aqueous solution of metal ions.

In the production method of the water purifying moldings, the cement solidification agent, calcium chloride, potassium chloride, ferric chloride, magnesium oxide, magnesium chloride, may include ammonium chloride.

  In the method for producing the molded body for water purification, the bacterium may be a bacterium that is in a dormant state due to drying.

In the production method of the water purifying moldings, the bacteria may be Empedobact e r bacterium SIID2926-1b strain (FERM AP- 10360).

  ADVANTAGE OF THE INVENTION According to this invention, the molded object for water purification which exhibits the water purification capability excellent over the long term by the contact with water, and its manufacturing method are provided.

  The molded article for water purification of the present invention is a composite comprising a fungus having a function of consuming and decomposing or changing charcoal powder and harmful substances in water (hereinafter referred to as a purification fungus) and an adhesive, This is a water purification molded body in which the carbon powder particles are connected via the adhesive to form a porous body. The purification bacteria are present on the surface and inside of the water purification molded article in a state of being supported on the carbon powder particles.

The purifying bacteria, Bacillus bacteria, Clostriduim bacteria, Thermus bacteria, Pseudomonas bacteria, include one or more bacteria selected from Empedobact e r bacterium. Among them, as the bacteria used for water purification molded article of the present invention, Empedobact e r bacteria are preferred. Among Empedobact e r bacteria, SIID2926-1b strain (FERM AP- 10360) is most preferable in the water purification performance of the water purifying molded article of the present invention.

  It is preferable that the purification | cleaning microbe contained in the molded object for water purification of this invention is a microbe which is in a dormant state by drying. In this case, when the water purification molded article is brought into contact with water, for example, the purification bacteria absorbs and activates the water, and the water purification is excellent in combination with the adsorption action of the carbon powder particles. Demonstrate ability.

  If the purification bacteria contained in the water purification molded body are wet and activated when the water purification molded body is not used, the bacteria will grow abnormally when the water purification molded body is unused. It may rot and water purification ability may not be fully demonstrated.

  Since the bacteria for purification are restricted in growth in relatively strong alkaline water, the water in the vicinity of the charcoal becomes alkaline when the water purification molded product is in contact with water, so that the bacteria for purification Excessive growth is suppressed. As a result, the generation of sludge due to excessive growth of the purification bacteria is suppressed, and the phenomenon that the excessive growth of bacteria prevents the contact between the sewage and the charcoal powder particles and the charcoal adsorption capacity is reduced is also suppressed. Ability is maintained for a long time.

  As the adhesive, resin-based adhesives such as those exemplified by epoxy resins and acrylic resins can be used, but cement is preferable. Since the adhesive is cement, the vicinity of the adhesive becomes more alkaline in the state where the molded product for water purification is placed in water, so that excessive proliferation of the bacteria for purification is further suppressed, and the purification ability is further prolonged. Maintained over time.

  As the charcoal powder, a granular material of a carbonaceous material derived from a plant such as wood, bamboo, rattan or rice husk is used. The particle size of the carbon powder particles is preferably 0.001 to 1 mm. As the charcoal powder, charcoal powder obtained by pulverizing charcoal made from South Sea wood is preferably used. South Seawood grows faster and has a coarser and larger cell structure than domestic timber, so the pore size of the porous carbide is large. As a result, the purification activity of the bacteria for purification is carried out smoothly, and an excellent water purification effect can be obtained as compared with the case of using charcoal powder of domestic material with dense cellular tissue such as scarecrow. In addition, when powdered activated carbon is used instead of charcoal powder, the size of the pores is even smaller than charcoal, so that the bacteria for purification are less likely to be stably supported, and an excellent water purification effect over a long period of time can be obtained. I can't.

  Examples of such South Sea materials include lamin, rubber, lawan, capol, terentan, meranti, gelongan, pisanpisan, falcata, puna, kempas, balun, bintangle, nyato, and agathis, but the growth is fast and the tissue is rough. If it is large, it is not limited to these.

  It is preferable that the air-drying specific gravity of the wood used in the present invention is not more than 0.5, not limited to the South Sea lumber, because carbides having a large pore size can be used. For example, wood such as paulownia, cedar and pine having an air-drying specific gravity of 0.5 or less is preferable.

  Further, as the charcoal used for the charcoal powder, it is preferable that the cellulosic material is carbonized and fired at 450 ° C. or higher and lower than 800 ° C. When the carbonization firing temperature is 800 ° C. or higher, as in, for example, so-called white coal or Bincho charcoal, the charcoal becomes excessively alkaline, and the growth and activity of the carried purification bacteria are hindered to maximize the purification capacity. There is a tendency not to be demonstrated. When the carbonization firing temperature is lower than 450 ° C., the charcoal becomes acidic, and the growth and activity of the carried purification bacteria are hindered, and the purification ability tends not to be exhibited to the maximum.

  The charcoal powder may be obtained by crushing charcoal with a known crushing means. You may obtain by baking the granular material of wood, such as sawdust and the ground material of wood.

  The molded article for water purification according to the present invention is a molded article precursor comprising a mixture containing charcoal powder, purification bacteria, an adhesive before curing or coagulation, and, if necessary, an adhesive curing agent or coagulant. However, when the adhesive is cement, if only water is used as the coagulant, a large amount of water is required to obtain the required strength of the molded product. Therefore, the molded body precursor contains a large amount of water. For this reason, the purification bacteria in the molded body precursor are immersed in the water, the purification bacteria immersed in water are activated, and the molded body precursor is solidified in the activated state. There exists a tendency for the bacteria for purification to be damaged by solidification. In addition, the solidification of the cement blocks most of the pores of the carbon powder, thereby inhibiting the activity of the purification bacteria in the pores. If an attempt is made to reduce the amount of cement to prevent clogging and obtain a porous molded body, the strength of the molded body may be low, which may hinder handling, and the handling method and application are limited.

  In the present invention, by using an aqueous solution containing metal ions as a coagulant for cement, it is possible to reduce the water necessary for solidification of the molded body precursor using cement as an adhesive and to obtain a molded body having sufficient strength. I understood it. Thereby, solidification of a molded object precursor can be performed in the dormant state by drying the microbe for purification | cleaning in a molded object precursor. Also, the pores of the carbon powder are less likely to be clogged by solidification of the cement, and when the molded product is poured into water for purification, the purification bacteria recover their activity and the purification bacteria in the pores are sufficiently active To be done.

  Thus, at the stage of the molded body precursor, the purification bacteria are preferably in a dormant state by drying. Also in the water purification molded body of the present invention obtained by solidifying such a molded body precursor, the purification bacteria carried on the molded body are in a stable dormant state due to drying, and The molded body for water purification can be stored for a long time in an unused state without degrading performance.

  Examples of suitable metal ions contained in the aqueous solution used as a coagulant for cement include calcium ions, potassium ions, ferric ions, and magnesium ions.

  Furthermore, when the aqueous solution used as a coagulant contains calcium chloride, potassium chloride, ferric chloride, magnesium oxide, magnesium chloride, or ammonium chloride, a high-strength molded product can be obtained by using a small amount of water, and molding When the body is poured into water for purification, the most sufficient activity of the purification bacteria in the pores is obtained.

  In the present invention, usually, when the purification bacteria are used, those in a mixed state with the culture are used. In addition, a culture of purification bacteria can be used instead of the purification bacteria. The culture refers to a culture medium used for culturing the bacteria for purification and a compound or enzyme released into the culture medium as the bacteria for purification are grown. Although the purification bacteria themselves can be decomposed by consuming the compounds in the water, the enzymes produced by the purification bacteria are considered to have the same function.

  As described above, the water purification molded article of the present invention comprises charcoal powder, purification bacteria and / or cultures thereof, an adhesive before coagulation or curing, and a curing agent or coagulation added as necessary. It can be obtained by stirring and mixing the agent to form a molded body precursor, and putting it in a predetermined mold to stiffen the adhesive by curing or coagulation. This molded body precursor is added to 100 parts by weight of carbon powder. On the other hand, it is preferable that 5 to 20 parts by weight of the purifying bacteria and / or culture thereof and 15 to 60 parts by weight of the adhesive before solidification or curing are blended.

  When the adhesive is cement, 0.5 to 3 parts by weight of a coagulant made of an aqueous solution containing metal ions is preferably added to the entire molded body precursor.

  When the adhesive is cement, the ratio of water contained in the molded body precursor is preferably 5 to 30% by weight with respect to the entire molded body precursor. If the proportion of this water is below this range, the strength of the molded product will be insufficient. If it exceeds this range, the bacteria for purification and / or the culture thereof swell, the solidification of the cement is hindered, the molded product becomes brittle, and handling is hindered.

When the adhesive is cement, when the mixing ratio of the purification bacteria contained in the molded body precursor and / or the dried product thereof is less than 5 to 20 parts by weight with respect to 100 parts by weight of the carbon powder, Water purification ability as a water purification molded product is not sufficient. Above this range, the germs for purification and / or their cultures swell and the molded body becomes brittle, which hinders handling.

  In the present invention, the purification bacteria and / or the dried product of the culture in the molded body precursor means that the moisture content of the purification bacteria and / or the culture is 50% by weight or less. For that purpose, it is preferable to mix the bacteria for purification and / or the culture thereof with an adhesive before curing in a dry state with a moisture content of 50% by weight or less.

  Further, in the present invention, a molded product precursor may be obtained by mixing charcoal powder with a liquid containing purification bacteria, adsorbing the purification bacteria to the carbon powder, and then mixing with an adhesive before curing. . In this case, it is preferable to dry the charcoal powder on which the purification bacteria are adsorbed before mixing with the adhesive. Or in this invention, you may obtain the molded object precursor by mixing the liquid containing the microbe for purification | cleaning, carbon powder, an adhesive agent, etc. In this case, the molded body precursor is preferably dried before solidification.

  The molded product for water purification according to the present invention can be purified in a mode in which it is placed in a part of a flow path of water and brought into contact with the flowing water, in addition to performing purification in a mode in which it is immersed in sewage and left standing. .

Example 1
(SIID2926-1b strain (FERM AP- 10360) of Empedobact e r bacteria) 0.5 parts by weight purifying bacteria culture water 400 parts by weight of purifying bacteria, glucose 10 parts by weight, peptone 5 parts, yeast extract 2 .5 parts by weight was added and cultured at 30 ° C. for 5 days to obtain a culture solution. Add 10000 parts by weight of rice bran, 1000 parts by weight of coffee bran, and 2 parts by weight of honey to 4000 parts by weight of this culture solution according to this blending ratio, and stir appropriately so as not to exceed 55 ° C. while paying attention to temperature rise due to fermentation heat. The culture was obtained by stationary culture for days. This culture was naturally dried to obtain a dry culture. The moisture content of this dry culture was 15%.

Charcoal powder Charcoal powder obtained by dry-distilling Falcarta, which is a South Sea material, at about 600 ° C. was pulverized to obtain charcoal powder having an average particle size of about 0.5 mm.
Molded body precursor

  100 parts by weight of the above carbon powder, 20 parts by weight of water, 50 parts by weight of ordinary Portland cement, and 1 part by weight of a coagulant for cement were stirred and mixed to obtain a mixture. To this mixture, 10 parts by weight of the dried culture was added and stirred to obtain a molded body precursor. The cement coagulant comprises 2 parts by weight of calcium chloride, 2 parts by weight of potassium chloride, 2 parts by weight of ferric chloride, 2 parts by weight of magnesium oxide, 2 parts by weight of magnesium chloride, 2 parts by weight of ammonium chloride, and 2500 parts by weight of water. It is an aqueous solution.

Water Purified Molded Body The molded body precursor was placed in a mold, pressed at about 5000 Pa, and allowed to stand for 24 hours to obtain a block-shaped water purification molded body having a size of 2 cm × 5 cm × 5 cm.

Purification test 1
Water collected from a river flowing through the city was used as sewage. The COD of this water (raw water) was 15 ppm.

  100 liters of raw water was added to each of the two tanks (capacity 200 liters) of tank A and tank B. In the tank A, 50 block-shaped water purification molded bodies were charged. 100 pieces of commercially available resin (PP) contact filter media (a disk shape having a diameter of about 5 cm) were put into the B tank.

  Next, COD after allowing water in each tank to pass for 48 hours in an aerated state was about 8 ppm for tank A and about 13 ppm for tank B, and the excellent purification capability of the water purification molded product was confirmed.

Purification test 2
20 liters of well water was placed in each of two aquarium tanks (a tank and b tank) (capacity: 50 liters), and 5 goldfishes of approximately 5 cm in Taimachi were raised. The three water purification molded bodies were put into the tank a and allowed to stand at the bottom of the tank. Table 1 shows the results of measuring the water quality after 6 days of breeding under normal aeration for each tank.

  In addition, tank a has less water-blooming than tank b and water transparency is high, and tank a has a water tank wall clouded by water, whereas tank a has almost no clouding of the water tank wall by water. It was.

Purification test 3
As shown in FIG. 1, the molded body precursor is cross-sectioned along the longitudinal direction of the rod-like material 2 at the bottom 4 of the rod-like material 2 obtained by vertically dividing a PVC pipe having a length of 5 m and an inner diameter of 20 cm into two. The product was spread in a shape and allowed to stand for 12 days to solidify to obtain a long composite 8 that is a composite of the bowl 2 and the kamaboko-type water purification molded product 6. A groove 14 extending in the longitudinal direction of the bowl-shaped object 2 is formed by the upper surface 10 of the kamaboko-type water purification molded body 6 and the exposed inner wall 12 of the bowl-shaped object 2. As shown in FIG. 2, the composite 8 is inclined from the horizontal with respect to the longitudinal direction and the groove 14 is opened upward, and water is supplied to the upper end 20 of the composite 8 by the circulation pump 16 and the water guide pipe 18. To flow down on the upper surface 10. The water flowing down on the upper surface 10 is received in the receiving tank 22 (capacity: 100 liters) from the lower end 21 of the composite 8, and the water is again guided to the upper one end 20 of the composite 8 by the circulation pump 16 and the water guide pipe 18. Circulation was performed at 5 liter / mim.

Only water was circulated for the first 24 hours.
Next, 100 g of commercially available granular fertilizer (8-8-8) was added to the receiving tank 22 and dissolved while the circulation was continued. The water in the receiving tank 22 immediately after this was sampled and used as sample 1. Thereafter, water flowing down on the upper surface 10 after 17 hours was collected for water quality measurement and used as sample 2.
Water was circulated as it was, and the circulation was stopped 48 hours after the start of circulation, and at the same time, the upper surface 10 of the composite 8 was washed with tap water using the pressure. The water used for washing was collected and used as sample 3.
Along with this washing, the circulating water was replaced with fresh water, and the water circulation was resumed. The water flowing down on the upper surface 10 after 24 hours from the restart was collected for water quality measurement and used as sample 4.

  Table 2 shows the water quality measurement results of each sample. It was confirmed that the fertilizer components (nitrogen component, phosphorus component) in the flowing water were purified by the flow of contact with the molded body for water purification.

Example 2
A molded body precursor similar to that obtained in Example 1 was placed in a mold and solidified in the same manner as in Example 1 to obtain a cylindrical water purification molded body having a diameter of 3 cm and a height of 3 cm. This molded product is designated as sample (1).

  600 cc of the medium (solution) was put into a beaker (capacity: 1 liter), and six samples (1) were put into the beaker. Then, while continuing the aeration of the culture medium with the aeration apparatus for fish culture, the pH, components (ions, glucose), COD of the culture medium after the sample was added were measured, and the results shown in Tables 4 and 5 were obtained.

  Table 3 shows the components in 1 liter of medium. The balance is distilled water. The pH of this medium was 7.0.

  The rate of change in Tables 4 and 5 indicates the ratio of the measured value of the corresponding item when the measured value of each item immediately after sample introduction (elapsed time 0) is 100.

  As shown in Tables 4 and 5, nitrate ions almost disappeared on the second day, and phosphate ions and nitrite ions almost disappeared on the second to third days. Ammonium ions were almost halved in 3 days.

  The increase in pH seems to be due to elution of alkali ions derived from cement components from the sample.

  The glucose decreased with the growth of the fungus. COD decreased on the way, and later rose again due to fungal metabolites and cell degradation products. In addition, although the DNA of the bacterium in the liquid was examined, it was mainly a gonococcus and did not match the bacterium contained in the sample (1). The decrease of ammonium ion, nitrate ion, nitrite ion and phosphate ion in the medium (solution) is not due to adsorption to the water purification molded product, but is consumed by the growth of bacteria in the water purification molded product. This is probably due to this.

Example 3
Water was added to a water lily bowl (diameter 80 cm, height 60 cm) to fix 10 water lily seedlings. After standing for one month, the water became cloudy and the growth of water lilies stagnated. Ten water purification molded bodies similar to those obtained in Example 1 were put into the bottom of the bowl. After 20 days, the water became clear and the water lily began to grow. One month later, water lilies grew in the pot that filled the water surface of the water lilies. During this time, the water remained very clear.

Comparative Example 1
Water was applied to a water lily pot similar to Example 3, and 10 water lily seedlings were fixed at the same time as Example 3. After standing for one month, the water became cloudy and the growth of water lilies stagnated. After 50 days, the water remained cloudy, the weeds grew and the water lily grew stagnant.

Example 4
Using the same molded body precursors obtained in Example 1, to obtain a block-shaped water-purifying compact of size 5 cm × 10 cm × 20 cm to stand put the molded body precursor into a mold. Twenty of these water purification molded bodies were put into a pond (20 m ² , depth 50 cm) in a state where the turbid bottom could not be seen due to the occurrence of the cocoons, and was allowed to stand on the pond bottom. After a month, the pond became clear and transparent to the bottom.

Comparative Example 2
A water purification molded article was obtained in the same manner as in Example 4 except that activated carbon having an average particle size of about 0.5 mm was used in place of the carbon powder. Twenty of these water purification molded bodies were put into a pond (20 m ² , depth 50 cm) in a state where the turbid bottom could not be seen due to the occurrence of the cocoons, and was allowed to stand on the pond bottom. At the beginning of the pond, the pond became slightly clear, but after a month, the pond became cloudy.

Example 5
100 parts by weight of the same carbon powder as used in Example 1, 20 parts by weight of an epoxy resin (trade name: Epicoat 828), and 0.2 parts by weight of a room temperature curing catalyst were mixed and stirred, and then the same as that used in Example 1 10 parts by weight of the dried culture was added and mixed and stirred to obtain a molded body precursor. This molded body precursor was put into a mold and allowed to stand at 35 ° C. for 48 hours to obtain a block-shaped molded body for water purification having a size of 2 cm × 10 cm × 10 cm. In the same manner as in Example 3, the obtained water purification molded article was put into the water bottom of a water lily pot where water lily seedlings were fixed and the water became cloudy and the growth of water lily stagnated. After 20 days, the water became clear and the water lily began to grow. One month later, water lilies grew in the pot that filled the water surface of the water lilies. During this time, the water remained clear.

Example 6
A molded product for water purification was obtained in the same manner as in Example 1 except that a dried product (active water sludge containing Bacillus genus bacteria) collected in a water purification tank was used as the dried culture. Obtained. One obtained water purification molding was put into a beaker containing 200 cc of sewage with a COD of 50 ppm. The COD of sewage after 24 hours from the introduction was 25 ppm.

  In addition, the present invention can be carried out in a mode in which various improvements, modifications, and changes are added based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

It is sectional drawing of the elongate composite_body | complex using the molded object for water purification of this invention used for water purification. It is a side surface schematic diagram which shows the aspect of the water purification experiment using the elongate composite_body | complex shown in FIG.

Explanation of symbols

2: Saddle-like object 8: Long composite 16: Circulation pump 18: Water guide pipe 22: Receiving tank

Claims (2)

100 parts by weight of charcoal powder derived from charcoal obtained by carbonizing and firing a South Sea material having a dry air specific gravity of 0.5 or less at 450 ° C. or more and less than 800 ° C.
15-60 parts by weight of cement,
5 to 20 parts by weight of either or both of a bacterium that consumes harmful substances in water and is in a dormant state due to drying, and a culture of the bacterium,
0.5-3 parts by weight of a coagulant for cement containing an aqueous solution of metal ions;
The manufacturing method of the molded object for water purification which solidifies the said cement by leaving still the mixture which contains the said water and the mixing ratio of the said water is 5-30 weight% of the whole. The method for producing a molded article for water purification according to claim 1, wherein the cement coagulant contains calcium chloride, potassium chloride, ferric chloride, magnesium oxide, magnesium chloride, and ammonium chloride.

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