WO2011048705A1

WO2011048705A1 - Method of rapidly removing phosphorus, cod substance, nitrogen, color, and odor from excreta or excretal wastewater and removal device using the method

Info

Publication number: WO2011048705A1
Application number: PCT/JP2009/068634
Authority: WO
Inventors: 敏明石井
Original assignee: 石井商事株式会社
Priority date: 2009-10-23
Filing date: 2009-10-23
Publication date: 2011-04-28
Also published as: JPWO2011048705A1; CN102791635A

Abstract

A method which enables phosphorus and other substances to be rapidly removed from an excretal wastewater without the need of adding any unnecessary ion or ingredient; and a removal/recovery device using the method. Powdery activated carbon and an iron powder are supplied to excreta or an excretal wastewater, and the mixture is stirred and flowed. The device is used for stirring and flowing the mixture.

Description

Method for rapid removal of phosphorus, COD, nitrogen, color and odor in human waste or human waste water and removal apparatus using the method

The present invention relates to a removal method for efficiently and rapidly removing phosphorus, COD, nitrogen, color and odor in human waste or human waste water (hereinafter referred to as human waste), and a phosphorus removal apparatus using the method It is a thing.

Contamination of environmental water is progressing on a global scale, and urgent measures are needed. One of the sources of environmental water pollution is drainage from the livestock industry. Livestock waste water is discharged after being purified to the standard value at the source livestock shed or farm, but for various reasons, the reduction of pollution has not progressed.

In addition, phosphorus is one of the sources of contamination by human waste. Since phosphorus can not be degraded by microorganisms, it is still difficult to reduce the concentration of phosphorus in environmental water.
Furthermore, although the provisional standard (total phosphorus 24 mg / L) is currently applied to the drainage standard for phosphorus related to livestock wastewater under the Water Pollution Control Law, the provisional standard is reviewed from now on, and the general standard level It is planned to be strengthened up to 8 mg / L of phosphorus.

Reducing COD in human waste is also a major issue for livestock farmers. So far, it has been treated by various methods such as activated sludge method and lagoon method, but the effect is limited from the economic point of view, and if it is drained into environmental water under inadequate treatment condition, the river It leads to pollution and water pollution.

In addition, sewage that has infiltrated underground will increase the concentration of nitrite and nitrate in groundwater. In the Ministry of the Environment, the reference value of groundwater of nitrite nitrogen and nitrate nitrogen is 10 mg / L. It is said that when the concentration of these nitrogen compounds is high, it may cause methaemoglobinemia etc. of infants. From such a social background, nitrogen pollution to environmental water is a serious problem.
In addition, it is said that the most frequent complaints to the livestock industry is an offensive odor. If this point can be solved, it will be a gospel to the livestock producer.

To solve these problems, as a method of removing phosphorus dissolved in waste water, Patent Document 1 uses an aggregating treatment agent such as ferric chloride or polyferric sulfate to treat livestock urine, We are removing phosphorus inside.

Further, Patent Literatures 2 and 3 show a technique of reacting iron salt or aluminum salt with phosphate ion to remove phosphorus dissolved in waste water.

Furthermore, in Patent Document 4, a coagulant such as polyferric sulfate or polyaluminum chloride is added to chemically convert phosphorus in waste water to iron phosphate in order to remove phosphorus in sewage and industrial waste water, Techniques for wastewater purification are shown.

There is also a technology that uses steel slag.
In the technology described in Patent Document 5, in order to remove phosphorus in the phosphorus-containing wastewater, it is removed by passing it through a steel slag. Blast furnace slag and cold-cooling slag are used for iron and steel slag. It is considered that iron and steel slag is porous for phosphorus removal.

Also, a method using pure iron instead of iron salt or slag has been proposed. For example, Patent Document 6 describes that phosphoric acid concentration can be reduced by adding powdered iron in human waste.
Patent Document 6 uses an iron base material, and the particle size of the iron base powder is 3000 μm or less, and the specific surface area is 0.005 m ² / g. The iron content is 70% or more, and the components other than iron are oxygen, magnesium, strontium, phosphorus and sulfur.
Water-soluble phosphate ions react with iron to become insoluble phosphorus compounds, depending on whether this iron-based material is sprayed, spread or mixed at a ratio of several% to animal feces and urine. Is disclosed.

JP, 2001-205273, A JP, 2006-281177, A JP 2008-68248 A JP 2003-340464 JP, 2008-142613, A JP 2000-140862 A

However, in the method of removing phosphorus using the iron salt or aluminum salt described in Patent Documents 1 to 4, there is a problem that ions and components other than iron ions and aluminum ions are also added to water.
That is, with the addition of iron salts or aluminum salts to the water to be treated, counter ions such as chloride ions or sulfate ions which combine with iron ions or aluminum ions to form iron salts or aluminum salts are also treated water As a result, the concentration of chloride ions and sulfate ions in the water to be treated is increased, which adversely affects the ecosystem.

Further, in the method of removing phosphorus using iron and steel slag described in Patent Document 5 and the method of removing phosphorus using an iron base material described in Patent Document 6, the iron component and the phosphorus compound form a water insoluble component. I can not speed up. That is, there is a problem that the removal rate of phosphorus is low. Moreover, the phosphorus concentration after the process seen in the Example of patent document 6 was about 0.1 mass% and 1000 mg / L.

That is, in the above-mentioned method, the removal rate of phosphorus was very slow, usually requiring one day. As such, when the treatment time is long, many treatment tanks for storing human waste are required. From such a current situation, a method capable of treating phosphorus and the like in human urine in a short time has been desired.

In addition, it has a unique color (see Figure 1).
The biggest problem in current livestock wastewater treatment is bleaching. Until now, decolorization has been carried out by adding a large amount of flocculant, but this is problematic due to cost and is not practical. Although decolorization is possible by ozone treatment, this treatment method also has many practical problems, such as introduction of an ozone generator, maintenance of an apparatus, securing of a driver, and the like.

Therefore, there is no effective means to reduce problems other than removal of phosphorus, that is, the concentration and COD value of nitrogen compounds, the color and odor of human waste (hereinafter referred to as phosphorus in the case of phosphorus etc.). Was the situation.
The present invention advantageously solves the above problems, a method capable of rapidly removing phosphorus etc. in human urine without the need to add unnecessary ions and components, and a removal and recovery apparatus using the method Intended to provide.

Hereinafter, an experiment which has succeeded in the present invention will be described.
First, iron powder was slightly dissolved when iron powder was put in manure, so it was examined whether phosphorus could be removed with iron alone. The iron powder used is of two types: reduced iron powder (80 to 150 μm manufactured by Entech Co., Ltd.) and iron oxide powder (75 to 150 μm manufactured by Ishii Shoji Yashio Plant).
The reduced iron powder is produced by reducing with mill scale (iron oxide generated on the surface of iron by watering during rolling of slabs and billets (iron bars)) with coke etc. and then heat-treated in a hydrogen atmosphere Iron powder, which has pores in the particles. The purity is iron powder of Fe: 90% by mass or more, and the balance is an unavoidable impurity.

On the other hand, iron oxide powder is iron powder obtained by burning and oxidizing slag-containing iron with a rotary kiln, and Fe: 85 to 90 mass%. Impurities are CaO, SiO ₂ , Al ₂ O ₃ , MgO, etc. of slag composition.
150 mL of human waste was placed in a 2-liter polyethylene wide-mouthed bottle, to which 3 g of iron powder was added. The addition rate of iron powder to human waste was 2% by mass. Carbon material is not added. The iron powder was put into a poly container in a dispersed state without being put in a bag. Experiment 1 is the case where reduced iron powder is used, and Experiment 2 is the case where iron oxide powder is used.

The poly container containing human waste and iron powder was placed on a rotary table of a ball mill and rotated at 10 rpm. The phosphate ion concentration before treatment was 75 mg / L. The time change of the phosphate ion concentration at that time is shown in Table 1. After 120 minutes, the phosphate ion concentration slightly decreased, and was 20 mg / L for reduced iron powder and 43 mg / L for iron oxide powder. Even with iron powder, the concentration of phosphate ion was lowered due to the dissolution of iron, but the decrease was slight.

Next, the influence of the particle size of iron powder was examined under three conditions. Iron powder used iron oxide powder. The particle size of the iron oxide powder is 75 μm or less in Experiment 3, 75 to 150 μm in Experiment 4, and 500 μm or less in Experiment 5. Three grams of each iron oxide powder was added to a 2 liter polybin. No carbide is used. The iron oxide powder was not dispersed in a bag, but was run in a dispersed state. The addition rate of iron oxide powder to human waste was 2% by mass.
The container containing human waste was placed on a rotary table of a ball mill and rotated at 10 rpm for a predetermined time. After a predetermined time elapsed, the phosphate ion concentration in human waste was measured. The change is shown in Table 2. The phosphate ion concentration before treatment was 75 mg / L. After 120 minutes, the phosphate ion concentration decreased slightly and became 43 mg / L in any case regardless of the particle size of the iron oxide powder. Again, it was found that with iron powder alone, the decrease in phosphate ion was not noticeable even if the particle size was changed.

Furthermore, it was examined whether the concentration of phosphate ion in human waste decreased with only the carbon material. As a carbon material, wood-based activated carbon (made in China) was used. 150 mL of human waste was placed in a 2-liter poly bottle, and 0.8 g of activated carbon (made in China) was added without using an iron material. The carbon material was used as it was in the dispersed state without being put in the bag. The poly bottle was spun at 10 rpm using a ball mill turntable. This experiment is referred to as Experiment 6. Changes in phosphate ion concentration after a predetermined time has elapsed are shown in Table 3. Along with the measurement of the phosphate ion concentration, the COD, the coloring condition and the odor are also confirmed, and the results are also shown in Table 3. The phosphate ion concentration was 113 mg / L before the start of the experiment. The phosphate ion concentration in human waste stirred for 120 minutes with activated carbon alone was 113 mg / L and no decrease in phosphate ion concentration was observed.

However, the color unique to human waste (yellowish brown) disappeared 5 minutes after the start of the experiment and became colorless. In addition, although it had a distinctive odor, by adding a carbon material and stirring, the excrement odor disappeared and the ammonia odor decreased. Furthermore, it was found that there was a change in COD, which was 160 mg / L before the experiment, but was lowered to 18.3 mg / L after 120 minutes.

Next, it was confirmed whether color and COD decrease with the phosphate ion concentration by adding other activated carbon in the human waste. 150 mL of human waste was placed in a 2 liter polybin. The iron material was not used, and 0.8 g of activated carbon (Kuraray Chemical Co., Ltd. product, Klarecol PW-D 0.25 mm or less) was used (referred to as Experiment 7).
Activated carbon was put into polybin and used as it was. The mixture of activated carbon and human waste was dispersed in polybin. The poly bottle was spun at 10 rpm for 120 minutes using a ball mill turntable. The change of the phosphate ion concentration at that time is shown in Table 4. At the same time, the COD, the coloring condition and the odor are also confirmed, and the results are shown in Table 4. The phosphate ion concentration did not decrease at 113 mg / L both before and after the experiment.

However, the color unique to human waste (yellowish brown) disappeared 5 minutes after the start of the experiment and became colorless. In addition, human waste has a distinctive odor, which is a serious social problem, but mixing with activated carbon eliminates human odor and reduces ammonia odor. Furthermore, there was a change in COD, which was 160 mg / L before the experiment but decreased to 16.5 mg / L after 120 minutes. Activated carbon was not effective in removing phosphorus in human urine, but was effective in COD, decolorization and deodorization.

Furthermore, we examined whether there was a difference in the removal of phosphorus in human urine depending on the type of activated carbon. 150 mL of human waste was placed in a 2 liter polybin. As an iron material, 5.2 g of pure iron powder (reduced iron powder, manufactured by JFE Steel Co., Ltd., JIPK K-1001, 0.25 mm or less) was used. Three types of activated carbon were used: wood-based (PW-D, experiment 8) manufactured by Kuraray Chemical Co., Ltd., coconut shell-based (PK-D, experiment 9) manufactured by Kuraray Chemical Co., Ltd., and activated carbon made in China (experiment 10) . The amount used was 0.8 g in each case. The addition ratio of iron material and activated carbon was 4% by mass.
The mixture of pure iron powder and activated carbon was dispersed in 2 liters of polybin as it was without putting it in a bag, and was rotated at 10 rpm using a ball mill turntable. The change in phosphoric acid concentration at that time is shown in Table 5. When activated carbon manufactured by Kuraray Co., Ltd. was used, the color of human waste disappeared and became colorless. In the case of activated carbon made in China, no decoloring was observed.

The COD was initially 160 mg / L, but after 120 minutes, it was about 10 mg / L for any activated carbon, and a remarkable lowering effect was observed. When iron oxide powder was used, the phosphate ion concentration was 113 mg / L at the beginning of the experiment, but in Experiment 8 it was 0 mg / L in 90 minutes and in Experiment 9 0.2 mg / L in 120 minutes. 10 decreased to 0.5 mg / L in 120 minutes.
There was also a change in the odor of human waste. At the beginning, there was a strong ammonia odor and a manure odor. However, after 30 minutes, the urinary odor disappeared and only the ammonia odor was found. Furthermore, after 60 minutes, the odor of ammonia also became thin. After that, as the time passed for 90 minutes and 120 minutes, the ammonia odor further decreased.

The effects of iron and carbon additions were examined. 150 mL of human waste was placed in a 2 liter polybin. The iron material used was slag-containing iron (manufactured by Ishii Shoji Co., Ltd., 1.4 mm or less). Slag-containing iron (Ishii Shoji Co., Ltd. made by Yasoi Co., Ltd.) separates and recovers slag (slab, steel plate) and molten steel when it is dispatched in a converter and an electric furnace at the iron production stage, but completely separate and recover It is impossible, and a part of molten steel mixes in slag. The portion in which this steel and slag are mixed is called steel flow, metal-containing slag.

In Ishii Shoji and Yashio, slag is separated from this steel flow (grind, magnetic separation, sieving) to produce iron powder. However, it is difficult to completely separate the slag, and it is referred to as "slag-containing iron" because some of the slag contains it. The purity may be contained in the slag and may vary depending on the lot, and the Fe content is about 70 to 90% by concentration. The impurities include CaO, SiO ₂ , Al ₂ O ₃ , MgO, etc., which are the composition of slag. In the experiment, 6.5 g of this slag-containing iron was used.

The carbon material used activated carbon (plastic type, powdery form) and changed the amount used to 0.5 g (experiment 11), 1.0 g (experiment 12) and 1.5 g (experiment 13). The
The addition rates of iron material and carbon material were 7.1% (experiment 11), 13.3% (experiment 12) and 18.8% (experiment 13).

The mixture of iron material and carbon material was placed in a non-woven fabric (6 cm × 6 cm). The non-woven fabric containing the additive was placed in a poly bottle and rotated at 10 rpm using a ball mill turntable. The change of the phosphate ion concentration at that time is shown in Table 6. Although the phosphate ion concentration at the start was 113 mg / L, no remarkable decrease was observed at 20 to 35 mg / L even after 120 minutes. When slag-containing iron was used, it was found that the decrease in phosphate ion concentration was slight and that no difference was observed due to the addition amount.

Next, the amount of iron powder was kept constant, and the removal effect of phosphorus in human waste when only the amount of activated carbon was changed was examined.
The iron powder material used 7.7 g of slag containing iron (Ishii Shoji Co., Ltd. product, 1.4 mm or less). The activated carbon used the activated carbon (plastic type, powdery form), and the amount used was changed into 0.6 g (experiment 14), 1.3 g (experiment 15), and 1.9 g (experiment 16). The addition rates of the iron powder material and the activated carbon were 7.2% by mass (experiment 14), 14.4% by mass (experiment 15) and 19.8% by mass (experiment 16).

150 mL of human waste was placed in a 2 liter polybin. A mixture of iron powder and activated carbon was placed in a non-woven fabric (6 cm × 6 cm), dispersed in a poly bottle, and rotated at 10 rpm for 120 minutes using a ball mill turntable. The change of the phosphate ion concentration at that time is shown in Table 7. The phosphate ion concentration was 113 mg / L at the beginning, but was 10 to 30 mg / L even after 120 minutes. By this treatment, the phosphate ion concentration was reduced, but not significantly. This is due to the use of slag-containing iron. Moreover, the difference by the addition amount of iron powder and activated carbon was not seen.

The influence of the addition rate of the mixture of iron powder and activated carbon on human waste was examined. As iron powder, 2.6 g (experiment 17), 3.9 g (experiment 18), and 5.2 g (experiment 19) of slag containing iron (Ishii Shoji Co., Ltd. product, 1.4 mm or less) were used. The activated carbon used is 0.4 g (Experiment 17), 0.6 g (Experiment 18) and 0.8 g (Experiment 19), using activated carbon (Kuraray Chemical Co., Ltd., Kuraray PW-D). did.

150 mL of human waste was placed in a 2 liter polybin. The mixture of iron powder and activated carbon was placed in a non-woven bag (6 cm × 6 cm), placed in a polybin, and rotated at 10 rpm for 2 hours using a ball mill turntable. The change in phosphate ion concentration at that time is shown in Table 8. When slag-containing iron was used, the phosphate ion concentration was 113 mg / L originally, but after 120 minutes it was 12.5 to 48 mg / L. Moreover, the phosphate ion concentration became low, so that the addition rate of iron powder and activated carbon became large with respect to the amount of human waste.

Furthermore, the influence by the addition rate of iron powder and activated carbon was examined. As iron powder, pure iron powder (reduced iron powder, manufactured by JFE Steel Corp., 0.25 mm or less) was used. The amounts used were 2.6 g (experiment 20), 3.9 g (experiment 21), 4.5 g (experiment 22), 5.2 g (experiment 23) and 5.8 g (experiment 24). As activated carbon, activated carbon (Kuraray Chemical Co., Ltd. product, KURARECOR PW-D) was used. The amounts used were changed to 0.4 g (experiment 20), 0.6 g (experiment 21), 0.7 g (experiment 22), 0.8 g (experiment 23) and 0.9 g (experiment 24). went.

The addition rate of iron powder and activated carbon to human waste is 2% by mass (experiment 20), 3% by mass (experiment 21), 3.5% by mass (experiment 22), 4% by mass (experiment 23) and 4.5% by mass (Experiment 24).
150 mL of human waste was placed in a 2 liter polybin. The mixture was placed in a non-woven fabric (6 cm × 6 cm) and spun on a ball mill turntable at 10 rpm for 2 hours. The change of the phosphoric acid concentration at this time is shown in Table 9. It was found that when pure iron powder was used for iron powder, the concentration of phosphate ions in human waste decreased, and when the amount of activated carbon added was large, the phosphorus removal effect was increased.

The mixture of iron powder and activated carbon was examined for its effect on the decrease in phosphate ion concentration due to the rotational speed when rotating on a ball mill turntable. As iron powder, 7.7 g of slag-containing iron (Ishii Shoji Co., Ltd. product, 1.4 mm or less) was used. As activated carbon, 1.3 g of activated carbon (plastic, powder) was used.
150 mL of human waste was placed in a 2 liter polybin. The mixture was placed in a non-woven (6 cm × 6 cm). The addition ratio of iron powder and activated carbon was 6% by mass. The additives were dispersed in poly bottles and spun on a ball mill turntable at 10 rpm (experiment 25), 30 rpm (experiment 26) and 45 rpm (experiment 27). Changes in phosphate ion concentration at that time are shown in Table 10. When using slag-containing iron, the decrease in phosphate ion concentration was slight. Moreover, the difference by rotation speed was slight.

For human waste, 150 mL was placed in a 2 liter polybin. As iron powder, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, 250 μm or less) was used. As the activated carbon, 0.8 g of activated carbon (manufactured by Kuraray Chemical Co., Ltd., PW-D) was used.
The addition rate of iron powder and activated carbon to human waste was 4% by mass. The additives were dispersed in poly bottles and spun on a ball mill turntable at 5 rpm (experiment 28), 10 rpm (experiment 29) and 15 rpm (experiment 30). Changes in phosphate ion concentration at that time are shown in Table 11. From the table, it can be seen that the concentration of phosphate ions in human waste is decreasing. Moreover, the difference by rotation speed was not seen so much.

When iron powder and activated carbon were used repeatedly, it was examined whether the phosphorus removal effect could be sustained by the number of repetitions. As iron powder, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, 250 μm or less) was used. As activated carbon, 0.8 g of activated carbon (Kuraray Chemical Co., Ltd. product, PW-D) was used.
150 mL of human waste was placed in a 2 liter polybin. The mixture was used in the dispersed state without using a non-woven fabric. The additives were dispersed in poly bottles and spun on a ball mill turntable for 10 minutes at 10 rpm. Then, the human waste in the poly container was removed, 150 mL of untreated human urine was added, and the mixture was further rotated for 2 hours. This operation was repeated four times. Changes in phosphate ion concentration at that time are shown in Table 12. The phosphate ion concentration was reduced to 3.5 mg / L even after four repetitions, and the phosphorus removal effect of iron powder and activated carbon was sustained.

In addition, COD was also measured together. The COD before treatment was about 100 mg / L, but was 11.5 mg / L at the first test (experiment 31). The reduction rate of COD was slightly reduced to 20 mg / L at the second time (experiment 32), 35 mg / L at the third time (experiment 33), and 50 mg / L at the fourth time (experiment 34). Furthermore, the color of human waste was yellow-brown before treatment but became colorless upon the first treatment. It became transparent in the second time, but started to be slightly colored in the third time.
In addition, although the odor of human waste was odorless in the first treatment (experiment 31), some odors remained in the second treatment (experiment 32) and the third treatment (experiment 33). Furthermore, at the 4th time (experiment 34), the odor was not obtained so much.

We examined the removal effect of phosphate ion when the addition ratio of the mixture of iron powder and activated carbon to the amount of human waste was changed by increasing the amount of human urine. The urine volume used for the experiment was four types of 150 mL (experiment 35), 300 mL (experiment 36), 450 mL (experiment 37) and 600 mL (experiment 38).
As iron powder, 5.2 g of pure iron powder (reduced iron powder, manufactured by JFE Steel Corp., 250 μm or less) was used. As the activated carbon, 0.8 g of PW-D manufactured by Kuraray Chemical Co., Ltd. was used. The addition rates of iron powder and activated carbon to the human waste are 4% by mass (experiment 35), 2% by mass (experiment 36), 1.5% by mass (experiment 37) and 1% by mass (experiment 38).

Each urine volume was placed in a 2 liter polybin. The mixture was put into the polybin in its dispersed state without using a non-woven fabric. The poly bottle was rotated on a ball mill turntable for 10 minutes at 10 rpm or until the phosphate ion concentration became 0.8 mg / L or less. The change of the phosphate ion concentration in that case is shown in Table 13. In the case of the addition rate of 4% by mass, the phosphate ion concentration was 0.8 mg / L in 60 minutes. The phosphate ion concentration was 0.8 mg / L in 90 minutes at an addition rate of 2% by mass.
The phosphate ion concentration was 2 mg / L even after 120 minutes at an addition rate of 1.5 mass%, and was 5 mg / L even after 120 minutes at an addition rate of 1 mass%. Meanwhile, COD was also affected. The initial COD was 160 mg / L at an addition rate of 4% by mass, but as the addition rate decreased, the COD increased to 12.3 mg / L and 14.8 mg / L, and at an addition rate of 1% by mass, 27%. It was as high as 0.5 mg / L.

Through the above experiments and discussions, the inventor has found that by flowing human waste to activated carbon and iron powder, it is possible to rapidly remove phosphorus, COD, nitrogen, color and odor in human urine. .
The present invention is based on the above findings.

That is, the gist configuration of the present invention is as follows.
1. A method for rapidly removing phosphorus, COD, nitrogen, color and odor in human waste or excrement, characterized in that powdered activated carbon and iron powder are supplied to excrement or excrement in human waste or excrement.

2. The powdery activated carbon is any one of powdery, granular or linear, and has a specific surface area of 300 m ² / g or more, and a diameter or long side of 2 mm or less. A method for rapidly removing phosphorus, COD, nitrogen, color and odor in human waste or human waste water as described in 1 above.

3. The iron powder is a reduced iron powder having a circle equivalent diameter of 1 mm or less, the phosphorus, COD, nitrogen, color and odor in human waste or human waste water according to 1 or 2 above. How to remove

4. The phosphorus, COD, nitrogen in human waste or human waste water according to any one of the items 1 to 3, wherein the ratio of the mass of the iron powder to the powdery activated carbon is 1/2 to 1/15. How to quickly remove color and odor.

5. The phosphorus in the human waste or human waste water according to any one of 1 to 4, characterized in that the ratio of the powdered activated carbon and the iron powder in the human waste or human waste water is 1 to 20% by mass. Rapid removal of COD, nitrogen, color and odor.

6. The phosphorus, nitrogen, color in the human waste or human waste water according to any one of the above 1 to 5, characterized in that the powdery activated carbon and the iron powder are contained in a container having water permeability and supplied. And rapid odor removal methods.

7. An apparatus for removing phosphorus, COD, nitrogen, color and odor in human waste and human waste water, comprising a reaction tank, means for supplying powdered activated carbon, means for supplying iron powder, and stirring of human waste and human waste water. And means for removing.

8. The removal device according to the above 7, further comprising a recovery port for iron phosphate which has sunk to the bottom of the device.

9. In the above-mentioned 7 or 8, the supply means of the powdery activated carbon and the iron powder is housed and supplied in the container having the permeability of the powdery activated carbon and the iron powder. Removal device as described.

10. The removal device according to any one of 7 to 9, wherein the stirring means is a stirring blade, and the rotational speed of the stirring blade is 0.5 rpm or more.

11. The removal apparatus according to any one of 7 to 9, wherein the stirring means is a rotation of the reaction tank, and a circumferential speed of the reaction tank is 0.5 rpm or more.

12. 10. The removal apparatus according to 10, wherein the water-permeable container is suspended from the upper portion of the reaction tank into the excrement or excrement.

13. The removal apparatus according to 10 or 11, wherein the water-permeable container is fixed to the reaction vessel.

According to the present invention, phosphorus and the like in water can be rapidly and efficiently reduced without adding unnecessary ions and components into the water.

It is a photograph showing human waste before bleaching. FIG. 1 shows the configuration of a rapid removal and recovery system according to the present invention. It is the conceptual diagram which showed the rapid phosphorus removal apparatus (for experiment). It is the conceptual diagram which showed the rapid phosphorus removal apparatus (cylindrical horizontal type | mold container rotation system) according to this invention. It is a conceptual diagram showing a rapid phosphorus removal device (cylindrical horizontal type and internal stirring type) according to the present invention. It is a conceptual diagram showing a rapid phosphorus removal device (cylindrical vertical type / internal stirring type) according to the present invention. It is the conceptual diagram which showed the rapid phosphorus removal apparatus (cone type and internal stirring type) according to this invention. It is a conceptual diagram showing a rapid phosphorus removal device (cone type, fluid bed type) according to the present invention. It is a photograph showing human waste after decoloration.

Hereinafter, the present invention will be specifically described.
In the present invention, powdered activated carbon (hereinafter referred to as activated carbon) and iron powder are allowed to stir and flow (hereinafter referred to as agitation) in a reaction tank, that is, activated carbon and iron powder in the reaction tank To remove phosphorus etc. in human urine by contacting it with human urine.
Even if iron powder is added to human waste, dissolution of iron in iron powder does not occur so much, as in the experiment shown above. In order to dissolve iron, it is further necessary to add activated carbon in human urine. The addition of activated carbon to human urine causes contact between the activated carbon and iron to form a kind of local battery, whereby the ionization of iron proceeds and the reaction with phosphate ions takes place, phosphate ions It becomes insoluble iron phosphate.

As described above, phosphate ions in human waste react with iron ions in iron powder to form iron phosphate. Since it is insoluble, it becomes a precipitate and coats the surfaces of iron powder and activated carbon, which interferes with the reaction. That is, surface deposits need to be exfoliated and separated, which requires stirring of human waste.

At the time of the stirring, the ratio of the mass of iron powder to activated carbon (in the present invention, the mass of activated carbon / the mass of iron powder) is preferably 1/2 to 1/15. More preferably, it is 1/2 to 1/10. Further, it is preferable that the ratio of iron powder and activated carbon (mass of iron powder and activated carbon / mass of human waste) in human waste is 1 to 20 mass%.
In addition, it is preferable to use an apparatus such as a ball mill because stirring, mixing and impact are performed and the dephosphorizing effect is promoted.

The stirring in the present invention is preferably performed by rotating the stirring blade or the reaction tank itself. At this time, in the case of a stirring blade, the rotational speed of the blade is preferably 0.5 rpm or more. More preferably, it is about 100 to 1000 rpm, but when it is desired to increase the processing speed, it can be about 5000 to 30000 rpm. In the case of rotation of the reaction tank itself, the peripheral speed is preferably 0.5 rpm or more, and the upper limit is not particularly limited, but about 100 rpm or less is desirable.

In the present invention, both activated carbon and iron powder are used as powders, and by setting the ratio of the mass of iron powder to activated carbon and the ratio of iron powder and activated carbon in human waste as described above, Contact to promote dissolution of iron ions, thereby increasing the rate of phosphorus removal.

Additionally, the mixture of activated carbon and iron powder can be stored in a water-permeable container to facilitate recovery.
This makes it possible to recover iron phosphate produced by the reaction of phosphate ion and iron ion, and also to reuse it as a resource.

The container for containing the mixture of iron powder and activated carbon is preferably a container (bag) made of fiber. The container is woven or non-woven or mesh. With such a container, water can pass but powder etc. can not pass. Moreover, the produced iron phosphate can not pass either. It is also possible to discard the whole container after treatment. Alternatively, it is also possible to take iron phosphate out of the container.

The activated carbon in the present invention is preferably in the form of powder, granules, or linear. Moreover, it is desirable that the specific surface area is 300 m ² / g or more, and the diameter or one long side is 2 mm or less.
The term "granular" refers to particles having a diameter of more than 0.1 mm, and the term powder refers to particles having a diameter of 0.1 mm or less. Here, the length of the diameter refers to the diameter in the case of spherical particles and the length of the diagonal in the case of rectangular particles. For example, a digital CCD microscope (Mortex, MS-804) is used Can be measured.

The iron powder in the present invention is preferably a reduced iron powder, and the purity of iron is preferably 90% by mass or more (the balance is an unavoidable impurity). The particle diameter of the powder is preferably 1 mm or less in equivalent circle diameter, and more preferably 250 μm or less. The equivalent circle diameter in the present invention is determined by a value measured using a digital CCD microscope (Mortex Co., Ltd., MS-804).

An example of a basic system for removing phosphorus etc. according to the present invention is shown in FIG. Human waste, activated carbon and iron powder are mixed in the reaction vessel to produce iron ions. The generated iron ions react with phosphate ions dissolved in human waste to form iron phosphate. After reaction for a predetermined time, the supernatant (or reaction solution) is sent to the precipitation tank 1. The precipitate accumulated in the lower part of the reaction vessel is sent to the settling vessel 2. In each settling tank, iron phosphate precipitates and separates. The supernatant, which contains no precipitate, is drained. The precipitate is recovered and reused as iron phosphate and the like.

The reaction vessel described above is not particularly limited as long as it can stir human waste with respect to activated carbon and iron powder, but the structure in which the reaction vessel itself rotates or the structure in which the rotary vane is provided inside the reaction vessel Is preferred.

Embodiments of the device according to the invention are given below, but it goes without saying that within the scope of the invention other embodiments may or may not be taken. Although not shown, the container containing the activated carbon and the iron powder can be fixed not only in the reaction tank but also fixed in the reaction tank or suspended in the case of a stirring blade system.
In addition, there are various restrictions such as the processing amount, the processing time, the place, the installation area, and which embodiment should be selected may be determined based on the situation of the site.

(1) Reaction tank rotation method (see Figure 3)
The example was performed in this manner. Phosphorus and the like are removed by placing a reaction vessel containing manure, activated carbon and iron powder on a rotating table using a rotating table of a ball mill and rotating for a predetermined time.

(2) Stirring method Put urine, activated carbon and iron powder in the reaction tank and remove phosphorus etc. Stirring and mixing are carried out to promote the contact between the three, but there are various methods depending on the stirring method.
Horizontal cylinder type container rotation system (see Fig. 4), cylindrical horizontal type internal stirring system (see Fig. 5), cylindrical vertical type internal stirring system (see Fig. 6), conical vertical type internal stirring system (see Fig. 7), etc. There is.

(3) High Speed Stirring Method In some of the examples shown below, a Jucer mixer was used. Since stirring is performed at high speed and blades for stirring are located at the lower part of the reaction vessel and the angle of the blades is upward, even iron powder having high density can be wound up on the upper part of the reaction vessel. Contact with activated carbon can also occur frequently, which is the optimum stirring mode for the present invention.

(4) Fluidized bed method (see Fig. 8)
This reaction is a heterogeneous system consisting of human waste, activated carbon and iron powder. Therefore, development of a device that brings the three parties into contact efficiently is essential. By using an apparatus for introducing air into the mixture at a high speed as shown in FIG. 8, human waste, activated carbon and iron powder are brought into contact with each other, stirred and mixed.

The dispersion of iron phosphate produced by the reaction of iron and phosphorus in human urine or mixing in sludge may be a problem in some cases. For this purpose, it is desirable to be able to recover the produced iron phosphate. That is, a recovery port can be provided at the bottom of the reaction vessel to recover iron phosphate.
In addition, iron phosphate and activated carbon can be collected in an aqueous container (bag) to enable recovery of iron phosphate. That is, iron powder, activated carbon and iron phosphate are present in the container, and iron phosphate is not mixed in excrement. After the phosphorus and the like are removed, it is possible to remove phosphorus by disposing only the container.

However, when the water-permeable container (bag) is small, the iron powder and the activated carbon remain in contact with each other. Since iron phosphate produced by the reaction of iron powder and activated carbon is insulating, dissolution of iron ions is inhibited, so it is better to avoid the use of a smaller bag (container). In that case, it is more advantageous to place iron powder and activated carbon directly into the reaction tank for treatment rather than treatment using a container. As described above, when the container is not used, the liquid is separated by separating the liquid and the precipitate after the reaction of iron and phosphorus, and the precipitate is recovered as a useful resource.
In this case, the precipitate can be recovered by a conventionally known method such as a filtration method using a usual filter cloth, a filter press method, or a centrifugal separation method.

The problem with using activated carbon is the price. Even if it has high performance, it is difficult to actually use it if the price is high. In order to solve such problems, we examined the color removal property and the price, and reached the activated carbon generated in the waste treatment stage.
By using the above-mentioned activated carbon as a carbon material powder, the colored night soil began to fade within 5 minutes and became colorless (see FIG. 9). At the same time, it was also possible to reduce the odor specific to human waste.

Example 1
150 mL of human waste was placed in a 2 liter reaction vessel (poly bottle). As iron powder, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, particle size: 250 μm or less, purity: 90% by mass or more (remainder is inevitable impurity)) was used. As the activated carbon, 0.8 g of PW-D manufactured by Kuraray Chemical Co., Ltd. was used.

The addition rate of iron powder and activated carbon to human waste was 4% by mass. The additives were dispersed in poly bottles and spun on a ball mill at 10 rpm (experiment 39). Changes in pH, COD, total nitrogen and total phosphorus concentration at that time are shown in Table 14. After 30 minutes, the COD was about 1/5, the total nitrogen was about 1/3, and the total phosphorus was about 1/100. The characteristic color of human waste disappeared in 5 minutes, and was colorless and transparent after that. The odor gradually faded.

In addition, pure iron powder and activated carbon are put into a large non-woven bag (volume about 400 ml) under the conditions described above (experiment 39), and this bag is put into a polybin, and the condition of 10 rpm on the rotary table of the ball mill. It was rotated by. At that time, pH, COD, total nitrogen and total phosphorus concentration were measured. After a lapse of a predetermined time, analysis was carried out, and as in the results of Table 14, COD was about 1/5 after 30 minutes, total nitrogen was about 1/3, and total phosphorus was about 1/100. In addition, iron phosphate generated by the reaction of iron and activated carbon did not exude too much.

(Example 2)
150 mL of human waste was placed in a 2 liter polybin. As iron powder, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, particle size: 250 μm or less, purity: 90% by mass or more (remainder is inevitable impurity)) was used. As the activated carbon, 1.6 g (experiment 40) and 2.4 g (experiment 41) of PW-D manufactured by Kuraray Chemical Co., Ltd. were used.
The addition ratio of iron powder and activated carbon to human waste was 4.5% by mass in Experiment 40 and 5.1% by mass in Experiment 41. The additives were dispersed in poly bottles and spun on a ball mill turntable at 10 rpm. Changes in pH, COD, total nitrogen and total phosphorus concentration at that time are shown in Table 15.
After 30 minutes, the COD was about 1/10, the total nitrogen was about 1/3, and the total phosphorus was about 1/8 to 1/16. After 60 minutes, the COD was about 1 / 13-20, the total nitrogen was about 1/3, and the total phosphorus was about 1/100. The characteristic color of human waste disappeared in 5 minutes, and was colorless and transparent after that. The smell gradually faded.

(Example 3)
150 mL of human waste was placed in a reaction vessel (pot) (500 mL) of a juicer mixer. As iron powder, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, particle size: 250 μm or less, purity: 90% by mass or more (remainder is inevitable impurity)) was used. As the activated carbon, 0.8 g of PW-D manufactured by Kuraray Chemical Co., Ltd. was used (Experiment 42).

The addition ratio of iron powder and activated carbon was 4% by mass. The additives were dispersed in the pot, and the rotating blades in the pot were rotated at about 13000 rpm. Changes in pH, COD, total nitrogen and total phosphorus concentration at that time are shown in Table 16. After 5 minutes, the COD was about 1/5, the total nitrogen was about 1/3, and the total phosphorus was about 1/4. In the 10-minute treatment, the COD was about 1/5, the total nitrogen was about 1/4, and the total phosphorus was about 1/100. In the 15-minute treatment, the COD was about 1/8, the total nitrogen was about 1/4, and the total phosphorus was about 1/700. The characteristic color of human waste disappeared in 5 minutes, and was colorless and transparent after that. The smell gradually faded.

(Example 4)
Human waste, activated carbon and iron powder were mixed and stirred in a juicer mixer (pot volume: 500 mL). As for the human waste, 150 mL was put into the pot of the juicer mixer. As the iron material, 5.2 g of pure iron powder (reduced iron powder, made of JFE steel, particle size: 250 μm or less, purity: 90 mass% or more (remainder is inevitable impurity)) was used. Activated carbon added by Kuraray Chemical Co., Ltd., and added 1.6 g (experiment 43) and 2.4 g (experiment 44) of PW-D.

The addition rates of activated carbon and iron powder were 4.5% by mass in Experiment 43 and 5.1% by mass in Experiment 44. The additives were dispersed in the pot, and the rotating blades in the pot were rotated at about 13000 rpm. Changes in pH, COD, total nitrogen and total phosphorus concentration at that time are shown in Table 17.

In Experiment 43, after 5 minutes, the COD was about 1/10, the total nitrogen was about 1/3, and the total phosphorus was about 1/8. After 10 minutes, the COD was about 1/13, the total nitrogen was about 1/3, and the total phosphorus was about 1/100. In the experiment 44 with a large amount of activated carbon, after 5 minutes, the COD was about 1/12, the total nitrogen was about 1/3, and the total phosphorus was about 1/15. After 10 minutes, the COD was about 1/20, the total nitrogen was about 1/3, and the total phosphorus was about 1/100. The characteristic color of human waste disappeared in 5 minutes, and was colorless and transparent after that. The smell gradually faded.

As shown in Table 17, it can be seen that by increasing the amount of activated carbon, the values of COD, total nitrogen and total phosphorus in the human waste are significantly decreased.

As described above, in the method for rapidly removing phosphorus, COD, nitrogen, color and odor in human urine according to the present invention of Examples 1 to 4, all rapidly remove phosphorus, nitrogen, color and odor in human urine, Furthermore, it can be seen that COD has also been reduced.

By using the rapid removal method according to the present invention, removal of phosphorus, COD, nitrogen, color, odor and the like in human urine can be effectively performed, thereby greatly contributing to the maintenance of the environment.

Claims

A method for rapidly removing phosphorus, COD, nitrogen, color and odor in human waste or excrement, characterized in that powdered activated carbon and iron powder are supplied to excrement or excrement in human waste or excrement.
The powdery activated carbon is any one of powdery, granular or linear, and has a specific surface area of 300 m 2 / g or more, and a diameter or long side of 2 mm or less. A method for rapidly removing phosphorus, COD, nitrogen, color and odor in human waste or human waste water according to claim 1.
The phosphorus, COD, nitrogen, color and odor in human waste or in human waste water according to claim 1 or 2, wherein the iron powder is a reduced iron powder and has a circle equivalent diameter of 1 mm or less. Rapid removal method.
The phosphorus or COD in human waste or human waste water according to any one of claims 1 to 3, characterized in that the ratio of the mass of said iron powder to said powdery activated carbon is 1/2 to 1/15. Rapid removal of nitrogen, color and odor.
The ratio of the said powdery activated carbon and the said iron powder in the said excrement or the manure waste water is 1 to 20 mass%, The phosphorus in the excrement or the manure waste water according to any one of claims 1 to 4 , COD, nitrogen, color and odor rapid removal method.
The phosphorus, COD in human waste or human waste water according to any one of claims 1 to 5, characterized in that the powdery activated carbon and the iron powder are contained and supplied in a container having water permeability. Rapid removal of nitrogen, color and odor.
An apparatus for removing phosphorus, COD, nitrogen, color and odor in human waste and human waste water, comprising a reaction tank, means for supplying powdered activated carbon, means for supplying iron powder, and stirring of human waste and human waste water. And means for removing.
The removal device according to claim 7, further comprising a recovery port for iron phosphate which has sunk to the bottom of the device.
9. The powdery activated carbon and the iron powder supply means are characterized in that the powdery activated carbon and the iron powder are contained in a container having water permeability and supplied. Remover as described in.
The removal device according to any one of claims 7 to 9, wherein the stirring means is a stirring blade, and the rotation speed of the stirring blade is 0.5 rpm or more.
10. The removal apparatus according to any one of claims 7 to 9, wherein the stirring means is a rotation of the reaction tank, and a circumferential speed of the reaction tank is 0.5 rpm or more.
11. The removal device according to claim 10, wherein the water-permeable container is suspended from the upper portion of the reaction tank into the excrement or excrement.
The removal apparatus according to claim 10, wherein the water-permeable container is fixed in the reaction vessel.