JP4882038B1 - Decolorization and water purification methods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for decoloring colored industrial wastewater, and also for simultaneously purifying the industrial wastewater such as removing a phosphorus ion therefrom. <P>SOLUTION: The colored industrial wastewater is decolored while the phosphorus ion is removed therefrom by adding a calcium compound and/or a magnesium compound to the industrial wastewater and immersing therein a purification means comprising an iron material and a carbon material, both of which are at least partly in contact with one another to promote the elution of an iron ion by enhancing the electric conductivity of the wastewater due to the presence of the calcium ion and/or the magnesium ion. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a method for decolorizing colored industrial effluent, especially industrial effluent, and simultaneously purifying the water quality.

  Industrial wastewater discharged from the livestock industry is discharged into rivers after wastewater treatment such as biological treatment. In addition, the industrial effluent discharged from the fish processing industry is discharged as industrial effluent after processing such as aeration, neutralization with chemicals, separation with a flocculant, and the like. Furthermore, industrial wastewater discharged from various industries that use phosphorus (for example, plating, food processing, milking farms, kitchens, fish farms, fishery processing, etc.) must be drained within the water quality standards set by the government. Is required.

However, in the case of industrial effluents that are difficult to decolorize, even if the water quality after the effluent treatment satisfies environmental standards, it is often brown or purple. It cannot be said that coloring in this way has any influence on the environment, and it is desirable that drainage discharged into rivers and seas be as colorless and transparent as possible.
Industrial drainage that is difficult to decolorize as described above includes industrial drainage generated from the livestock industry. When this treated wastewater is discharged, it is natural that the water quality is within the standards set by each local government, but from the viewpoint of color, it may be discharged without being completely decolored.

On the other hand, various techniques have been developed for the decolorization of industrial wastewater related to livestock. As described in Patent Documents 1 to 6, they are oxidative decolorization techniques using chemicals or ozone, or decolorization techniques using photocatalysts.
However, the above-described decolorization techniques have problems such as polluting the environment with chemicals, using a large amount of energy, or creating a new load on the environment due to excessive sterilization. In the case of a photocatalyst, there was a difficulty in scaling up. Any of these techniques has left various problems for practical use.

  In view of this, the inventors have so far conducted intensive studies to decolorize colored wastewater related to livestock and to remove phosphorus inevitably mixed in such colored wastewater. As a result, when iron powder and carbon material powder (activated carbon) were added to the colored swine effluent and stirred and mixed, a technology capable of decoloring in about 10 minutes to 1 hour was developed and disclosed in Patent Document 7 . This technique can reduce COD, total nitrogen, and total phosphorus in the drainage in a short time, and can also reduce the odor peculiar to pig farm drainage.

  In addition, some livestock farmers are required to decolorize and purify the drainage liquid without using a special device even if the processing time takes a certain amount of time. In response to this requirement, the inventors tried to apply a purifying material “Superpitor (registered trademark)” composed of carbon fiber and iron plate, and gave satisfactory results to the above requirement. . In addition, this purification material has already been utilized as a water-blooming prevention agent (refer patent document 8).

JP 2004-337761 A JP 2008-229450 A JP 2009-022940 JP 2001-321772 A JP 2002-011483 A JP 2003-024957 A Application No.PCT / JP2009 / 068634 Specification Japanese Patent Application No. 2009-018799

  However, the technique described in Patent Document 7 requires a stirrer as dedicated equipment as described above, and requires a large amount of iron and carbon powder as consumables. In addition, the purifying material “Superpitor (registered trademark)” described in Patent Document 8 is effective for removing phosphorus, reducing COD, and the like, but is not necessarily sufficient for decolorization of the drainage.

  The present invention has been developed in view of the above-described situation, and an object of the present invention is to provide a water purification technique that can effectively decolorize colored industrial effluent and efficiently remove phosphorus ions. And

Hereinafter, an experiment that has completed the present invention will be described.
(Decoloration and purification of human waste fluid by stirring)
It was investigated whether the excreta discharged from livestock could be decolorized by mixing with stirring. Specifically, iron and carbon were charged into a container containing human waste, and the container containing urine was placed on a mixing ball mill mount and rotated to mix human waste with iron and carbon. The drainage used here was deodorized drainage discharged from the fiber ball deodorizer. The results of analyzing the liquid quality of this drainage were pH: 8.77, COD: 660 mg / L, total phosphorus: 10.9 mg / L, and total nitrogen: 1882 mg / L. The rotation speed of the ball mill for stirring and mixing was 10 rpm. Moreover, each concentration of pH, COD, phosphoric acid and nitrogen was analyzed by a pack test described in Examples described later.
Deodorized drainage liquid: 1000mL and a metal fiber net (expanded metal 64mm x 157mm) with a carbon fiber fabric inserted between two pieces put in a rotating container (plastic, capacity: 2L), rotated for a predetermined time, The color and odor of the contents of the container were observed. The concentrations of pH, COD, nitric acid, ammonia and phosphoric acid were analyzed by the pack test as described above. The mass of the expanded metal was 14.40 g for one piece and 28.79 g for two pieces. The mass of the carbon fiber fabric (64 mm × 187 mm) was 6.68 g.
The analysis results are shown in Table 1.

  As shown in the table, the pH of the effluent changed from 8.7 to 6.1 on the acidic side. Phosphoric acid concentration and COD were slightly decreased. The ammonia concentration dropped to about 1/2. The nitric acid concentration increased by a factor of two. However, the color of the drainage did not disappear.

(Decoloration and purification of human waste by aeration)
We examined whether the excreta discharged from livestock can be decolorized by mixing by aeration. The used effluent was the deodorized effluent discharged from the fiber ball deodorizer. As a result of analyzing the liquid quality of this drainage liquid, it was pH: 8.77, COD: 660 mg / L, total phosphorus: 10.9 mg / L, total nitrogen: 1882 mg / L. The concentrations of pH, COD, phosphoric acid and nitrogen were analyzed by the pack test described above.
The above-mentioned deodorizing drainage: 5 L and three expanded metals (64 mm × 157 mm) wrapped in carbon fiber fabric were put in a container (made of plastic, capacity: 5 L). The weight of the expanded metal was 33 g (101 g). The carbon fiber fabric (64 mm × 187 mm) was 6.68 g. For comparison, only 5 L of deodorized effluent was put in another container. The aeration rate was 1 L / min.
After a predetermined time, the color and odor of the contents of the container were observed. The pH, COD, phosphoric acid and nitrogen concentrations were analyzed by the pack test as described above.
As for the analysis results, the case of only drainage is shown in Table 2-1, and the case of adding carbon fiber and iron material to the drainage is shown in Table 2-2.

As shown in Tables 2-1 and 2-2, in the case of only drainage, the pH slightly changed from 8.8 to 8.4, and the COD slightly decreased. Ammonia concentration decreases to about 1/2. The nitric acid concentration increased to 1.2 times. Also, the color of the drainage did not disappear.
On the other hand, when carbon fiber and iron material were added to the effluent, the pH slightly changed from 8.8 to 8.3. There is no change in phosphoric acid concentration. COD decreased slightly. The ammonia concentration decreased to about 1/2, and the nitric acid concentration increased to 1.2 times. Also, the color of the drainage did not disappear.

  From the above two experimental results, it was found that decolorization of the drainage liquid cannot be realized only by stirring and aeration using iron and a carbon material.

As described above, iron and carbon materials were added to colored effluent, and further, decolorization of human waste effluent was attempted by operations such as stirring and aeration, but this was not realized.
Here, the drainage discharged from the coating process is colored blackish brown. It is difficult to remove this color and it is impossible to remove the color. Therefore, a purification material in which iron nails were inserted into a carbon fiber fabric was installed in the drainage. Then, the color faded with time, and after 4 days, the degree of coloring was less than before treatment.
That is, when a purification material composed of iron and a carbon material is used, it has been found that colored environmental water tends to be decolored, although it takes a long time.

(Decolorization of human waste fluid by additives)
Based on the above results, it was suggested that the combination of iron and carbon material may have a decoloring action, although it takes a long time. Therefore, the inventors further studied and thought that if some electrolyte substance was added to the effluent, the dissolution rate of metallic iron would increase, and the processing speed of decolorization and purification would increase. .
Therefore, electrolytic electrolyte sodium chloride as a substance, selected calcium chloride and hydrochloric acid, these electrolyte material was stirred with the drainage, and evaluating the effect of the bleaching and water purification. Specifically, four polybins (wide mouth, capacity: 2 L) are prepared, each of which is filled with 1 L of drained liquid discharged from the deodorizer, and then an iron pipe wrapped with a carbon fiber fabric ( Hereinafter, a nipple (see FIG. 1 (a)) was inserted. The size of the nipple used was a nominal diameter: 32 mm and a length: 125 mm. The surface of the nipple material was polished with sandpaper, the zinc layer coated on the surface was removed, and the metal iron layer was exposed.
Carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the nipple surface, and one was put in each container.

Furthermore, in the container a, the drainage liquid: 1 L is sealed, in the container b, the drainage liquid: 1 L, sodium chloride: 10.0 g (addition amount: 1 mass%) is sealed, and in the container c, the drainage liquid: 1 L, calcium chloride. : 10.0 g was enclosed.
Calcium chloride is an electrolyte substance that is generally easily available and safe to handle, and is widely used as a snow melting agent and a desiccant. The calcium chloride used in the above experiment was a dihydrate made by Tokuyama Corporation, containing 73 mass% or more of calcium chloride, and the balance was inevitable impurities. Therefore, the amount of calcium chloride used in the container c is 7.3 g, and the addition rate is 0.73 mass%.
Further, in the container d, a liquid in which hydrochloric acid was added to the drainage liquid and the pH of the whole drainage liquid was adjusted to 4.5 was sealed.
The above containers a to d were rotated at 100 rpm on a ball mill frame, and pH and phosphoric acid concentration after 2 hours were measured by the pack test as described above. FIG. 1 (b) shows a state in which the carbon fiber is removed after the carbon fiber is wound around the nipple and stirred for 2 hours in human wastewater.

As a result of the above-described experiment, the reddish brown effluent changed to light yellow by adding calcium chloride.
Here, no change in color was observed with calcium chloride alone, but as described above, when the carbon material and iron coexisted, decolorization progressed and the color became almost colorless after 2 hours.
Table 3 shows the water quality analysis results of the containers a to d.

  The phosphoric acid concentration in each container after 2 hours was greatly different depending on the type of additive. That is, in the container b, the phosphoric acid concentration was 21.0 mg / L, but in the container d, it decreased to 9.0 mg / L and 1/3. Here, the container c was the largest change, and the phosphoric acid concentration was reduced to 3.5 mg / L.

(Purification of wastewater from processing plants by type of additive)
Wastewater from the fish processing industry contains high concentrations of phosphorus. In order to make this wastewater within the environmental standards, cost and time are required. Therefore, development of a new technology that is simple and reasonable has been desired.
From the above experimental results, it was found that the addition of calcium chloride decreased the phosphoric acid concentration. This is considered to be due to the decrease in the phosphoric acid concentration due to the formation of calcium phosphate. However, the entry of chloride ions is not a problem if the final discharge area is the sea, but if it is inland, it will be discharged into the river, which requires treatment of chloride ions.

Therefore, calcium compounds other than calcium chloride were examined. In addition, since calcium is a group 2 element in the periodic table, a magnesium compound which is the same group was also examined.
As a result, calcium carbonate, calcium hydroxide, and magnesium hydroxide were selected as candidates for the experiment from the viewpoints of availability, ease of handling, and price, and the performance of phosphate removal was examined using these. did.

First, three 200 mL beakers were prepared, and each was filled with 100 mL of wastewater from a fish processing factory. To each beaker, calcium carbonate: 1.02 g, calcium hydroxide: 1.02 g, and magnesium hydroxide: 1.02 g were added, and the mixture was stirred with a magnetic stirrer for 30 minutes. The wastewater used had a pH of 6.8, COD of 100 mg / L, phosphoric acid concentration of 60 mg / L, and a salt content of 0.5 mass%.
When each of the above-mentioned additives was added, the contents of each beaker became cloudy. Therefore, the stirrer was stopped after 30 minutes, and the precipitate was allowed to settle.

After about 30 hours had passed, the supernatant was collected, and the supernatant aqueous solution was analyzed for water quality.
Table 4 shows the measurement results.

As shown in the table, the pH was 8.0 for calcium carbonate, 14.0 for calcium hydroxide, and 9.0 for magnesium hydroxide.
The measurement results of COD were 140 mg / L for calcium carbonate, 80 mg / L for calcium hydroxide, and 80 mg / L for magnesium hydroxide. The measurement results of the phosphoric acid concentration were 60 mg / L for calcium carbonate, 0.1 mg / L for calcium hydroxide, and 3 mg / L for magnesium hydroxide.

  From these experimental results, it was found that the drainage decolorization and water purification effects can be obtained not only with calcium chloride, but also with magnesium, and with compounds such as hydroxides and carbonates. .

(Decolorization and dephosphorization of human wastewater with calcium hydroxide)
It was examined whether decolorization, dephosphorization, and COD proceed by adding calcium, particularly calcium hydroxide, to the deodorized effluent having a strong ammonia smell and reddish brown color. Deodorized waste liquid: 100 mL, calcium chloride: 1.0 g (0.73 g as CaCl ₂ ) and calcium hydroxide: 1.0 g were added to the treatment container. That is, the ratio to the drainage is 0.73 mass% for calcium chloride and 1.0 mass% for calcium hydroxide. Subsequently, it was rotated at 100 rpm for 5 minutes on a ball mill frame.
FIG. 2 shows a state after the processed product is filtered. The color of the contents immediately after the treatment was dark brown in the case of calcium chloride but brown in the case of calcium hydroxide. When this was filtered with filter paper, the filtration rate was much faster with calcium hydroxide. In addition, the calcium chloride filtrate was dark brown (reddish), while the calcium hydroxide filtrate was brown.
The water quality of these treated products was analyzed by the above pack test, and the results are shown in Table 5.

  As shown in the table, the pH was slightly lower with calcium chloride and higher with calcium hydroxide. Both phosphate ions were drastically reduced, especially at 0.3 mg / L for calcium hydroxide. The COD was 200 mg / L for calcium chloride, but decreased to 100 mg / L for calcium hydroxide.

(Decolorization and dephosphorization of human waste by adding calcium hydroxide)
The above-mentioned deodorization waste liquid was removed by adding calcium hydroxide, and phosphoric acid and COD decreased. Next, the amount of calcium hydroxide added was changed, and the situation affecting decolorization, dephosphorization, and de-COD was confirmed. Deodorizing waste liquid as described above: 100 mL, calcium hydroxide (1.0 g, 0.7 g, 0.3 g, 0.1 g, addition rate to the drainage is 1.0 mass%, 0.7 mass%, 0.3 mass%, 0.1 mass%) 1.0 g of calcium was added, and the mixture was rotated and mixed at 100 rpm for 5 minutes. The state of the treatment liquid is shown in FIG. In the case of calcium chloride, the color of the content immediately after the rotation was dark brown, but in the case of calcium hydroxide, decolorization proceeded. When this was filtered with a filter paper, a light yellow precipitate remained when 1.0 g of calcium hydroxide was added. Further, when the amount of calcium hydroxide added was reduced, the color of the precipitate changed from yellow to brown.
The water quality of these supernatants was analyzed by the aforementioned pack test, and the results are shown in Table 6.

As shown in the table, the pH was slightly lowered with calcium chloride and shifted to the alkali side with calcium hydroxide. The addition of 1.0 g of calcium hydroxide decreased the phosphoric acid concentration to 0.1 mg / L. On the other hand, the phosphoric acid concentration tended to increase as the amount of calcium hydroxide added decreased. Compared to the case of calcium chloride, the effect of adding calcium hydroxide was greater. Further, COD is a chloride calcium U beam was 200 mg / L, the calcium hydroxide was reduced to 100 mg / L.
Colored human urine drainage can be concentrated by adding calcium chloride, and then charging the drainage with a new type of super steel, which is a round bar-shaped metallic iron wrapped with carbon fiber. It turned out that the brown drainage became light yellow or colorless. That is, as a result of the above-described experiment, it has been found that the problem of drainage coloring, which is most troubled by livestock farmers, can be solved.

Here, the inventors consider the mechanism of decolorization of the above-described drainage as follows.
In general, known decolorization mechanisms include oxidative decolorization with an oxidizing agent, oxidative decolorization with ozone, Fenton reaction that occurs in the coexistence of iron and hydrogen peroxide, and bleach decolorization with a chlorine compound. However, the decoloring mechanism in the present invention is completely different from any of the above-described techniques, and is considered to be derived from the aggregating action of iron ions.
That is, by adding calcium chloride, the electrical conductivity of the drainage is increased, and when the iron material and the carbon material are brought into contact with each other in this state, a kind of battery reaction is activated. As a result, the production amount of iron ions is more effective than usual. It is thought that this increases effectively.

  On the other hand, there are various suspended matters such as various fine particles such as feces and decomposition products, insoluble components in urine, sand, clay, feed lees, sludge lees, food lees, etc. in the drainage. Usually they have a negative potential. On the other hand, since the iron ions generated by the battery reaction have a positive potential, they act as a coagulant by the Coulomb force and can effectively aggregate various substances floating in water. As a result, colored components are also aggregated, and the drainage becomes colorless.

  Accordingly, the decolorization of the drainage according to the present invention is an improvement in the electrical conductivity of the drainage due to the addition of calcium chloride, the battery action between the iron material and the carbon material is activated, and a large amount of iron ions are dissolved out. Various phenomena such as ions aggregating colored components in the drainage liquid by Coulomb force are manifested by synergistic effects.

  As described above, the inventors add a compound such as calcium chloride to colored or urine drainage, and then purify the iron and carbon materials, for example, the iron plate and carbon fibers. It has been found that the use of the material “Superpitor” (registered trademark) significantly increases the decolorization ability and can further effectively reduce the phosphorus concentration and COD.

It was also found that decolorization, dephosphorization, and COD reduction can be achieved by using calcium hydroxide or calcium carbonate instead of calcium chloride. However, when calcium hydroxide is used, since the treated water becomes alkaline, it cannot be discharged into nature as it is. In such a case, there is a method of neutralizing by adding an acid, but this is not preferable because it increases COD. However, after adding calcium hydroxide, it was also confirmed that pH, phosphoric acid concentration, COD, and coloring level can all be within the environmental standards if appropriate additional treatment is performed. .
The present invention is based on the above findings.

That is, the gist configuration of the present invention is as follows.
1. One or two or more calcium compounds selected from calcium hydroxide and calcium chloride and / or magnesium hydroxide, magnesium chloride and magnesium carbonate selected from colored industrial effluents adding magnesium compounds consisting of, by immersing the cleaning means consisting of iron and carbon material at least partially in contact, in the presence of calcium ions and / or magnesium ions, electrical conductivity of said product industry drainage A method for decolorization and water purification that promotes elution of iron ions while decolorizing the colored industrial effluent and removing phosphorus ions while enhancing the properties,
A carbon fiber member comprising a carbon fiber net body and a carbon fiber bundle attached around the carbon fiber net is used as the carbon material.

  According to the present invention, in the presence of conductive ions, the elution of iron ions can be promoted while increasing the electrical conductivity of the industrial drainage. Phosphorus removal can be performed quickly and efficiently.

(a) and (b) are photographs showing nipples and carbon fibers used in the experiment. It is a photograph which shows the condition for every predetermined time progress of a process liquid. It is a photograph which shows the condition for every predetermined time progress of a process liquid. It is a figure which shows the example of a purification material. (a) And (b) is a figure which shows the example of installation of a purification material, (c) is a schematic diagram of staggered arrangement | positioning. (a) is a photograph showing a change in the color of a treatment liquid after a predetermined time has elapsed with respect to a treatment liquid to which calcium chloride is added, and (b) is a treatment liquid in which charcoal and iron are added to calcium chloride. (a) is a photograph showing a change in the color of a treatment liquid after a predetermined time has elapsed with respect to a treatment liquid to which calcium chloride is added, and (b) is a treatment liquid in which charcoal and iron are added to calcium chloride. (a) is a photograph showing a change in the color of a treatment liquid after a predetermined time has elapsed with respect to a treatment liquid to which calcium chloride is added, and (b) is a treatment liquid in which charcoal and iron are added to calcium chloride. (a) is a photograph showing a change in the color of a treatment liquid after a predetermined time has elapsed with respect to a treatment liquid to which calcium chloride is added, and (b) is a treatment liquid in which charcoal and iron are added to calcium chloride. (a) is a photograph showing a change in the color of a treatment liquid after a predetermined time has elapsed with respect to a treatment liquid to which calcium chloride is added, and (b) is a treatment liquid in which charcoal and iron are added to calcium chloride. It is a photograph which shows the situation for every time progress of a processing liquid.

Hereinafter, the present invention will be specifically described.
The present invention can purify the quality of treated water while decolorizing the colored industrial effluent, and at the same time, adding at least one calcium compound and / or magnesium compound to the colored industrial effluent. The purifying means consisting of an iron material and a carbon material that are in contact with each other is immersed.

(Calcium compound and / or magnesium compound)
As the calcium compound and / or magnesium compound, a hydroxide (calcium hydroxide, magnesium hydroxide) and a chloride (calcium chloride, magnesium chloride) having high solubility in environmental water are preferable. Carbonates (calcium carbonate, magnesium carbonate) are also included.
When about 0.1 to 1 mass% of a compound such as calcium chloride is added to a colored industrial effluent, the electrical conductivity of the effluent increases and the electrical resistance decreases. Therefore, the electrical resistance of the waste liquid and the waste liquid to which calcium chloride was added was measured.
The electrical resistance was measured using a tester (HIOKI 3030-10) with the electrode spacing fixed at 1 cm. For example, the electrical resistance of the waste liquid from the fiber ball deodorizer was 400 Ω · cm, but when 0.5 mass% of calcium chloride was added, the electrical resistance slightly decreased to 380 Ω · cm. Furthermore, when the amount of added calcium chloride was increased to 0.75 mass% and 1.0 mass%, the electrical resistance decreased to 360 Ω · cm and 340 Ω · cm. From these experimental results, in the presence of calcium ions and / or magnesium ions, elution of iron ions can be promoted while enhancing the electrical conductivity of the industrial effluent, and the decolorization ability is remarkably enhanced. The inventors have confirmed that it is advantageous for promoting the elution of iron ions that the addition ratio of the conductive compound such as calcium chloride is about 0.1 to 2 mass% with respect to the drainage. Yes.

(Iron material)
The iron material used in the present invention may be any iron material having a carbon content of 10 mass% or less, such as pure iron, soft iron, steel, pig iron, and cast iron. Further, any iron-based alloy containing 70 mass% or more of iron having a carbon content of 10 mass% or less can be used.
The shape of the iron material is selected from a mesh shape, a net shape, a plate shape, a plate shape having a through hole, a linear shape, a cylindrical shape, a foil shape, a film shape, and the like. In particular, when installed in environmental water, a structure that reduces the resistance of water, a mesh shape, a net shape, a plate shape having a through hole, a linear shape, and the like are preferable.

(Carbon material)
In the present invention, the means for bringing the iron material and the carbon material into contact with each other is not particularly limited, but lashing with a rubber band or insiloc is suitable .

Further, there is no particular limitation on the means for adding the calcium compound and / or the magnesium compound to the effluent and immersing the iron material and the carbon material, and conventionally known addition methods and immersing means can be used.
For example, in the case of the above compound, when the compound is solid, it may be added as it is, but it can also be diluted with water.

  In the case of the iron material and the carbon material, it is immersed in the drainage in the contact state as described above, but at this time, if the vibration is applied or the stirring is performed, the generation of iron ions becomes more remarkable, The decoloring ability of the present invention is more effectively exhibited.

Therefore, in the specific embodiments of the present invention, the following cases 1 to 3 are preferable cases.
Case 1 livestock wastewater → biological treatment tank → solid-liquid separation → calcium chloride added → iron + carbon materials immersion → discharge.
Case 2 livestock wastewater → biological treatment tank → solid-liquid separation → calcium hydroxide added → iron + carbon materials immersion → discharge.
Case 3 livestock wastewater → biological treatment tank → solid-liquid separation → calcium hydroxide added → calcium chloride added → iron + soaking → discharge of coal material.
In the present invention, the above calcium chloride addition and carbon material immersion may be performed simultaneously.

In the present invention, it is particularly advantageous to use a purification material in which the iron material and the carbon material shown in FIG. 4 are integrated. This purifying material, as a carbon material, has carbon fibers having a carbon fiber net body and a carbon fiber bundle attached around the carbon fiber net. There is an advantage that organic substances can be efficiently decomposed.

Further, as an advantageous embodiment of the present invention, as shown in FIG. 5 (a) and (b), set up purification material vertically to FRP tank, circulating the effluent in water pump (agitator) It can also be a facility. In addition, as for arrangement | positioning of a cylindrical purification material, it is preferable to make it a staggered arrangement as shown in FIG.5 (c). Further, in the figure, the outlet is attached to the lower part of the water tank, but it can also be attached to the upper part.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. In the following examples, pH, phosphorus concentration, COD, chromaticity and total nitrogen concentration were measured by the following methods.

(PH)
It was measured using a pack test (KR-pH, manufactured by Kyoritsu Riken Laboratories, Inc.).
(Phosphorus concentration)
It was measured using a pack test (WAK-PO4, manufactured by Kyoritsu Riken Co., Ltd., trademark).
(COD)
The measurement was performed using a pack test (WAK-COD, manufactured by Kyoritsu Riken Co., Ltd., trademark).
(Chromaticity)
Measurement was performed at a wavelength of 456.8 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-mini-1240). In the present invention, this chromaticity is evaluated as having been able to be decolored at about 500 or less.
(Total nitrogen)
It measured using portable simple total nitrogen and a total phosphorus meter (TOA Co., Ltd. make, TM-10 type | mold).

[Example 1]
(Decolorization and purification of human waste liquid by adding calcium chloride (1 mass%))
Two polybins (wide mouth, capacity: 2 L) were prepared, and 1 L of deodorized effluent was added to each. A nipple wrapped with a carbon fiber fabric was placed therein. The used nipple had a nominal diameter of 32 mm and a length of 125 mm, and the surface was polished with sandpaper. A carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the surface of this nipple. It was rotated at 100 rpm on a ball mill mount. The pH, COD, and phosphoric acid concentration after the lapse of a predetermined time were measured by the above pack test.
In addition, the container I added 10.0 g of calcium chloride (7.3 g as CaCl ₂ , addition rate: 0.73 mass%) to 1 L of drainage. In another container II, drainage: 1 L of calcium chloride 10.0 g (7.3 g as CaCl ₂ , addition rate: 0.73 mass%) is added, and a metal pipe (nipple) wrapped with carbon fiber fabric is placed in this. I put it in.

The change in the color of the treatment liquid after a predetermined time has elapsed is shown in FIG. 6 (a) for the container I and in FIG. 6 (b) for the container II. By adding calcium chloride, the reddish brown effluent was decolorized to light yellow. With calcium chloride alone, no further color change was observed, but when the iron material and the carbon material coexisted, the color disappeared and the color became almost colorless after 2 hours.
Table 7 shows the results of water quality analysis.

  As shown in the table, the phosphoric acid concentration was reduced to about 1/10 at a stretch by adding calcium chloride. However, the addition of calcium chloride alone does not further reduce the phosphoric acid concentration. On the other hand, the coexistence of iron and carbon materials further lowered the phosphoric acid concentration, reaching 0.4 mg / L after 2 hours and reaching 0.1 mg / L after 5 hours. That is, it can be seen that effective decolorization and purification can be achieved at the same time by coexisting an iron material and a carbon material after addition of calcium chloride.

[Example 2]
(Decoloration and purification of human wastewater by adding calcium chloride (0.75 mass%))
Two polybins (wide mouth, capacity: 2 L) were prepared, and 1 L of deodorized effluent was added to each. A nipple wrapped with a carbon fiber fabric was placed therein. The used nipple had a nominal diameter of 32 mm and a length of 125 mm, and the surface was polished with sandpaper. A carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the surface of this nipple. It was rotated at 100 rpm on a ball mill mount. The pH, COD, and phosphoric acid concentration after the lapse of a predetermined time were measured by the above pack test.
In addition, in one container I in which the experiment was performed, 7.5 g of calcium chloride (5.5 g as CaCl ₂ , addition rate: 0.55 mass%) was added to 1 L of waste water.
In another container II, 7.5 g of calcium chloride (5.5 g as CaCl ₂ , addition rate: 0.55 mass%) was added to 1 L of waste water, and one nipple wrapped with a carbon fiber fabric was put therein.

The change in the color of the treatment liquid after a predetermined time has elapsed is shown in FIG. 7 (a) for the container I and in FIG. 7 (b) for the container II. By adding calcium chloride, the reddish brown drainage was decolorized and turned pale yellow. With calcium chloride alone, no further color change was observed, but when the iron material and the carbon material coexisted, the color disappeared further and became almost colorless after 2 hours.
Table 8 shows the water quality analysis results.

  As shown in the table, the phosphoric acid concentration was reduced to about 1/10 at a stretch by adding calcium chloride. Here, when only calcium chloride is added, there is no further decrease in the phosphoric acid concentration. However, when iron and carbon materials coexist, the phosphoric acid concentration further decreases, and 0.15 mg / L after 2 hours and 5 hours later. Reached 0.1mg / L. That is, it can be seen that effective decolorization and purification can be achieved at the same time by coexisting an iron material and a carbon material after addition of calcium chloride.

Example 3
(Decoloration and purification of human waste liquid by adding calcium chloride (0.5 mass%))
Two polybins (wide mouth, capacity: 2 L) were prepared, and 1 L of deodorized waste water was added to each. A nipple wrapped with a carbon fiber fabric was placed therein. The used nipple had a nominal diameter of 32 mm and a length of 125 mm, and the surface was polished with sandpaper. A carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the surface of this nipple. It was rotated at 100 rpm on a ball mill mount. The pH, COD, and phosphoric acid concentration after the lapse of a predetermined time were measured by the above pack test.
In addition, in the container I, calcium chloride: 5.0 g (3.7 g as CaCl ₂ , addition rate: 0.37 mass%) was added to 1 L of drainage. In another container II, calcium chloride: 5.0 g (3.7 g as CaCl ₂ , addition rate: 0.37 mass%) was added to 1 L of waste water, and one nipple wrapped with a carbon fiber fabric was put therein.

The change in the color of the treatment liquid after a predetermined time has elapsed is shown in FIG. 8 (a) for the container I and in FIG. 8 (b) for the container II. By adding calcium chloride, the reddish brown drainage was decolorized and turned pale yellow. However, with calcium chloride alone, no further color change was observed, but when an iron material and a carbon material coexisted, the color further disappeared and the color became almost colorless after 2 hours.
Table 9 shows the water quality analysis results.

  As shown in the table, the phosphoric acid concentration was reduced to about 1/6 at a stretch by adding calcium chloride. However, when only calcium chloride is added, no further decrease in phosphoric acid concentration is observed, but when iron and carbon materials coexist, the phosphoric acid concentration further decreases, and 0.15 mg / L after 2 hours, After 5 hours, it reached 0.1 mg / L. That is, it can be seen that effective decolorization and purification can be achieved at the same time by coexisting an iron material and a carbon material after addition of calcium chloride.

Example 4
(Decoloration and purification of human waste liquid by adding calcium chloride (0.25 mass%))
Two polybins (wide mouth, capacity: 2 L) were prepared, and 1 L of deodorized effluent was added to each. A nipple wrapped with a carbon fiber fabric was placed therein. The used nipple had a nominal diameter of 32 mm and a length of 125 mm, and the surface was polished with sandpaper. A carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the surface of this nipple. It was rotated at 100 rpm on a ball mill mount. The pH, COD, and phosphoric acid concentration after the lapse of a predetermined time were measured by the above pack test.
In addition, the container I added 2.5 g of calcium chloride (1.83 g as CaCl ₂ , addition rate: 0.18 mass%) to 1 L of drainage. In another container II, 2.5 g of calcium chloride (1.83 g as CaCl ₂ , addition rate: 0.18 mass%) was added to 1 L of drainage, and one nipple wrapped with a carbon fiber fabric was put therein.

The change in the color of the treatment liquid after the lapse of a predetermined time is shown in FIG. 9A for the container I and FIG. 9B for the container II. By adding calcium chloride, the reddish brown drainage was decolorized and turned pale yellow. With calcium chloride alone, no further color change was observed, but when the iron material and the carbon material coexisted, the color disappeared further and became almost colorless after 2 hours.
Table 10 shows the results of water quality analysis.

  The phosphoric acid concentration was reduced to about 1/4 at a stretch by adding calcium chloride, but there was no decrease in the concentration thereafter. However, the coexistence of iron and carbon materials further reduced the phosphoric acid concentration, reaching 0.90 mg / L after 1 hour, 0.75 mg / L after 5 hours, and 0.30 mg / L after 24 hours. . That is, it can be seen that effective decolorization and purification can be achieved at the same time by coexisting an iron material and a carbon material after addition of calcium chloride.

Example 5
(Decolorization and purification of human waste liquid by contact area between iron and carbon)
The effect of the contact area between iron and carbon on decolorization and purification capacity was investigated. Three polybins (wide mouth, capacity: 2 L) were prepared, and 1 L of deodorized effluent was added to each. A nipple wrapped with a carbon fiber fabric was placed therein. The used nipple had a nominal diameter of 32 mm and a length of 125 mm, and the surface was polished with sandpaper. A carbon fiber fabric (Fukuoka Machine Co., Ltd., 14 cm × 15 cm) was wrapped around the surface of this nipple. The effect of the contact area between carbon fiber and iron was examined by changing the length of the nipple. The container containing the sample and drainage was rotated at 100 rpm on a ball mill stand. The pH, COD, and phosphoric acid concentration after the lapse of a predetermined time were measured by the above pack test.
In addition, in the container I, 10.0 g of calcium chloride (7.3 g as CaCl ₂ , addition rate: 0.73 mass%) was added to 1 L of waste water. In another container II, 10.0 g of calcium chloride (7.3 g as CaCl ₂ , addition rate: 0.73 mass%) was added to 1 liter of drainage, and a carbon fiber fabric was wrapped in this nipple (nominal diameter: 32 mm, length: 125 mm, straight cylinder length 76 mm, and straight cylinder part area: 102 cm ² ) were placed.
Another container III is a nipple (nominal diameter: 32 mm, length) in which 10.0 g of calcium chloride (7.3 g as CaCl ₂ , addition rate: 0.73 mass%) is added to 1 liter of waste water, and a carbon fiber fabric is wrapped in this. : 125 mm, straight body length: 101 mm, and straight body part area: 135 cm ² ).

The change in the color of the treatment liquid after a predetermined time has elapsed is shown in FIG. 10 (a) for the container I and in FIG. 10 (b) for the container III. By adding calcium chloride, the reddish brown drainage was decolorized and turned pale yellow. With calcium chloride alone, no further color change was observed, but when the iron material and the carbon material coexisted, the color disappeared further and became almost colorless after 2 hours.
Table 11 shows the water quality analysis results.

As shown in the table, the phosphoric acid concentration was reduced to about 1/10 at a stroke by adding calcium chloride, but no subsequent concentration decrease was observed. However, coexistence of iron and carbon materials further reduces the phosphoric acid concentration, and the straight barrel area of 135 cm ² (container III) is 0.15 mg / L after 2 hours and 0.1 mg / l after 5 hours. Reached up to L. Although straight body area intended 102cm ² (container II) was 0.45 mg / L after 2 hours, after 5 hours reached to 0.1 mg / L. That is, it is preferable that the contact area between the iron material and the carbon material is large.

Example 6
(Decolorization of dairy cow drainage)
Decolorization of drainage discharged from milking cows was examined. At the ranch where about 1200 dairy cattle are bred, wastewater is treated by biological treatment, etc., purified to the standard value and released. However, the wastewater is colored yellow, and it is diluted twice in the discharge stage and 200 tons of treated water is discharged every day.
Therefore, the above drainage: 1L, calcium chloride: 10.0g, and carbon fiber fabric (Fukuoka Kikai Co., Ltd.) wrapped around the surface of an iron nipple (white, long, surface polished product) on a polybin (wide mouth, capacity: 2L) One was placed and rotated at 100 rpm on a ball mill stand.

After a predetermined time, the color, pH, COD and phosphoric acid amount were measured by the pack test described above. The nipple used was made of iron, nominal diameter: 32 mm, length: 125 mm, straight body length: 76 mm, and straight body part area: 102 cm ² . The state of the treatment liquid is shown in FIG.
Table 12 shows the water quality analysis results.

  The phosphoric acid concentration decreased to 0.1 mg / L after only 0.1 hours by the coexistence of calcium chloride, iron, and carbon. That is, it can be seen that effective decolorization and water purification can be achieved at the same time by allowing the iron material and the carbon material to coexist after calcium chloride is added.

Example 7
(Extremely small amount of calcium hydroxide added)
Since calcium hydroxide is a solid, it is very difficult to accurately add a small amount. Then, the effect of adding a small amount of calcium hydroxide was confirmed by preparing a saturated solution of calcium hydroxide and diluting the saturated solution with water.
Specifically, a saturated calcium hydroxide solution is prepared by first adding about 0.4 g of calcium hydroxide to 100 mL of pure water and stirring. Then, leave it for about 2 hours, draw out only the supernatant and use it as a saturated solution. The solubility of calcium hydroxide is 0.17 g / 100 mL water.
Hereinafter, a 2-fold dilution (0.085 g / mL) and a 10-fold dilution (0.017 g / mL) of the saturated solution were used for the test. PH of each dilution, the 2 BaiNozomi dilution in 12 and 10-fold dilutions was 9.
A saturated solution: 20 mL was added to 100 mL of wastewater from a fish processing company, and the mixture was stirred with a stirrer. The concentration of calcium hydroxide in each waste water treatment liquid was 1.7 mass% at 2-fold dilution and 0.34 mass% at 10-fold dilution.
After standing, the pH and the phosphoric acid concentration were measured by the pack test described above. Table 13 shows the pH and phosphoric acid concentration of each treatment solution.

  It has been found that the phosphoric acid concentration has a reducing effect even with addition of about 0.34 mass%. That is, even dilution addition has the effect of the present invention, and a small amount of calcium hydroxide or the like can be added by the procedure described above.

  According to the present invention, it is possible to decolorize industrial effluent effectively and purify its water quality, such as factories, agriculture, livestock, fishery processing industry, kitchen drainage, food processing industry and dyeing industry. Not only industrial wastewater, but also environmental water (freshwater, brackish water, seawater), sewage from septic tanks, human waste treatment plants, breeding water for fish farms and sardines, pools, water tanks for high-rise buildings, bill pits Contributes to decolorization of water and purification of treated water.

Claims (1)

One or two or more calcium compounds selected from calcium hydroxide and calcium chloride and / or magnesium hydroxide, magnesium chloride and magnesium carbonate selected from colored industrial effluents adding magnesium compounds consisting of, by immersing the cleaning means consisting of iron and carbon material at least partially in contact, in the presence of calcium ions and / or magnesium ions, electrical conductivity of said product industry drainage A method for decolorization and water purification that promotes elution of iron ions while decolorizing the colored industrial effluent and removing phosphorus ions while enhancing the properties,
A carbon fiber member comprising a carbon fiber net body and a carbon fiber bundle attached around the carbon fiber net is used as the carbon material.

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