CN102791635A - Method of rapidly removing phosphorus, COD substance, nitrogen, color, and odor from excreta or excretal wastewater and removal device using the method - Google Patents
Method of rapidly removing phosphorus, COD substance, nitrogen, color, and odor from excreta or excretal wastewater and removal device using the method Download PDFInfo
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- CN102791635A CN102791635A CN200980163089.0A CN200980163089A CN102791635A CN 102791635 A CN102791635 A CN 102791635A CN 200980163089 A CN200980163089 A CN 200980163089A CN 102791635 A CN102791635 A CN 102791635A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/005—Black water originating from toilets
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
Technical field
The present invention relates to a kind of in order to remove efficiently and apace fecaluria or fecaluria waste water (below; Note is made fecaluria) in phosphorus, COD (Chemical Oxygen Demand, COD), nitrogen, color and the removal method of foul smell and the removal device that uses the phosphorus of this method.
Background technology
The pollution dirt of Environmental Water spreads just in the world, and needs urgent countermeasure.One of source of pollution of this Environmental Water have the waste water from livestock industry.Discharge the back herding waste water is sanitised to benchmark value in animal house that produces the source or farm till, but because of various reasons, practical situation are not pollute to reduce.
In addition, be phosphorus by one of livestock waste produced pollution source.Therefore phosphorus still be difficult to reduce at present the phosphorus concentration in the Environmental Water owing to can't decompose through mikrobe.
And then; Dirt prevents that the discharging benchmark of the phosphorus relevant with herding waste water of method from just using tentative benchmark (total phosphorus is 24mg/L) at present based on water quality; But estimate to fix tentatively restudying of benchmark from now on, and be enhanced to till the general datum-plane (total phosphorus is 8mg/L).
For livestock products farmers', the reduction of the COD of fecaluria also is big problem.Up to now, utilize the whole bag of tricks such as activated sludge process or oxidation pond (lagoon) mode to handle, but effect is limited with regard to economic aspect,, then can causes pollution, the water environment pollution in rivers and creeks if under inadequate treated state, be disposed in the Environmental Water.
In addition, infiltrating extremely, subterranean sewage can improve phreatic nitrous acid concentration or concentration of nitric acid.Japan Environment Ministry is made as 10mg/L with the phreatic benchmark value of nitrite nitrogen, nitric nitrogen.Generally speaking, if the concentration of these nitrogen compounds uprises, then might cause newborn child's methemoglobinemia disease etc.Because this kind social background, therefore the polluted by nitrogen for Environmental Water is just becoming serious problem.
In addition, generally speaking, be stench for maximum complaint of livestock industry.If also can address this problem, then for the stock farmer Gospel.
To these problems, be dissolved in the method for the phosphorus in the waste water as removal, in patent documentation 1, the processing that agglomeration process agent such as iron(ic)chloride, bodied ferric sulfate are used for the herding fecaluria removes the phosphorus of waste water.
In addition, in patent documentation 2 and patent documentation 3, announcement has makes molysite or aluminium salt and phosphate ion react the technology that is dissolved in the phosphorus in the waste water that removes.
And then in patent documentation 4, disclosing has following technology: in order to remove the phosphorus in addle or the plant effluent, make the phosphorus chemistry in the waste water be varied to tertiary iron phosphate and add flocculation agent such as bodied ferric sulfate or Poly aluminum Chloride (PAC), carry out purification of waste water then.
In addition, also there is the technology of using the iron and steel slag.
In the technology of in patent documentation 5, being put down in writing, in order to remove the phosphorus in the waste water that contains phosphorus, pass the dephosphorization of making a return journey of iron and steel slag through making waste water.The iron and steel slag uses blast furnace slag and removes cold slag.For removing phosphorus, preferred iron and steel slag is a porous matter.
In addition, also propose the pure iron of use is arranged but not molysite or scoriaceous method.For example, in patent documentation 6, record following main points:, and can reduce phosphoric acid concentration through adding micro mist iron in fecaluria.
Patent documentation 6 uses the iron-based material, and the particle diameter of its iron-based material powder is that specific surface area reaches 0.005m below the 3000 μ m
2/ g.In addition, iron level is more than 70%, and the composition beyond the iron is oxygen, magnesium, strontium, phosphorus, sulphur.
Announcement has the following technology of main points: through the fecaluria with respect to animal, scatter or be paved with or sneak into this iron-based material etc. with the ratio of counting %, water miscible phosphate ion and iron react and become insoluble phosphorus compound.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid is opened the 2001-205273 communique
[patent documentation 2] Japanese Patent Laid is opened the 2006-281177 communique
[patent documentation 3] Japanese Patent Laid is opened the 2008-68248 communique
[patent documentation 4] Japanese Patent Laid is opened the 2003-340464 communique
[patent documentation 5] Japanese Patent Laid is opened the 2008-142613 communique
[patent documentation 6] Japanese Patent Laid is opened the 2000-140862 communique
But use molysite of in said patent documentation 1～patent documentation 4, being put down in writing or aluminium salt are made a return journey in the method for dephosphorization, exist ion or composition beyond iron ion or the aluminum ion also to be added into the problem in the water.
Promptly; There is following problem: follow and in process object water, add molysite or aluminium salt; Tying counter ion such as the chloride ion that forms molysite or aluminium salt or sulfate ion with iron ion or aluminum ion key also is added in the process object water; Chloride ion concentration in the process object water or sulfate ion concentration rise, and the ecosystem is produced detrimentally affect.
In addition, the use iron and steel slag of in said patent documentation 5, being put down in writing make a return journey dephosphorization method, and patent documentation 6 in the use iron-based material put down in writing make a return journey in the method for dephosphorization, can't promote the speed of iron and phosphorus compound formation water insoluble active ingredient.That is the low problem of removal speed that, has phosphorus.In addition, the phosphorus concentration after the processing of in the instance of patent documentation 6, being seen is about 0.1 quality %, 1000mg/L.
That is, in said method, the removal speed of phosphorus is extremely slow, needs 1 usually.If the treatment time such as said as elongated, then need many treatment troughs that accumulate fecaluria.Because this kind present situation, therefore expect a kind of method that can handle phosphorus in the fecaluria etc. at short notice.
In addition, fecaluria has unique color (with reference to Fig. 1).
The problem of the maximum in the present herding wastewater treatment is decolouring.Up to now, the heavy addition through flocculation agent decolours, but on the funds existing problems and and impracticable.In addition, also can decolour, but also there is maintenance, the operator's of importing, the device of ozone generation device the problem of many practical aspects such as guaranteeing in this treatment process through ozonize.
Therefore, practical situation are the problems beyond the removal for phosphorus, and promptly the reductionization of the color of the concentration of nitrogen compound or COD value, fecaluria or foul smell (below, the situation that will be called phosphorus etc. is made as the situation that comprises them) does not have effective means.
Summary of the invention
The present invention is the invention that advantageously solves said problem, and its purpose is to provide a kind of and need not to add unwanted ion or composition and can remove the method for phosphorus in the fecaluria etc. apace and use the removal retrieving arrangement of this method.
Below, the experiment that the present invention is hit pay dirk is described.
At first,, then can see the dissolving of iron slightly, therefore to whether only utilizing iron just can remove phosphorus research if iron powder is added in the fecaluria.Employed iron powder is these two kinds of reduced iron powder (N-TECH manufactured 80 μ m～150 μ m) and brown iron oxides (stone well business (share) eight damp factories make 75 μ m～150 μ m).
Reduced iron powder is to utilize coke etc. with iron scale (red stone that produces on the surface of iron through spreading water when the calendering of slab, square billet (angle section of iron)) reduction, under the hydrogen environment, heat-treats the iron powder of manufacturing then, and has emptying aperture in the particle.Reduced iron powder is that Fe purity is the above iron powders of 90 quality %, and remainder is a unavoidable impurities.
On the other hand, brown iron oxide is to utilize calcined by rotary kiln to contain the iron powder that scoriaceous iron forms its oxidation, and Fe is 85 quality %～90 quality %.Impurity is CaO, the SiO that slag is formed
2, A1
2O
3, MgO etc.
Fecaluria 150mL is loaded in 2 liters the Vilaterm system wide-necked bottle, then to wherein adding iron powder 3g.Iron powder becomes 2 quality % with respect to the interpolation rate of fecaluria.Do not add the carbon material.Iron powder is not loaded in the sack, and directly is loaded in the Vilaterm container made with dispersion state.With the situation of using reduced iron powder as experiment 1, with the situation of using brown iron oxide as experiment 2.
The Vilaterm container made that is incorporated with fecaluria and iron powder carried put on the universal stage of ball mill and make its rotation with the condition of 10rpm.Phosphate ion concentration before handling is 75mg/L.The time variation of phosphate ion concentration at this moment is shown in table 1.After 120 minutes, the phosphate ion concentration somewhat reduces, and under the situation of reduced iron powder, becomes 20mg/L, under the situation of brown iron oxide, becomes 43mg/L.Even if only utilize iron powder, because dissolved ferric iron, so also step-down of phosphate ion concentration, but its reduction degree is small.
[table 1]
Table 1
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of the kind of iron powder (mg/L)
| Experiment No. | Experiment 1 | Experiment 2 |
| The iron powder kind | Reduced iron powder | Brown iron oxide |
| Before handling (mg/L) | 75（24.8） | 75（24.8） |
| 30 minutes (mg/L) | 35（11.6） | 50（16.5） |
| 60 minutes (mg/L) | 28（9.2） | 43（14.2） |
| 90 minutes (mg/L) | 20（6.6） | 43（14.2） |
| 120 minutes (mg/L) | 20（6.6） | 43（14.2） |
(iron powder: 3g, the interpolation rate of iron powder: 2 quality %, 10rpm does not use sack)
Secondly, with 3 kinds of conditions to studying by the influence that particle diameter was produced of iron powder.Iron powder uses brown iron oxide.The particle diameter of brown iron oxide is made as below the 75 μ m in experiment 3, in experiment 4, is made as 75 μ m～150 μ m, in experiment 5, is made as below the 500 μ m.Each brown iron oxide 3g is loaded in 2 liters the polyethylene bottle.Do not use carbide.Brown iron oxide is not loaded in the sack, and so that its dispersive state experimentize.Brown iron oxide is 2 quality % with respect to the interpolation rate of fecaluria.
The container that is incorporated with fecaluria carried put on the universal stage of ball mill, make its rotation specified time with the condition of 10rpm.Through after the specified time, measure the phosphate ion concentration in the fecaluria.Its variation is shown in table 2.Phosphate ion concentration before handling is 75mg/L.After 120 minutes, the phosphate ion concentration somewhat reduces, no matter the particle diameter of brown iron oxide how, under any circumstance all becomes 43mg/L.Can know that when still only utilizing iron powder even if make change of size, it is remarkable that the reduction of phosphate ion can not become yet.
[table 2]
Table 2
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of the kind of iron powder (mg/L)
| Experiment No. | Experiment 3 | Experiment 4 | Experiment 5 |
| The particle diameter of iron powder (μ m) | Below 75 | 75～150 | Below 500 |
| Before handling (mg/L) | 75（24.8） | 75（24.8） | 75（24.8） |
| 60 minutes (mg/L) | 50（16.5） | 50（16.5） | 50（16.5） |
| 90 minutes (mg/L) | 43（14.2） | 43（14.2） | 43（14.2） |
| 120 minutes (mg/L) | 43（142） | 43（14.2） | 43（14.2） |
(iron powder: 3g, the interpolation rate of iron material: 2 quality %, rotating speed: 10rpm, sack uses: do not have)
And then whether the phosphate ion concentration when only utilizing the carbon material in the fecaluria reduces is studied.The carbon material uses the activated carbon (made in China) of wooden system.Fecaluria 150mL is loaded in 2 liters the polyethylene bottle, do not use iron material, and add activated carbon (made in China) 0.8g.The carbon material is not loaded in the sack, and under original dispersion state, uses.Utilize the universal stage of ball mill, make the polyethylene bottle rotation with the condition of 10rpm.This experiment is made as experiment 6.The variation that to pass through the phosphate ion concentration after the specified time is shown in table 3.Measure phosphate ion concentration, and also COD, painted situation and foul smell are confirmed, its result is documented in the table 3 in the lump.Phosphate ion concentration is 113mg/L before the experiment beginning.The phosphate ion concentration of only utilizing activated carbon to stir in the fecaluria after 120 minutes is 113mg/L, does not see the reduction of phosphate ion concentration.
But the unique color (tawny) of fecaluria disappears after experiment begins 5 minutes and becomes colourless.In addition, though fecaluria has distinctive smell, through adding the carbon material and stirring, the fecaluria stink disappears, and the ammonia stink also reduces.And then variation has taken place in COD, can know the preceding 160mg/L of being of experiment, is reduced to till the 18.3mg/L after 120 minutes.
[table 3]
Table 3
Activated carbon is for phosphate ion, COD and de-odorised influence (experiment 6) " in () is total phosphorus concentration "
(iron powder: do not have, activated carbon: 0.8g, the interpolation rate: 0.13 quality %, 10rpm, sack uses: do not have)
Secondly, to through other activated carbon are added in the fecaluria, also whether phosphate ion concentration and color or COD reduction confirm.Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Do not use iron material, and use activated carbon (Kuraray chemistry (share) is made, below the Kuraray Coal PW-D 0.25mm) 0.8g (being made as experiment 7).
Activated carbon is loaded in the polyethylene bottle with original state uses.The mixture of activated carbon and fecaluria is disperseed in polyethylene bottle.Utilize the universal stage of ball mill, make polyethylene bottle rotation 120 minutes with the condition of 10rpm.The variation of phosphate ion concentration at this moment is shown in table 4.Also COD, painted situation, foul smell are confirmed simultaneously, its result is documented in the table 4 in the lump.Phosphate ion concentration is 113mg/L before experiment and after the experiment, do not reduce.
But the unique color (tawny) of fecaluria disappears after experiment begins 5 minutes and becomes colourless.In addition, fecaluria has distinctive smell, and becomes big social concern, but through mixing with activated carbon, the fecaluria stink disappears, and the ammonia stink reduces.And then variation has taken place in COD, is 160mg/L before the experiment, is reduced to till the 16.5mg/L after 120 minutes.Though it is there is not the effect of removing the phosphorus in the fecaluria in activated carbon, effective for COD, decolouring, deodorizing.
[table 4]
Table 4
Activated carbon is for phosphate ion, COD and de-odorised influence (experiment 7) " in () is total phosphorus concentration "
(iron powder: do not have, activated carbon: 0.8g, the interpolation rate: 0.13 quality %, 10rpm, sack uses: do not have)
And then, whether the removal of the phosphorus in the fecaluria there are differences according to the kind of activated carbon study.Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Iron material uses straight iron powder (reduced iron powder, Kawasaki, Japan system iron (JFE Steel) (share) is made, below the JIPK K-1001,0.25mm) 5.2g.Activated carbon is made as following 3 kinds: Exocarpium cocois (Cocos nucifera L) system (PK-D, experiment 9) and China's system activated carbon (experiment 10) that the wooden system that Kuraray chemistry (share) is made (PW-D, experiment 8), Kuraray chemistry (share) are made.Usage quantity all is made as 0.8g.Moreover the interpolation rate of iron material and activated carbon is 4 quality %.
The mixture with straight iron powder and activated carbon is not loaded in the sack, and it is disperseed in 2 liters polyethylene bottle with original state, utilizes the universal stage of ball mill, makes its rotation with the condition of 10rpm.The variation of phosphoric acid concentration at this moment is shown in table 5.When using the activated carbon of Kuraray (share) manufacturing, the color of fecaluria disappears and becomes colourless.If China's system activated carbon is not then seen decolouring.
In addition, COD is initially 160mg/L, no matter after 120 minutes be which kind of activated carbon, COD all becomes about about 10mg/L, can see significant reduction effect.Phosphate ion concentration when using brown iron oxide is 113mg/L in when beginning experiment, in experiment 8, be decreased to 0mg/L after 90 minutes till, in experiment 9, be decreased to 0.2mg/L after 120 minutes till, in experiment 10, be decreased to 0.5mg/L after 120 minutes till.
Variation has also taken place in the foul smell of fecaluria.During beginning, send intensive ammonia stink and fecaluria stink.But after 30 minutes, the fecaluria stink disappears, and only becomes the ammonia stink.And then after 60 minutes, the ammonia stink is also thin out.Thereafter, followed effluxion 90 minutes, 120 minutes, the ammonia stink is further thin out.
[table 5]
Table 5
Variation " in () is total phosphorus concentration " by caused phosphate ion of the kind of activated carbon and COD (mg/L)
(iron powder: 5.2g, activated carbon: 0.8g, the interpolation rate of iron material and carbon material: 4 quality %, 10rpm does not use sack)
To studying by the influence that addition produced of iron and carbon.Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Iron material uses and contains scoriaceous iron (stone well business (share) is made, below the 1.4mm).Contain scoriaceous iron (stone well business (share) eight tide make) in the manufacturing stage of iron, when utilize converter and electric furnace go out to the time slag (scum, slag) with the separated recovery of molten steel, but Separation and Recovery fully, the part of molten steel is sneaked into to slag.This steel mixes the slag that the part that exists is called as molten slag, sneaks into feed metal with slag.
Stone well business eight tides separate (pulverizing, magnetic separation, screening) with slag and make iron powder from this molten slag.But, be difficult to fully separate slag, owing to contain some slag, therefore be called " containing scoriaceous iron ".About purity, owing to also contain slag sometimes, in addition, because of batch also having deviation, so the purity of Fe is about 70 concentration %～90 concentration %.As impurity, comprise CaO, SiO as scoriaceous composition
2, A1
2O
3, MgO etc.In experiment, use this to contain scoriaceous iron 6.5g.
The carbon material uses activated carbon (plastics system, Powdered), makes its usage quantity be changed to 0.5g (experiment 11), 1.0g (experiment 12) and 1.5g (experiment 13) and experimentizes.
The interpolation rate of iron material and carbon material is 7.1% (experiment 11), 13.3% (experiment 12) and 18.8% (experiment 13).
The mixture of iron material and carbon material is put into to non-woven fabrics (6cm * 6cm).The non-woven fabrics of having put into additive is loaded to polyethylene bottle, utilizes the universal stage of ball mill, make its rotation with the condition of 10rpm.The variation of phosphate ion concentration at this moment is shown in table 6.Phosphate ion concentration during beginning is 113mg/L, even if after 120 minutes, be 20mg/L～35mg/L also, does not see significant reduction.Can know that the phosphate ion concentration somewhat reduces, and does not see the difference that is produced by addition when use contains scoriaceous iron.
[table 6]
Table 6
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of activated carbon usage quantity
| Experiment No. | Experiment 11 | Experiment 12 | Experiment 13 |
| Activated carbon (g) | 0.5 | 1.0 | 1.5 |
| Iron powder (g) | 6.5 | 6.5 | 6.5 |
| Interpolation rate (quality %) | 7.1 | 13.3 | 18.8 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 70（23.1） | 55（18.2） | 70（23.1） |
| 60 minutes (mg/L) | 48（15.8） | 35（11.6） | 55（18.2） |
| 90 minutes (mg/L) | 35（11.6） | 25（8.3） | 40（13,2） |
| 120 minutes (mg/L) | 35（1L6） | 20（6.6） | 30（9.9） |
Secondly, fix making the iron powder amount, the removal effect of the phosphorus in the fecaluria when only making the activated carbon quantitative change is studied.
The iron powder material uses and contains scoriaceous iron (stone well business (share) is made, below the 1.4mm) 7.7g.Activated carbon uses plastics system, powdered activated carbon, makes its usage quantity be changed to 0.6g (experiment 14), 1.3g (experiment 15) and 1.9g (experiment 16) and experimentizes.The interpolation rate of iron powder material and activated carbon is 7.2 quality % (experiment 14), 14.4 quality % (experiment 15) and 19.8 quality % (experiment 16).
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.The mixture of iron powder and activated carbon put into (6cm * 6cm), it is disperseed utilizes the universal stage of ball mill, makes its rotation 120 minutes with the condition of 10rpm to non-woven fabrics in polyethylene bottle.The variation of phosphate ion concentration at this moment is shown in table 7.Phosphate ion concentration is 113mg/L when beginning, even if also be 10mg/L～30mg/L after 120 minutes.Though phosphate ion concentration is reduced, be not to reduce significantly through this processing.Scoriaceous iron causes because of use contains for this.In addition, do not see the difference that addition produced by iron powder and activated carbon.
[table 7]
Table 7
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of activated carbon usage quantity
| Experiment No. | Experiment 14 | Experiment 15 | Experiment 16 |
| Activated carbon (g) | 0.6 | 1.3 | 1.9 |
| Contain scoriaceous iron powder (g) | 7.7 | 7.7 | 7.7 |
| Interpolation rate (quality %) | 7.2 | 14.4 | 19.8 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 70（23.1） | 40（13.2） | 55（18.2） |
| 60 minutes (mg/L) | 40（13.2） | 20（6.6） | 35（11.6） |
| 90 minutes (mg/L) | 35（11.6） | 15（5.0） | 30（10.0） |
| 120 minutes (mg/L) | 30（9.9） | 10（3.3） | 25（8.3） |
To studying with respect to the influence that the interpolation rate of fecaluria is produced by the mixture of iron powder and activated carbon.The iron powder use contains scoriaceous iron (stone well business (share) is made, below the 1.4mm) 2.6g (experiment 17), 3.9g (experiment 18), reaches 5.2g (experiment 19).As activated carbon, the activated carbon Kuraray Coal PW-D that uses Kuraray chemistry (share) to make is made as 0.4g (experiment 17), 0.6g (experiment 18) and 0.8g (experiment 19) with its usage quantity.
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.The mixture of iron powder and activated carbon put into (6cm * 6cm), place it in then in the polyethylene bottle utilizes the universal stage of ball mill, makes its rotation 2 hours with the condition of 10rpm to the fabric sack of nonwoven.The variation of phosphate ion concentration at this moment is shown in table 8.When use contained scoriaceous iron, initial phosphate ion concentration was 113mg/L, becomes 12.5mg/L～48mg/L after 120 minutes.In addition, the interpolation rate of iron powder and activated carbon must be big more with respect to the fecaluria quantitative change, and it is low more that phosphate ion concentration becomes.
[table 8]
Table 8
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of interpolation rate of iron and carbon material
| Experiment No. | Experiment 17 | Experiment 18 | Experiment 19 |
| Activated carbon (g) | 0.4 | 0.6 | 0.8 |
| Contain scoriaceous iron powder (g) | 2.6 | 3.9 | 5.2 |
| Interpolation rate (quality %) | 2.0 | 3.0 | 4.0 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 70（23.1） | 70（23.1） | 55（18.2） |
| 60 minutes (mg/L) | 70（23.1） | 55（18.2） | 40（13.2） |
| 90 minutes (mg/L) | 55（18.2） | 40（13.2） | 25（8.3） |
| 120 minutes (mg/L) | 48（15.8） | 25（8.3） | 12.5（4.1） |
And then, the influence that the interpolation rate by iron powder and activated carbon is produced is studied.Iron powder is used straight iron powder (reduced iron powder, JFE Steel (share) makes, below the 0.25mm).Its usage quantity is made as 2.6g (experiment 20), 3.9g (experiment 21), 4.5g (experiment 22), 5.2g (experiment 23) and 5.8g (experiment 24).As activated carbon, use activated carbon (Kuraray chemistry (share) is made, Kuraray Coal PW-D).Making its usage quantity be changed to 0.4g (experiment 20), 0.6g (experiment 21), 0.7g (experiment 22), 0.8g (experiment 23) and 0.9g (experiment 24) experimentizes.
The interpolation rate with respect to fecaluria of iron powder and activated carbon is 2 quality % (experiment 20), 3 quality % (experiment 21), 3.5 quality % (experiment 22), 4 quality % (experiment 23) and 4.5 quality % (experiment 24).
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Mixture put into (6cm * 6cm) on the universal stage of ball mill, makes its rotation 2 hours with the condition of 10rpm to non-woven fabrics.The variation of phosphate ion concentration at this moment is shown in table 9.Can know that then the phosphate ion concentration in the fecaluria reduces if straight iron powder is used for iron powder, if the addition of activated carbon increases, then the removal effect of phosphorus becomes big.
[table 9]
Table 9
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of interpolation rate of iron and carbon material
| Experiment No. | Experiment 20 | Experiment 21 | Experiment 22 | Experiment 23 | Experiment 24 |
| Activated carbon (g) | 0.4 | 0.6 | 0.7 | 0.8 | 0.9 |
| Straight iron powder (g) | 2.6 | 3.9 | 4.5 | 5.2 | 5.8 |
| Interpolation rate (quality %) | 2.0 | 3.0 | 3.5 | 4.0 | 4.5 |
| During beginning (mg/L) | 113（37.3） | ?113（37.3） | ?113（37.3） | ?113（37.3） | ?113（37.3） |
| 30 minutes (mg/L) | 55（18.2） | 30（10） | 25（8.3） | 20（6.6） | 15.0（5.0） |
| 60 minutes (mg/L) | 3.5（1.2） | 2.0（0.7） | 2.0（0.7） | 2.0（0.7） | 1.5（0.5） |
| 90 minutes (mg/L) | 2.0（0.7） | 0.4（0.1） | 0.2（ND） | 0.2（ND） | 0.2（ND） |
| 120 minutes (mg/L) | 0.5（0.2） | 0.2（ND） | 0.2（ND） | 0.2（ND） | 0.2（ND） |
Rotating speed when the mixture that makes iron powder and activated carbon is rotated on the ball mill universal stage is studied for the influence that reduces of phosphate ion concentration.Iron powder is used and is contained scoriaceous iron (stone well business (share) is made, below the 1.4mm) 7.7g.As activated carbon, use plastics system, powdered activated carbon 1.3g.
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Mixture is put into to non-woven fabrics (6cm * 6cm).The interpolation rate of iron powder and activated carbon is 6 quality %.Additive is disperseed in polyethylene bottle, and the condition with 10rpm (experiment 25), 30rpm (experiment 26) and 45rpm (experiment 27) makes its rotation on the ball mill universal stage then.The variation of phosphate ion concentration at this moment is shown in table 10.When use contained scoriaceous iron, the phosphate ion concentration somewhat reduced.In addition, small by the difference that rotating speed produced.
[table 10]
Table 10
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of interpolation rate of iron and carbon material
| Experiment No. | Experiment 25 | Experiment 26 | Experiment 27 |
| Rotating speed (rpm) | 10 | 30 | 45 |
| Activated carbon (g) | 1.3 | 1.3 | 1.3 |
| Contain scoriaceous iron powder (g) | 7.7 | 7.7 | 7.7 |
| Interpolation rate (quality %) | 6.0 | 6.0 | 6.0 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 40（13.2） | 35（11.6） | 40（13.2） |
| 60 minutes (mg/L) | 20（6.6） | 13（4.3） | 20（6.6） |
| 90 minutes (mg/L) | 15（5.0） | 8（2.6） | 13（4.3） |
| 120 minutes (mg/L) | 10（3.3） | 2（0.7） | 8（2.6） |
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Iron powder is used straight iron powder (reduced iron powder, JFE Steel makes, below the 250 μ m) 5.2g.The activated carbon PW-D 0.8g that activated carbon uses Kuraray chemistry (share) to make.
The interpolation rate with respect to fecaluria of iron powder and activated carbon is 4 quality %.Additive is disperseed in polyethylene bottle, and the condition with 5rpm (experiment 28), 10rpm (experiment 29) and 15rpm (experiment 30) makes its rotation on the ball mill universal stage then.The variation of phosphate ion concentration at this moment is shown in table 11.Can know that according to this table the phosphate ion concentration in the fecaluria reduces.In addition, see not too to difference by rotating speed produced.
[table 11]
Table 11
Variation " in () is total phosphorus concentration " by the caused phosphate ion concentration of the rotating speed of reaction vessel
| Experiment No. | Experiment 28 | Experiment 29 | Experiment 30 |
| Rotating speed (rpm) | 5 | 10 | 15 |
| Activated carbon (g) | 0.8 | 0.8 | 0.8 |
| Straight iron powder (g) | 5.2 | 5.2 | 5.2 |
| Interpolation rate (quality %) | 4.0 | 4.0 | 4.0 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 40（13.2） | 30（10） | 40（13.2） |
| 60 minutes (mg/L) | 10（3.3） | 2（0.7） | 20（6.6） |
| 90 minutes (mg/L) | 2（0.7） | 0.2（ND） | 2（0.7） |
| 120 minutes (mg/L) | 0.8（0.3） | 0.2（ND） | 0.5（0.1） |
To when reusing iron powder and activated carbon, whether the phosphorus removal effect can continue to study through the multiple number of times.Iron powder is used straight iron powder (reduced iron powder, JFE Steel makes, below the 250 μ m) 5.2g.As activated carbon, the activated carbon PW-D 0.8g that uses Kuraray chemistry (share) to make.
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Do not use non-woven fabrics, and use mixture with dispersion state.Additive is disperseed in polyethylene bottle, and the condition with 10rpm makes its rotation 120 minutes on the ball mill universal stage then.Then, take out the fecaluria in the Vilaterm container made, add untreated fecaluria 150mL, make it be further rotated 2 hours then.This operation is repeated 4 times.The variation of phosphate ion concentration at this moment is shown in table 12.Even if repeat 4 times, phosphate ion concentration also is reduced to till the 3.5mg/L, and the phosphorus removal effect of iron powder and activated carbon continues.
In addition, also together measure COD.COD before handling is about 100mg/L, handles in (experiment 31) at the 1st time to become 11.5mg/L.Handling in (experiment 32) at the 2nd time is 20mg/L, and handling in (experiment 33) at the 3rd time is 35mg/L, and handling in (experiment 34) in the 4th is 50mg/L, and the decrement of COD diminishes slightly.And then the color of fecaluria is tawny before processing, becomes colourless through the 1st time processing.In the 2nd time is handled, become transparently, but in the 3rd time is handled, begin painted a little.
In addition, the foul smell of fecaluria becomes odorless in the processing of the 1st time (experiment 31), and residual a little in the processing of the 2nd time (experiment 32) and the 3rd time (experiment 33) have a foul smell.And then how foul smell is not eliminated in the processing of the 4th (experiment 34).
[table 12]
Table 12
The repeated use of additive is for the influence " in () is total phosphorus concentration " of phosphate ion concentration
| Experiment No. | Experiment 31 | Experiment 32 | Experiment 33 | Experiment 34 |
| Multiplicity (inferior) | 1 | 2 | 3 | 4 |
| Activated carbon (g) | 0.8 | 0.8 | 0.8 | 0.8 |
| Straight iron powder (g) | 5.2 | 5.2 | 5.2 | 5.2 |
| Interpolation rate (quality %) | 4.0 | 4.0 | 4.0 | 4.0 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 3.5（1.0） | 25（8.3） | 40（13.2） | 55（18.2） |
| 60 minutes (mg/L) | 0.8（0.3） | 3.5（1.2） | 10（3.3） | 20（6.6） |
| 90 minutes (mg/L) | 0.2（ND） | 1.5（0.5） | 3.5（1.2） | 7.5（2.3） |
| 120 minutes (mg/L) | 0.2（ND） | 1.0（0.3） | 2（0.7） | 3.5（1.2） |
| COD（mg/L） | 11.5 | 20 | 35 | 50 |
| Color | Transparent | Transparent | Painted slightly | Painted slightly |
| Foul smell | Do not have | Few | Few | Strongly |
To through increasing the fecaluria amount, and the removal effect of the phosphate ion of the mixture that makes iron powder and activated carbon during with respect to the interpolation ratio vary of fecaluria amount is studied.Employed fecaluria amount is following 4 kinds in the experiment: 150mL (experiment 35), 300mL (experiment 36), 450mL (experiment 37) and 600mL (experiment 38).
Iron powder is used straight iron powder (reduced iron powder, JFE Steel (share) makes, below the 250 μ m) 5.2g.The PW-D 0.8g that activated carbon uses Kuraray chemistry (share) to make.The interpolation rate with respect to fecaluria of iron powder and activated carbon becomes 4 quality % (experiment 35), 2 quality % (experiment 36), 1.5 quality % (experiment 37) and 1 quality % (experiment 38).
Each fecaluria amount all is loaded in 2 liters the polyethylene bottle.Do not use non-woven fabrics, and under original dispersion state, mixture is loaded in the polyethylene bottle.On the universal stage of ball mill, make polyethylene bottle rotation 120 minutes, or rotate to till phosphate ion concentration becomes below the 0.8mg/L with the condition of 10rpm.The variation of phosphate ion concentration at this moment is shown in table 13.When the interpolation rate was 4 quality %, phosphate ion concentration became 0.8mg/L after 60 minutes.When the interpolation rate was 2 quality %, phosphate ion concentration became 0.8mg/L after 90 minutes.
In addition, when the interpolation rate is 1.5 quality %, even if phosphate ion concentration also is 2mg/L after 120 minutes, when the interpolation rate is 1 quality %, even if phosphate ion concentration also is 5mg/L after 120 minutes.On the other hand, also influential for COD.When the interpolation rate was 4 quality %, initial COD was 160mg/L, followed the interpolation rate to descend, and COD increases to 12.3mg/L, 14.8mg/L, and when the interpolation rate was 1 quality %, it was 27.5mg/L that COD increases.
[table 13]
Table 13
The variation of the phosphate ion concentration when making the fecaluria quantitative change " is total phosphorus concentration " in ()
| Experiment No. | Experiment 35 | Experiment 36 | Experiment 37 | Experiment 38 |
| Fecaluria amount (mL) | 150 | 300 | 450 | 600 |
| Activated carbon (g) | 0.8 | 0.8 | 0.8 | 0.8 |
| Straight iron powder (g) | 5.2 | 5.2 | 5.2 | 5.2 |
| Interpolation rate (quality %) | 4.0 | 2.0 | L5 | 1.0 |
| During beginning (mg/L) | 113（37.3） | 113（37.3） | 113（37.3） | 113（37.3） |
| 30 minutes (mg/L) | 3.5（1.0） | 10（3.3） | 20（7.7） | 30（10） |
| 60 minutes (mg/L) | 0.8（0.3） | 3.5（1.2） | 10（3.3） | 20（6.6） |
| 90 minutes (mg/L) | 0.2（ND） | 0.8（0.3） | 3.5（1.2） | 10（3.3） |
| 120 minutes (mg/L) | 0.2（ND） | 0.2（ND） | 2（0.7） | 5（1.7） |
| COD（mg/L） | 11.5 | 12.3 | 14.8 | 27.5 |
| Color | Transparent after 5 minutes | Transparent after 10 minutes | Transparent after 15 minutes | Transparent after 20 minutes |
| Foul smell | Do not have | Few | Few | Strongly |
Process as above experiment, investigation, the inventor finds can remove phosphorus, COD, nitrogen, color and foul smell in the fecaluria fast through fecaluria is flowed with respect to activated carbon and iron powder.
The present invention is based on the invention of said discovery.
That is, purport of the present invention is constructed as follows.
1. the quick removal method of phosphorus, COD, nitrogen, color and the foul smell in fecaluria or the fecaluria waste water is characterized in that: in fecaluria or fecaluria waste water, supply with powdered activated carbon and iron powder, and stir and it is flowed.
2. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in said 1 described fecaluria or the fecaluria waste water, it is characterized in that: said powdered activated carbon is any shape in Powdered, granular or the wire, and specific surface area is 300m
2More than/the g, one in diameter or the long limit is below the 2mm.
3. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in said 1 or 2 described fecalurias or the fecaluria waste water, it is characterized in that: said iron powder is a reduced iron powder, and its equivalent circle diameter is below the 1mm.
4. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in each described fecaluria in said 1 to 3 or the fecaluria waste water, it is characterized in that: said iron powder is 1/2～1/15 with respect to the ratio of the quality of said powdered activated carbon.
5. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in each described fecaluria in said 1 to 4 or the fecaluria waste water, it is characterized in that: the said powdered activated carbon in said fecaluria or the fecaluria waste water and the ratio of said iron powder are 1 quality %～20 quality %.
6. according to the quick removal method of phosphorus, nitrogen, color and foul smell in each described fecaluria in said 1 to 5 or the fecaluria waste water, it is characterized in that: said powdered activated carbon and said iron powder are accommodated in the container with water-permeable supply with.
7. removal device; It is the device that the phosphorus in fecaluria and the fecaluria waste water, COD, nitrogen, color and foul smell are removed, and it is characterized in that: the agitating unit of feed unit, this fecaluria and fecaluria waste water that comprises feed unit, the iron powder of reactive tank, powdered activated carbon.
8. according to said 7 described removal devices, it is characterized in that: the recovery mouth that comprises the tertiary iron phosphate of the bottom that sinks down into said device.
9. according to said 7 or 8 described removal devices, it is characterized in that: the feed unit of said powdered activated carbon and said iron powder is accommodated in said powdered activated carbon and said iron powder in the container with water-permeable and supplies with.
10. according to each described removal device in said 7 to 9, it is characterized in that: said agitating unit is an agitating vane, and the rotating speed of this agitating vane is made as more than the 0.5rpm.
11. according to each described removal device in said 7 to 9, it is characterized in that: said agitating unit is the rotation of reactive tank, and the SFM of this reactive tank is made as more than the 0.5rpm.
12., it is characterized in that: said container with water flowing property is hung down to fecaluria or fecaluria waste water from said reactive tank top according to said 10 described removal devices.
13., it is characterized in that: said container with water flowing property is fixed in the said reactive tank according to said 10 or 11 described removal devices.
(effect of invention)
According to the present invention, can unwanted ion or composition be added in the water, and reduce phosphorus in the water etc. fast and efficiently.
Description of drawings
Fig. 1 is the photo of the fecaluria before the expression decolouring.
Fig. 2 is the figure of the formation of expression quick removal recovery system of the present invention.
Fig. 3 is the concept map of the quick phosphorus removal device of expression (experiment is used).
Fig. 4 is the concept map of expression quick phosphorus removal device of the present invention (the horizontal type container of cylinder rotation mode).
Fig. 5 is the concept map of expression quick phosphorus removal device of the present invention (the inner stirring-type of the horizontal type of cylinder).
Fig. 6 is the concept map of expression quick phosphorus removal device of the present invention (the inner stirring-type of cylinder longitudinal type).
Fig. 7 is the concept map of expression quick phosphorus removal device of the present invention (the inner stirring-type of pyramid type).
Fig. 8 is the concept map of expression quick phosphorus removal device of the present invention (pyramid type fluidized bed type).
Fig. 9 is the photo of the fecaluria after the expression decolouring.
Embodiment
Below, the present invention is specified.
The present invention carries out the removal of the phosphorus etc. in the fecaluria through following mode: in reactive tank; To the powdered activated carbon (below; Note is made activated carbon), iron powder and fecaluria stir and make they flow (below; Note stirs), promptly in reactive tank, activated carbon and iron powder are contacted with fecaluria.
Even if iron powder is added in the fecaluria, as the experiment as noted above, the dissolving of the iron in the iron powder also less produces.In order to make dissolved ferric iron, must further in fecaluria, add activated carbon.Through in fecaluria, adding activated carbon, produce between activated carbon and the iron and contact, and form a kind of local element, the ionize of iron is carried out thus, produces the reaction with phosphate ion, and phosphate ion becomes insoluble tertiary iron phosphate.
As stated, phosphate ion in the fecaluria and the iron ion in the iron powder react and generate tertiary iron phosphate.Because tertiary iron phosphate is insoluble, therefore become throw out, the surface of coated iron powder and activated carbon, and reaction is counteracted.That is, must the dirt settling on surface be peeled off, separate, must stir fecaluria for this reason.
When said stirring, comparatively ideal be iron powder with respect to the ratio (quality of the quality/iron powder of expression activated carbon in the present invention) of the quality of activated carbon is 1/2～1/15.More preferably 1/2～1/10.In addition, preferably the ratio (quality of the quality/fecaluria of iron powder and activated carbon) of iron powder in the fecaluria and activated carbon is made as 1 quality %～20 quality %.
In addition, if use as ball mill as device, then become and stir, mix and impacts, dephosphorization effect obtains promotion, so preferably.
Stirring among the present invention is preferably carried out through the rotation of agitating vane or reactive tank itself.At this moment, under the situation of agitating vane, more than the preferred 0.5rpm of the rotating speed of blade.More preferably about 100rpm～1000rpm, when desire promotes processing speed, can be made as about 5000rpm～30000rpm.In addition, under the situation of the rotation of reactive tank itself, preferably SFM is made as more than the 0.5rpm, the upper limit does not have special restriction, but comparatively ideal be below the 100rpm degree.
In the present invention; Activated carbon and iron powder are all used powder; Through be made as said iron powder with respect to the ratio of the quality of activated carbon, and fecaluria in the scope of iron powder and the ratio of activated carbon etc.; Make both pass through mobile the grade and contact energetically, the stripping of promotion iron ion can improve the speed of removing phosphorus thus.
And then, become easily in order to make to reclaim, can the mixture of activated carbon and iron powder be accommodated in the container with water-permeable.
Thus, the recyclable tertiary iron phosphate that generates through the reaction of phosphate ion and iron ion, and also can be used as resource and utilization again.
Taking in the container of mixture of iron powder and activated carbon comparatively ideal is by the made container of fiber (sack).This container is fabric or non-woven fabrics or net (reticulattion).If this kind container, then water can pass through, but powder etc. can't pass through.In addition, the tertiary iron phosphate that is generated also can't pass through.After processing, also can be together discarded together with container.Perhaps, also can take out tertiary iron phosphate from container.
Any shape in activated carbon preferred powder powder among the present invention, the granular or wire.In addition, comparatively ideal is that its specific surface area is 300m
2More than/the g, one in diameter or the long limit is below the 2mm.
Moreover, so-called granular, be meant that the length of diameter surpasses the particle shape of 0.1mm, so-called Powdered, the length that is meant diameter is the particle shape below the 0.1mm.Here, the length of so-called diameter is meant diameter under the situation of spherical particle, under the situation of rectangle particle, is meant cornerwise length, and (Moritex (share) MS-804) measures for example can to use digital CCD microscope.
The preferred reduced iron powder of iron powder among the present invention, the purity of iron is comparatively ideal to be 90 quality % above (remainder is a unavoidable impurities).In addition, the particle diameter of powder is haggled over equivalent circle diameter and it is desirable to below the 1mm, and better is below the 250 μ m.Moreover the equivalent circle diameter among the present invention is that (Moritex (share) makes, and the value of MS-804) being measured is obtained through using digital CCD microscope.
One of the ultimate system of removal phosphorus of the present invention etc. is illustrated in Fig. 2.In reactive tank, mix fecaluria, activated carbon and iron powder and generate iron ion.The iron ion that is generated be dissolved in phosphate ion in the fecaluria and react and generate tertiary iron phosphate.After the reaction of having carried out the specified time, supernatant (or reaction solution) is delivered in the settling bath 1.The throw out of the bottom that is accumulated in reactive tank is delivered in the settling bath 2.In each settling bath, tertiary iron phosphate sinks to separating.To not contain sedimentary supernatant discharges.Throw out is reclaimed, utilizes as tertiary iron phosphate etc.
Moreover said reactive tank does not then have special restriction so long as can stir the structure of fecaluria with respect to activated carbon and iron powder, but the structure that structure that preferred reaction groove itself rotates or reactive tank inside have rotating paddle.
Below represent the example of device of the present invention, but so long as in the scope of the present invention, then take other examples also harmless certainly.In addition, though not shown, take in the container of activated carbon and iron powder and not only can directly put into, and can be fixed in the reactive tank, or under the situation of agitating vane mode, also can hang to reactive tank.
Moreover, select any example that treatment capacity, treatment time, place are arranged, various restrictions such as area are set, as long as judge with the practical situation at scene.
(1) reactive tank rotation mode (with reference to Fig. 3)
Instance carries out through this mode.Utilize the universal stage of ball mill, the reactive tank that is incorporated with fecaluria, activated carbon and iron powder is carried put on this universal stage, carry out the rotation of specified time then, carry out the removal of phosphorus etc. thus.
(2) alr mode
Fecaluria, activated carbon and iron powder are loaded in the reactive tank, carry out the removal of phosphorus etc.In order to promote three's contact, and stir, mix, but have variety of way according to stirring means.
The container rotation mode (with reference to Fig. 4) of the horizontal type of cylinder, the inside alr mode (with reference to Fig. 5) of the horizontal type of cylinder, the inside alr mode (with reference to Fig. 6) of cylinder longitudinal type, the inside alr mode (with reference to Fig. 7) of circular cone longitudinal type etc. are arranged.
(3) high-speed stirring mode
Below shown in the part of instance be to use the fruit juice stirrer to carry out.Because to stir at a high speed, the blade that perhaps stirs usefulness is positioned at the reactive tank bottom, and the angle of blade becomes up, even if the therefore high iron powder of density also can be rolled up to reactive tank top.Can produce on high frequency ground with contacting also of activated carbon, this mode is optimum alr mode of the present invention.
(4) fluidized-bed mode (with reference to Fig. 8)
This reaction is the heterogeneous body system that comprises fecaluria, activated carbon and iron powder.Therefore, must develop the device that a kind of three of making contacts efficiently.As shown in Figure 8 import the device of air through being made as, and make fecaluria, activated carbon and iron powder contact, and stir and mix to mixture high speed ground.
The tertiary iron phosphate that reaction through iron and phosphorus generates is dispersed in the fecaluria or sneaks into to mud and becomes problem sometimes.Therefore, comparatively ideal is to set the recyclable tertiary iron phosphate that generates in advance for.That is,, can be provided with in the bottom of reactive tank and reclaim mouth in order to reclaim tertiary iron phosphate.
In addition, through iron powder and activated carbon are loaded in the container (sack) of water-permeable recyclable tertiary iron phosphate in advance.That is, container is at iron powder, activated carbon and tertiary iron phosphate, and tertiary iron phosphate is not sneaked into to fecaluria.After removals such as phosphorus, only discarded container also can carry out phosphorus thus and remove processing.
But, under the little situation of the container (sack) of water-permeable, become the state that iron powder and activated carbon keep in touch.Because the tertiary iron phosphate that the reaction through iron powder and activated carbon generates is an insulativity, so the stripping of iron ion hindered, so preferably avoid the use of pouch (container).In the case, advantageously iron powder and activated carbon directly are fed in the reactive tank and handle, but not use the processing of container.When not using container as said, after iron and phosphorus react, liquid is separated with throw out, liquid is discharged thus, and throw out is reclaimed as useful resources.
The sedimentary recovery of this moment can be reclaimed through following previous known method: use the filter type, pressure filter mode, spinning mode of common filter cloth etc.
Problem when in addition, using activated carbon is a price.Even if having high-performance,, then also be difficult to actual use if price is high.In order to address this problem, from decolourising property with study in price, and grope the activated carbon that generates in the stage of offal treatment.
Through using said activated carbon as carbon material powder, painted fecaluria faded with interior the beginning at 5 minutes, and became colourless (with reference to Fig. 9).In addition, the distinctive foul smell of fecaluria is reduced.
[instance]
(instance 1)
Fecaluria 150mL is loaded in 2 liters the reactive tank (polyethylene bottle).Iron powder use straight iron powder (reduced iron powder, JFE Steel makes, particle diameter: below the 250 μ m, purity: 5.2g 90 quality % above (remainder is a unavoidable impurities)).The PW-D 0.8g that activated carbon uses Kuraray chemistry (share) to make.
The interpolation rate with respect to fecaluria of iron powder and activated carbon is 4 quality %.Additive is disperseed in polyethylene bottle, then on the universal stage of ball mill, make its rotation with the condition of 10rpm (experiment 39).The variation of pH, COD, total nitrogen and total phosphorus concentration at this moment is shown in table 14.COD becomes approximately 1/5 after 30 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/100.The distinctive color of fecaluria disappeared after 5 minutes, was thereafter colourless, transparent.Foul smell is thin out gradually.
[table 14]
Table 14
Fecaluria under the top condition is handled (experiment 39)
(activated carbon: 0.8g, straight iron powder: 5.2g, the interpolation rate: 4 quality %, 10rpm, sack uses: do not have)
Moreover; Under the condition of said (experiment 39) record, straight iron powder and activated carbon are loaded in the fabric sack of big nonwoven (the about 400ml of volume), this sack is loaded in the polyethylene bottle; Then on the universal stage of ball mill, make its rotation with the condition of 10rpm.Measure pH, COD, total nitrogen and the total phosphorus concentration of this moment.Through the result who analyzes after the specified time, with coming to the same thing of table 14, COD becomes approximately 1/5 after 30 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/100.In addition, the tertiary iron phosphate that generates of the reaction through iron and activated carbon does not ooze out in large quantities.
(instance 2)
Fecaluria 150mL is loaded in 2 liters the polyethylene bottle.Iron powder use straight iron powder (reduced iron powder, JFE Steel makes, particle diameter: below the 250 μ m, purity: 5.2g 90 quality % above (remainder is a unavoidable impurities)).PW-D 1.6g (experiment 40) and 2.4g (experiment 41) that activated carbon uses Kuraray chemistry (share) to make.
The interpolation rate with respect to fecaluria of iron powder and activated carbon is 4.5 quality % in experiment 40, in experiment 41, is 5.1 quality %.Additive is disperseed in polyethylene bottle, then on the ball mill universal stage, make its rotation with the condition of 10rpm.The variation of pH, COD, total nitrogen and total phosphorus concentration at this moment is shown in table 15.
After 30 minutes, it is about 1/10 that COD becomes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/8～1/16.After 60 minutes, it is about 1/13～1/20 that COD becomes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/100.The distinctive color of fecaluria disappeared after 5 minutes, was thereafter colourless, transparent.Smell is thin out gradually.
[table 15]
Table 15
Fecaluria under the top condition is handled (experiment 40 and test 41)
(activated carbon: 1.6g (experiment 40), 2.4g (experiment 41), straight iron powder: 5.2g, 10rpm, sack uses: do not have)
(instance 3)
The reactive tank (jar) that fecaluria 150mL is loaded to the fruit juice stirrer (500mL) in.Iron powder use straight iron powder (reduced iron powder, JFE Steel makes, particle diameter: below the 250 μ m, purity: 5.2g 90 quality % above (remainder is a unavoidable impurities)).The PW-D 0.8g (experiment 42) that activated carbon uses Kuraray chemistry (share) to make.
The interpolation rate of iron powder and activated carbon is 4 quality %.Additive is disperseed in jar, under the condition of about 13000rpm, make the rotating paddle rotation in the jar then.The variation of pH, COD, total nitrogen and total phosphorus concentration at this moment is shown in table 16.After 5 minutes, it is about 1/5 that COD becomes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/4.If carry out handling in 10 minutes, then COD becomes approximately 1/5, and it is about 1/4 that total nitrogen becomes, and total phosphorus becomes about 1/100.If carry out handling in 15 minutes, then COD becomes approximately 1/8, and it is about 1/4 that total nitrogen becomes, and total phosphorus becomes about 1/700.The distinctive color of fecaluria disappeared after 5 minutes, was thereafter colourless, transparent.Smell is thin out gradually.
[table 16]
Table 16
Fecaluria under the high-speed stirring is handled (experiment 42)
(activated carbon: 0.8g, straight iron powder: 5.2g, 10rpm, sack uses: do not have, the interpolation rate is 4 quality %)
(instance 4)
Fecaluria, activated carbon and iron powder are loaded to fruit juice stirrer (tank volume: mix stirring 500mL).Fecaluria 150mL is loaded in the jar of fruit juice stirrer.Iron material use straight iron powder (reduced iron powder, JFE Steel makes, particle diameter: below the 250 μ m, purity: 5.2g 90 quality % above (remainder is a unavoidable impurities)).PW-D 1.6g (experiment 43) and 2.4g (experiment 44) that activated carbon uses Kuraray chemistry (share) to make.
The interpolation rate of activated carbon and iron powder is 4.5 quality % in experiment 43, in experiment 44, is 5.1 quality %.Additive is disperseed in jar, under the condition of about 13000rpm, make the rotating paddle rotation in the jar then.The variation of pH, COD, total nitrogen and total phosphorus concentration at this moment is shown in table 17.
[table 17]
Table 17
Fecaluria under the high-speed stirring is handled (experiment 43 and test 44)
(activated carbon: 1.6g and 2.4g, straight iron powder: 5.2g, 10rpm, sack uses: do not have, the interpolation rate is 4.5 quality % and 5.1 quality %)
In experiment 43, COD becomes approximately 1/10 after 5 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/8.COD becomes approximately 1/13 after 10 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/100.In the many experiments 44 of activated carbon amount, COD becomes approximately 1/12 after 5 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/15.COD becomes approximately 1/20 after 10 minutes, and it is about 1/3 that total nitrogen becomes, and total phosphorus becomes about 1/100.The distinctive color of fecaluria disappeared after 5 minutes, was thereafter colourless, transparent.Smell is thin out gradually.
Shown in table 17, can know that it is remarkable that the reduction of the value of the COD of fecaluria, total nitrogen and total phosphorus becomes through increasing the activated carbon amount.
Know according to above, in the quick removal method of phosphorus, COD, nitrogen, color and the foul smell in the fecaluria of the present invention of instance 1～instance 4, all remove phosphorus, nitrogen, color and foul smell in the fecaluria apace, and then COD reduces also.
[utilizability on the industry]
The quick removal method of the application of the invention can be carried out the removal of phosphorus, COD, nitrogen, color and foul smell etc. in the fecaluria effectively, therefore keeping of environment is made huge contribution.
Claims (according to the modification of the 19th of treaty)
1. the phosphorus in fecaluria or the fecaluria waste water and the removal method of nitrogen is characterized in that: in fecaluria or fecaluria waste water, supply with powdered activated carbon and straight iron powder, and stir and it is flowed.
2. the phosphorus in fecaluria according to claim 1 or the fecaluria waste water and the removal method of nitrogen is characterized in that: said powdered activated carbon is any shape in Powdered, granular or the wire, and specific surface area is 300m
2More than/the g, one in diameter or the long limit is below the 2mm.
3. the phosphorus in fecaluria according to claim 1 and 2 or the fecaluria waste water and the removal method of nitrogen is characterized in that: said straight iron powder is a reduced iron powder, and its equivalent circle diameter is below the 1mm.
4. according to the removal method of phosphorus in each described fecaluria or the fecaluria waste water in the claim 1 to 3 and nitrogen, it is characterized in that: said straight iron powder is 1/2～1/15 with respect to the ratio of the quality of said powdered activated carbon.
According to the phosphorus in each described fecaluria or the fecaluria waste water in the claim 1 to 4 and nitrogen, the removal method, it is characterized in that: the said powdered activated carbon in said fecaluria or the fecaluria waste water and the ratio of said straight iron powder are 1 quality %～20 quality %.
6. according to the removal method of phosphorus in each described fecaluria or the fecaluria waste water in the claim 1 to 5 and nitrogen, it is characterized in that: said powdered activated carbon and said straight iron powder are accommodated in the container with water-permeable supply with.
7. removal device, it is the device that the phosphorus in fecaluria and the fecaluria waste water and nitrogen are removed, and it is characterized in that, comprising: the agitating unit of the feed unit of reactive tank, powdered activated carbon, the feed unit of straight iron powder, this fecaluria and fecaluria waste water.
8. removal device according to claim 7 is characterized in that, comprising: the recovery mouth of tertiary iron phosphate that sinks down into the bottom of said device.
9. according to claim 7 or 8 described removal devices, it is characterized in that: the feed unit of said powdered activated carbon and said straight iron powder is accommodated in said powdered activated carbon and said straight iron powder in the container with water-permeable and supplies with.
Claims (13)
1. the quick removal method of phosphorus, COD, nitrogen, color and the foul smell in fecaluria or the fecaluria waste water is characterized in that: in fecaluria or fecaluria waste water, supply with powdered activated carbon and iron powder, and stir and it is flowed.
2. the quick removal method of phosphorus, COD, nitrogen, color and the foul smell in fecaluria according to claim 1 or the fecaluria waste water is characterized in that: said powdered activated carbon is any shape in Powdered, granular or the wire, and specific surface area is 300m
2More than/the g, one in diameter or the long limit is below the 2mm.
3. the quick removal method of phosphorus, COD, nitrogen, color and the foul smell in fecaluria according to claim 1 and 2 or the fecaluria waste water is characterized in that: said iron powder is a reduced iron powder, and its equivalent circle diameter is below the 1mm.
4. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in each described fecaluria or the fecaluria waste water in the claim 1 to 3, it is characterized in that: said iron powder is 1/2～1/15 with respect to the ratio of the quality of said powdered activated carbon.
5. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in each described fecaluria or the fecaluria waste water in the claim 1 to 4, it is characterized in that: the said powdered activated carbon in said fecaluria or the fecaluria waste water and the ratio of said iron powder are 1 quality %～20 quality %.
6. according to the quick removal method of phosphorus, COD, nitrogen, color and foul smell in each described fecaluria or the fecaluria waste water in the claim 1 to 5, it is characterized in that: said powdered activated carbon and said iron powder are accommodated in the container with water-permeable supply with.
7. removal device; It is the device that the phosphorus in fecaluria and the fecaluria waste water, COD, nitrogen, color and foul smell are removed; It is characterized in that, comprising: the agitating unit of the feed unit of reactive tank, powdered activated carbon, the feed unit of iron powder, this fecaluria and fecaluria waste water.
8. removal device according to claim 7 is characterized in that, comprising: the recovery mouth of tertiary iron phosphate that sinks down into the bottom of said device.
9. according to claim 7 or 8 described removal devices, it is characterized in that: the feed unit of said powdered activated carbon and said iron powder is accommodated in said powdered activated carbon and said iron powder in the container with water-permeable and supplies with.
10. according to each described removal device in the claim 7 to 9, it is characterized in that: said agitating unit is an agitating vane, and the rotating speed of said agitating vane is made as more than the 0.5rpm.
11. according to each described removal device in the claim 7 to 9, it is characterized in that: said agitating unit is the rotation of said reactive tank, and the SFM of said reactive tank is made as more than the 0.5rpm.
12. removal device according to claim 10 is characterized in that: said container with water flowing property is hung down to fecaluria or fecaluria waste water from said reactive tank top.
13. according to claim 10 or 11 described removal devices, it is characterized in that: said container with water flowing property is fixed in the said reactive tank.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2009/068634 WO2011048705A1 (en) | 2009-10-23 | 2009-10-23 | Method of rapidly removing phosphorus, cod substance, nitrogen, color, and odor from excreta or excretal wastewater and removal device using the method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102791635A true CN102791635A (en) | 2012-11-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980163089.0A Pending CN102791635A (en) | 2009-10-23 | 2009-10-23 | Method of rapidly removing phosphorus, COD substance, nitrogen, color, and odor from excreta or excretal wastewater and removal device using the method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2011048705A1 (en) |
| CN (1) | CN102791635A (en) |
| WO (1) | WO2011048705A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6139315B2 (en) * | 2013-07-23 | 2017-05-31 | 株式会社東芝 | Phosphorus recovery equipment |
| JP7005067B2 (en) * | 2021-07-21 | 2022-01-21 | 有限会社エコルネサンス・エンテック | Pollution control method using activated carbon |
| CN116395728B (en) * | 2023-03-24 | 2024-02-13 | 中国矿业大学 | Preparation method of fly ash-based hydrotalcite-like compound, and product and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08294683A (en) * | 1995-04-26 | 1996-11-12 | Takayasu Ookubo | Water deodorizing and purifying agent |
| JPH08323343A (en) * | 1995-05-30 | 1996-12-10 | Iwasaki Electric Co Ltd | Adsorption treating material and adsorptive treating device using the same |
| JP2004174407A (en) * | 2002-11-28 | 2004-06-24 | Toshihiro Okita | Inorganic sludge modifying/flocculating/purifying agent |
| JP2005074363A (en) * | 2003-09-02 | 2005-03-24 | Miura Co Ltd | Water treatment agent and water treatment method |
| JP2005103518A (en) * | 2003-10-02 | 2005-04-21 | Air Water Inc | Heavy metal wastewater treatment system and heavy metal wastewater treatment method |
| CN1668535A (en) * | 2002-07-12 | 2005-09-14 | 修复产品公司 | Compositions for removing hydrocarbons and halogenated hydrocarbons from contaminated environments |
| CN2729054Y (en) * | 2004-02-20 | 2005-09-28 | 北京恩菲环保股份有限公司 | Telescopic variable current whirl combined reactor |
| JP2006015256A (en) * | 2004-07-01 | 2006-01-19 | Masashi Yoshioka | Water clarification method utilizing charcoal particle |
| JP2006110518A (en) * | 2004-10-18 | 2006-04-27 | Taiheiyo Cement Corp | Method for highly treating waste water |
| JP2007105557A (en) * | 2005-09-15 | 2007-04-26 | Aichi Steel Works Ltd | Organic matter decomposition material, and method for decomposing organic matter-containing material to be decomposed by using the same |
| JP2008067728A (en) * | 2006-09-12 | 2008-03-27 | Niigata Shiki Kogyo Kk | Simplified urine purifying apparatus |
| CN201264920Y (en) * | 2008-08-04 | 2009-07-01 | 清华大学 | Apparatus for removing noxious ion in ground water by means of powder sorbent |
| CN201321400Y (en) * | 2008-12-29 | 2009-10-07 | 芜湖凯奥尔环保科技有限公司 | Novel sewage treatment device |
| CN101560001A (en) * | 2009-05-22 | 2009-10-21 | 上海润德环境工程有限公司 | Integrated nitrogen and phosphorus recovery device with low energy consumption |
-
2009
- 2009-10-23 JP JP2011537082A patent/JPWO2011048705A1/en active Pending
- 2009-10-23 CN CN200980163089.0A patent/CN102791635A/en active Pending
- 2009-10-23 WO PCT/JP2009/068634 patent/WO2011048705A1/en active Application Filing
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08294683A (en) * | 1995-04-26 | 1996-11-12 | Takayasu Ookubo | Water deodorizing and purifying agent |
| JPH08323343A (en) * | 1995-05-30 | 1996-12-10 | Iwasaki Electric Co Ltd | Adsorption treating material and adsorptive treating device using the same |
| CN1668535A (en) * | 2002-07-12 | 2005-09-14 | 修复产品公司 | Compositions for removing hydrocarbons and halogenated hydrocarbons from contaminated environments |
| JP2004174407A (en) * | 2002-11-28 | 2004-06-24 | Toshihiro Okita | Inorganic sludge modifying/flocculating/purifying agent |
| JP2005074363A (en) * | 2003-09-02 | 2005-03-24 | Miura Co Ltd | Water treatment agent and water treatment method |
| JP2005103518A (en) * | 2003-10-02 | 2005-04-21 | Air Water Inc | Heavy metal wastewater treatment system and heavy metal wastewater treatment method |
| CN2729054Y (en) * | 2004-02-20 | 2005-09-28 | 北京恩菲环保股份有限公司 | Telescopic variable current whirl combined reactor |
| JP2006015256A (en) * | 2004-07-01 | 2006-01-19 | Masashi Yoshioka | Water clarification method utilizing charcoal particle |
| JP2006110518A (en) * | 2004-10-18 | 2006-04-27 | Taiheiyo Cement Corp | Method for highly treating waste water |
| JP2007105557A (en) * | 2005-09-15 | 2007-04-26 | Aichi Steel Works Ltd | Organic matter decomposition material, and method for decomposing organic matter-containing material to be decomposed by using the same |
| JP2008067728A (en) * | 2006-09-12 | 2008-03-27 | Niigata Shiki Kogyo Kk | Simplified urine purifying apparatus |
| CN201264920Y (en) * | 2008-08-04 | 2009-07-01 | 清华大学 | Apparatus for removing noxious ion in ground water by means of powder sorbent |
| CN201321400Y (en) * | 2008-12-29 | 2009-10-07 | 芜湖凯奥尔环保科技有限公司 | Novel sewage treatment device |
| CN101560001A (en) * | 2009-05-22 | 2009-10-21 | 上海润德环境工程有限公司 | Integrated nitrogen and phosphorus recovery device with low energy consumption |
Non-Patent Citations (4)
| Title |
|---|
| 唐次来: "Fe0还原黄土高原地下水中NO3-污染的模拟研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑(月刊)》 * |
| 张增强等: "Fe0去除地下水中硝酸盐的条件研究", 《中国农业大学学报》 * |
| 立本英机等: "《活性炭的应用技术—其维持管理及存在问题》", 31 July 2002 * |
| 辛伟中: "《磁种分选理论与实践》", 31 July 1994 * |
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| Publication number | Publication date |
|---|---|
| WO2011048705A1 (en) | 2011-04-28 |
| JPWO2011048705A1 (en) | 2013-03-07 |
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