CN100595166C - Substance for treatment of sewage and waste water, carrier containing the substance and method for preparing the same - Google Patents

Substance for treatment of sewage and waste water, carrier containing the substance and method for preparing the same Download PDF

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Publication number
CN100595166C
CN100595166C CN200610111558A CN200610111558A CN100595166C CN 100595166 C CN100595166 C CN 100595166C CN 200610111558 A CN200610111558 A CN 200610111558A CN 200610111558 A CN200610111558 A CN 200610111558A CN 100595166 C CN100595166 C CN 100595166C
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water
wastewater treatment
biological
carrier
microbe carrier
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CN101058459A (en
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崔龙洙
洪锡垣
李相协
朴钟勋
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Korea Advanced Institute of Science and Technology KAIST
Korea Institute of Science and Technology KIST
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C02F3/308—Biological phosphorus removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

The present invention provides an active material for biological treatment of sewage and waste water, microbic carrier containing the active material and method for preparing the same. As to the mentioned carrier, the must nutriment such as iron, potassium, magnesium, calcium, natrium, manganese, silicon, aluminum etc gushing from the active material is transmitted into the microbic film forming on the carrier surface, which is benefit to improve the activity degree of the microbic group. Thus, it can use the biological method to treat the sewage and waste water. Furthermore, the cations suchas aluminum, calcium, iron, magnesium etc gushing from the active material combine with the phosphate of the treatment water, which reduces the total phosphorus concentration of the ultimate treatmentwater availably. Moreover, the mentioned active material has no two-time pollution problem, except for the loess which is natural material, the other raw materials is cheap themselves because of flexibly using the castoff such as bf slag, water purification field sludge, eggshell, shell etc. The active material is economical in recycle aspects and plays the effect of circumstance affinity especially.

Description

Be used for water and the material of wastewater treatment, the carrier that includes this material and method for making thereof down
Technical field
The present invention relates to be used for biological water and the active substance of wastewater treatment, the microbe carrier that contains this active substance and manufacture method thereof down.More specifically, the present invention relates to include with the waste that can supply with loess and various inorganic substance active substance as raw material at the microbe carrier that is used for biological down water and wastewater treatment, can realize carrying intravital microorganism growth and improve activity degree, can provide thus to be easy to the space that microorganism grows up and the active substance that is used for biological water down and wastewater treatment of condition, contain the microbe carrier and the manufacture method thereof of this active substance.
Background technology
Now, under life, extensively utilize activated sludge process (activated sludge) in water and the wastewater treatment.Active sludge is meant, the general name of used microorganism in the biological processes of following water and waste water processing station, ordinary skill method as above-mentioned activated sludge process, have to remove the standard activity mud technological method of biochemical oxygen demand (BOD) (BOD), the biological height treatment technology method of its change being removed simultaneously denitrification (N) and phosphorus (P) is arranged.
Above-mentioned biological height treatment technology method is roughly divided into swims growth formula technological method and adheres to growth formula technological method.The above-mentioned growth formula technological method that swims is to stir with aeration to make microorganism contact the technological method of handling with following water, above-mentionedly adheres to the technological method that growth formula technological method is to use the carrier that microorganism can adhere to.
In recent years, people carry out on a large scale exploitation in order to be used for the above-mentioned growth formula technological method that adheres to of the above-mentioned growth formula technological method that swims, be enclosed in the microbe carrier of aerator tank, increase by increasing with the long-pending microorganic adhesion amount that makes of the surface in contact of microorganism, its result has the advantage that can shorten the hydraulic residence time.And then therefore the mentioned microorganism carrier also has the advantage that can improve processing efficiency with least cost owing to the large-scale redevelopment that does not have treatment facility just can be packed into.
This microbe carrier generally is divided into as the organic system of polyvinyl chloride, polyethylene, urethane etc. with as the inorganic system of porousness zeolite, granular carbon, pottery etc. according to its material difference.Carrier exploitation in the past constantly develops to the direction that mainly is increase void content, specific surface area and surfaceness for microorganism is adhered to from the teeth outwards in large quantities.As relevant therewith technology, known have a following technology: utilize active carbon powder to form pore together, thereby make the technology that the specific surface area of sponge increases＜with reference to patent documentation 1 〉; Make the technology that specific surface area increases＜at the surface coverage powder body of particulate vector〉with reference to patent documentation 2; Have big specific surface area and fine pore is formed by regulating calcination time and gas release, thus the technology of the ceramic porous property carrier of manufacturing microorganic adhesion excellent performance＜with reference to patent documentation 3〉etc.
Yet when utilizing conventional art that the microorganic adhesion amount is increased, if this adhesion amount surpasses the threshold value of regulation, the amount of the microorganism of freeing from microbe carrier also increases, and therefore has the problem of the water quality management difficulty for the treatment of water.And then, also exist and cause the carrier blocking problem, but also exist in order suitably to keep dissolved oxygen owing to microorganism too much adheres to, aspect aeration, spend the problem of a large amount of power.
On the other hand, for growth and the propagation of microorganism, the constituent of energy and cell is essential.That is, about 80% of microorganism is that to contain water and other various high molecular, and these polymers are formed by a plurality of unit molecules.Therefore, in order to generate microbial cell, must make unit molecule, at this moment, require necessary various nutritive substances, regardless of the concentration of other nutrient substances, shortage that must nutrient substance or unbalanced growth that all can restriction micro-organisms.
The necessary nutritive substance of mentioned microorganism is different separately, and its amount is also different, but as the necessary nutrient substance of cell, is necessary for more amount (10 -4M or more) quantitative nutrient substance (macro-nutrient) and be necessary for a spot of micro-nutrients (micro-nutrient).
Above-mentioned quantitative nutrition have carbon (C), nitrogen (N), oxygen (O), hydrogen (H), phosphorus (P), sulphur (S), potassium (K), magnesium (Mg), and wherein, microbial cell constitutes desired carbon, nitrogen and phosphorus etc. and contains in large quantities in Xia Shui, waste water.Hydrogen is once supplied with from carbon compound; Sulphur is as the necessary material of generation of protein (PROTEIN) or a part of enzyme, with (NH 4) 2SO 4The vitriol form or the amino acid form that contains sulphur be supplied to.Oxygen is by from atmosphere or inject air artificially and supply with.
As the trace element that above-mentioned micro-nutrients the most generally needs, iron (Fe), manganese (Mn), zinc (Zn) etc. are arranged; As trace element essential under specific growth condition, calcium (Ca), sodium (Na), copper (Cu), cobalt (Co), molybdenum (Mo), chlorine (Cl), nickel (Ni), selenium (Se) etc. are arranged.In addition, as being necessary for a spot of trace element aluminium (Al), silicon (Si), boron (B), chromium (Cr) etc. are arranged, these elements need very little to supply with (10 -6M or still less), reach 10 -4M or show toxicity more for a long time.
If above-mentioned nutrient substance is described in detail, then above-mentioned potassium is the necessary nutrient substances of all microorganisms, microorganism must have potassium in the metabolism (particularly protein metabolism) of various enzymes, magnesium is used in the activity of various enzymes owing to having the function that makes rrna, cytolemma and nucleic acid stabilityization.On the other hand, above-mentioned iron is to be present in the important cofactor in Triphosphopyridine nucleotide photoreductase (ferredoxin) and the cytopigment (cytochrome) and mainly to be used in the cellular respiration, and manganese makes the enzyme reaction activation as coenzyme.Above-mentioned calcium mainly has the effect that makes the microorganism wall stabilization, makes the statospore stabilization.Above-mentioned sodium is present in the extracellular liquid in cell less and mainly, be correctly keep osmotic pressure, be essential for the growth of several specified microorganisms.Above-mentioned silicon plays an important role for synthetic thymus nucleic acid (DexyriboNucleic Acid, DNA) and polysaccharase (polymerase) thereof.
Most of such nutrient substance is containing in following water and waste water, but different according to the characteristic of following water and waste water, and the concentration of existence is also different, occurs the shortage phenomenon of the necessary nutrient substance of a part sometimes, during the nutrient substance deficiency, (lag phase can take place lag period; Time till active cell proliferation takes place) unfavorable condition that reduces of elongated, yield.
The special permission of [patent documentation 1] Republic of Korea discloses the 2004-0100224 communique
The special permission of [patent documentation 2] Republic of Korea discloses the 2005-0121494 communique
The special permission of [patent documentation 3] Republic of Korea discloses the 2004-0068824 communique
Summary of the invention
The present invention In view of the foregoing finishes, its purpose is to provide following biological water and the active substance of wastewater treatment, the microbe carrier that contains this active substance and the manufacture method thereof down of being used for: not only realize the increase of microbe carrier microorganic adhesion amount, and can directly supply with the necessary necessary nutrient substance of microorganism, promote the activity degree of removing the direct acting useful attached microbial of performance thus, thereby can greatly improve processing efficiency pollution substance.
Other purposes of the present invention are to provide following biological water and the active substance of wastewater treatment, the microbe carrier that contains this active substance and the manufacture method thereof down of being used for: can gush out from above-mentioned active substance and can reduce the concentration of the phosphorus in the treating water with phosphoric acid salt bonded ion the water, can further improve the processing capacity of water and waste water down.
Other purposes of the present invention are to provide following biological water and the active substance of wastewater treatment, the microbe carrier that contains this active substance and the manufacture method thereof down of being used for: when making above-mentioned active substance, by main recirculation natural materials and waste and also excellent in excellence aspect the environment affinity and economic aspect.
Above-mentioned purpose is used for the active substance of biological down water and wastewater treatment to be finished, and it is characterized in that, contains any one or two kinds or more kinds of and loess in blast-furnace slag, water purification field mud, eggshell or the shell.
The purpose of the invention described above is used for the microbe carrier of biological water down and wastewater treatment to be finished, and it is characterized in that, is contained in the carrier in the above-mentioned active substance.
The purpose of the invention described above is used for the manufacture method of the microbe carrier of biological water down and wastewater treatment and finishes, it is characterized in that, comprise the steps: to provide the step (S1) of any one or two kinds or more kinds of and the loess of blast-furnace slag, water purification field mud, eggshell or shell as the active substance raw material; From above-mentioned active substance raw material, select step (S2) with the separated powder particle; Cooperate above-mentioned powder particle, with water blended step (S4); Said mixture is configured as the step (S5) of desirable shape; Calcine the step (S6) of above-mentioned molding; And make and be contained in the step (S7) of making microbe carrier in the carrier in the above-mentioned sintered compact.
In above-mentioned S1 step, preferably further comprise step (S1-1) with above-mentioned blast-furnace slag and eggshell pulverizing.
In above-mentioned S1 step, preferably further comprise step (S1-2) with above-mentioned water purification field drying sludge.
In above-mentioned S2 step, above-mentioned raw materials is selected and the separated powder particle by 200～250 purpose sieves respectively, particularly more preferably select the powder particle of 425 μ m.
Aforesaid method preferably further comprises carrying out exsiccant step (S3) after the above-mentioned powder particle washing except the mud of above-mentioned water purification field, in above-mentioned drying step, more preferably carried out drying 12 hours under 105 ℃ or the longer time.
In above-mentioned S4 step, when containing above-mentioned loess, blast-furnace slag, water purification field mud and eggshell, preferably reach 40～60%, 15～25%, 15～25% and 5～15% mode respectively with its weight ratio and cooperate, particularly above-mentioned eggshell more preferably cooperates to reach 10% mode.
In above-mentioned S4 step,, preferably mix 5～20% water by weight with respect to the powder particle of above-mentioned cooperation.
In above-mentioned S5 step, preferably when above-mentioned shaping, be configured as and have the spherical of 10～20mm particle diameter.
In above-mentioned S6 step, preferably under 900～1100 ℃, calcine.
In above-mentioned S7 step, a plurality of above-mentioned sintered compacies of preferably packing in the visible object of regulations such as quadrangle or circle cover its outside and to make carrier with filamentary material, and at this moment, above-mentioned filamentary material is non-woven fabrics preferably.
In above-mentioned S7 step, a plurality of above-mentioned sintered compacies of preferably packing in sponge are made carrier.
Description of drawings
[Fig. 1] is the schema of the manufacture method of the expression microbe carrier that includes active substance of the present invention.
[Fig. 2] is the photo by the active material sintered body of one embodiment of the present invention.
[Fig. 3] is the photo of the microbe carrier that includes active substance made with sponge of the air filter of the use polyurethane material of expression by one embodiment of the present invention.
[Fig. 4] is the figure of the mean value of the expression concentration of gushing out of each material of embodiment in the experimental example 1 of the present invention and comparative example being measured the organic substance that obtains for each 3 times.
[Fig. 5] be expression in this experimental example 2 through the time the figure that changes of phosphate concn.
Embodiment
Below, enumerate embodiment and be used for biological down water and the active substance of wastewater treatment, the microbe carrier that contains this active substance and manufacture method thereof are described in detail, but the present invention is not limited to these modes of the present invention.
In the present invention, as microorganism grow up necessary element, except the nitrogen and phosphorus that in down water and waste water, fully contain, reason is in the characteristic of waste water and content deviation is violent, What is more, contain hardly, so in order to supply easy insufficient nutrient substance, by being contained in the microbe carrier in the active substance that allows to the above-mentioned nutrient substance of stripping, make the microorganism that is attached to carrier surface, can directly absorb the nutrient substance of gushing out from this carrier surface, by inducing growth and the activity degree of supplying necessary nutrient substance and can promoting microorganism.Thus, carrier by having improved various aerobic and growth and activity degrees amphimicrobian microorganism (faculative anaerobes), can increase substantially processing efficiency on the basis of the effect of adhering in a large number, growing up of having born microorganism.And then, because the aluminium gushed out, calcium, iron, magnesium plasma and the phosphoric acid salt in the water combine and can further improve the height handling property of time water and waste water.
The used above-mentioned active substance of the present invention is that the loess that mixes following substances and natural materials forms, and described material is one or more kinds that are selected from shell such as blast-furnace slag, water purification field mud and eggshell, shellfish or oyster as waste and other the impartial materials.Like this, owing to use blast-furnace slag, water purification field mud, eggshell, be called as the shell the like waste of shellfish (shell fish) or oyster (oyster) as active substance, use the loess of natural materials, therefore can improve the environment affinity, but also can reduce production costs and satisfy economic requirement.
If describe above-mentioned active substance respectively in detail, it is about 10% that then the loess of above-mentioned natural materials covers the face of land, and as the stores of the particle of the particle diameter 0.002～0.005mm that mainly contains (silt) size that has flour sand, it contains a large amount of lime carbonate (CaCO 3), in addition, also contain silicon-dioxide (SiO 2), aluminum oxide (Al 2O 3), iron, magnesium, sodium, potassium etc. (for example, the constituent of the loess of Korea S what can be different because of the region, it is maximum generally to contain silicon, is 48%, aluminium 35%, iron 11%, magnesium 6% etc.).
Effect through above-mentioned lime carbonate, loess has the destructive of being difficult to viscous force, add the character that entry will become clay as long as have, but in the present invention, as mentioned above, utilization adds the character that entry then can become the loess of clay, makes it possible to will contain as the necessary nutrient substance of microorganism and shell combination efficiently such as blast-furnace slag, water purification field mud and the chorion of the waste of the multiple a large amount of inorganic substance that use, shellfish, oyster.
Above-mentioned blast-furnace slag is to be carried out the waste material of recirculation as cement raw material, concrete with aggregate, building usefulness, silicic acid matter fertilizer etc., produce when in smelting furnace, making the pig iron by iron ore (per 1 ton of pig iron produces 500～1000kg).This is the material of the accumulation of impurities beyond the iron, has following composition usually: silicon-dioxide 30～36%, aluminum oxide 12～18%, ferric oxide (Fe 2O 3) 0.25～0.35%, calcium oxide (CaO) 38～45%, magnesium oxide (MgO) 10.0% or still less, oxysulfide (SO 3) 4.0% or still less.
Above-mentioned water purification field mud, the inorganic substance of clay class are its main components, are not the materials with putrid character difference as the mud of following water, but utilize the mud of the water purification field that the high-rate fitration method obtains.Wherein contain the clay particle and the main aluminium that in the water source, contain at first in a large number as flocculation agent.The chemical constitution of above-mentioned water purification field mud contains that organic content is about 6～30%, silicon-dioxide 30～50%, aluminum oxide 20～35%, ferric oxide 4～6%, as the trace metal of residual portion.Wherein, organism helps to form the space in the calcination process of 800 ℃ or higher temperature.
Compare with following water treatment, because very a small amount of real estate raw sludge in the clean water treatment process, so near the rivers will directly being discharged at most of by product that the water purification field produces in the past, but because the maximization of water purification facilities and the minimizing of rivers flow, such a current drainage is handled and is difficult to, regulation for environment is reinforced in addition, has forbidden directly being discharged to mud in the surface water or abandoning on the soil.Therefore, by the present invention, can handle water purification field mud in a large number and efficiently.
Above-mentioned eggshell, it forms about 93% is lime carbonate, the 5%th, organism, the 1%th, magnesiumcarbonate (MgCO 3), be calcium phosphate (Ca as 1% of residual portion 3(PO 4) 2).Above-mentioned eggshell begins to take place calcination reaction under 650 ℃, finish calcination reaction by the following reaction about 780 ℃.
For shells such as above-mentioned oyster, shellfish, particularly contain the calcium ion of high density, therefore above-mentioned calcium ion preferably uses shells such as above-mentioned oyster, shellfish together because the precipitin reaction of phosphate ion takes place is chemical precipitation agent very efficiently.
Aforesaid active substance, being provided in the growth of microorganism and the breeding desired iron, manganese, calcium, sodium, potassium, magnesium, aluminium, silicon etc. must nutrient substance, moreover, the aluminium of gushing out, calcium, iron, magnesium plasma combine with phosphoric acid salt, the effect of the phosphorus concentration under performance reduces thus in water and the waste water.Below general formula represent that this ion of gushing out combines with phosphoric acid salt and reduces the situation of phosphorus concentration.
[Chemical formula 1]
Al 3++PO 4 3-→Al (PO 4)
[Chemical formula 2]
3Ca 2++2(PO 4 3-)→Ca 3(PO 4) 2
[chemical formula 3]
Fe 3++PO 4 3-→Fe (PO 4)
[chemical formula 4]
3Mg 2++2(PO 4 3-)→Mg 3(PO 4) 2
Below, detailed description includes the manufacturing processed of the microbe carrier of active substance of the present invention.
Fig. 1 is the schema of manufacture method of the microbe carrier of expression one embodiment of the present invention, and Fig. 2 is the photo of sintered compact of the active substance of one embodiment of the present invention.
As shown in Figure 1, in order to make active substance as shown in Figure 2, at first, provide the active substance raw material (S1) of loess, blast-furnace slag, water purification field mud, eggshell, shell.
Wherein, in order to select blast-furnace slag and eggshell, pulverize (S1-1) with designated size.On the other hand, water purification field mud contains aqueous vapor, must carry out the drying step (S1-2) with its removal.
To pass through 200～250 purpose sieves respectively through the raw material that said process is prepared, select, separate the powder particle (S2) of each material thus.
In said process, on the basis of the easiness of the homogenizing of guaranteeing microbiological active material and shaping, preferably select the powder particle about 425 μ m.
Specifically,, then not only in the manufacturing processed of active substance, be not easy to be shaped, and the amount of the feasible nutrient substance of gushing out is also irregular or minimizing if former state is used blast-furnace slag and eggshell or shell.Therefore, each ready material is sieved with mesh sieve, select particle with afore mentioned rules particle diameter.
Above-mentioned powder particle (except water purification field mud) descended dry 12 hours or the longer time (S3) in 105 ℃ after washing.In order to remove impurity and gravimetry accurately, preferably after washing with above-mentioned powder particle in 105 ℃ of dry 12 hours or longer times down.
On the other hand, when containing above-mentioned loess, blast-furnace slag, water purification field mud, eggshell, these materials cooperate in the mode that its weight ratio reaches 40～60%, 15～25%, 15～25% and 5～15% (preferred 10%) respectively, with respect to the material that cooperates, the mode that water preferably reaches 5～20% (preferred 15%) is by weight added and is made viscous mixt (S4).At this moment, during the adding proportion less than 5% of water, then desirable shape, for example the shaping of the active substance of spherical or desirable size is all carried out not smoothly; The adding proportion of water surpasses at 20% o'clock, then before the calcining or the shape of the thing that is difficult to keep in its process to be shaped.
Then, the size that is configured as regulation is spherical (S5) about particle diameter 10～20mm, calcines under 900～1100 ℃ at last (S6).The calcination process beyond all else of active substance of the present invention is important, in this process, and carbon compound perfect combustion, this is in order to remove tar and to evaporate into the non-carbon component that grades, and the cause of the nutrient substance of only residual essential inorganic substance.When calcining temperature is lower than above-mentioned scope, reduce owing to show intensity, labile phenomenon in water, thereby be inefficent.On the other hand, when calcining temperature is higher than above-mentioned scope, cause the amount of the nutrient substance gushed out to reduce sharply because of melting phenomenon.
Then, in order to make carrier, the sintered compact of a plurality of active substances of in the visible object of regulations such as quadrangle or circle, packing into, and it is outside with the filamentary material covering than high porosity of having as non-woven fabrics.
On the other hand, Fig. 3 is the photo that includes the carrier of the active substance that the air filter that uses polyurethane material by one embodiment of the present invention makes with sponge.At this, Fig. 3 a is the photo of expression with the state before the sintered compact of sponge covering active substance, and Fig. 3 b is the photo that covers the sintered compact state afterwards of active substance with sponge.
As shown in Figure 3, can open the space from the surface to inside, the sintered compact of a plurality of active substances of packing in the inside of the sponge with interconnective quadrangle in each space or circular isotactic setting attitude is made carrier (S7).At this, employed air filter is used sponge, because the space of inside and outside interconnects, therefore can convection cell or air-flow mobile bring obstruction, the necessary nutrient substance of the iron of gushing out from active substance of the present invention, potassium, magnesium, calcium, sodium, manganese, silicon, aluminium etc. passes on the microbial film that is formed at carrier surface, and is very suitable for the activity degree that improves microflora.
Above-mentioned sponge has proper intensity, makes not produce corrosion or the distortion that causes because of the aeration intensity of water and waste water down, because the space interconnects, so can provide the microorganism needed enough surface-area of fixing, grow up.And then, when particularly its thickness is 3～5cm left and right sides, because in the outside and inner concentration difference that produces dissolved oxygen of carrier, therefore spatially forming the outside is oxygen free condition for aerobic inside, because interval different dominant microbe species are also different, therefore induce the oxidation of ammonium-nitrogen in the outside of carrier, induce the denitrogenationization of nitrogen oxygen nitrogen in inside, obtain in a reactive tank, removing the effect of denitrification.
[embodiment]
Outburst amount determination experiment-the experimental example 1 of＜inorganic substance 〉
In this experiment, measure the amount of the inorganic substance of gushing out from active substance.At first, select loess, blast-furnace slag, water purification mud and eggshell active substance as embodiment.By weight, its proportioning is made as 50%, 20%, 20%, 10% respectively,, mixes 15% water by weight and make molding about particle diameter 10mm, under 950 ℃, calcine at last with respect to the material that cooperates.On the other hand, as a comparative example, only use loess, use the method identical to make and calcine, make size also identical with shape with embodiment.
In order to measure the representational concentration of gushing out from the various materials of the foregoing description and comparative example that must nutrient substance, be the concentration of iron, potassium, magnesium, calcium, sodium, manganese, silicon, aluminium etc., with each a kind of putting into after the Erlenmeyer flask of each material of the foregoing description and comparative example, inject the distilled water of 200mL.Above-mentioned Erlenmeyer flask is prepared 3 respectively, is amounted to 6.These materials were stirred 24 hours down at 25 ℃, after the filtering supernatant, iron, potassium, magnesium, calcium, sodium, manganese, silicon, the aluminium isoconcentration of gushing out carried out inductively coupled plasma (Inductively Coupled Plasma; ICP) assay determination.Used machine is the Optima 2000DV of Po Jin-Ai Ermo instrument (Perkin Elmer Instruments) corporate system.
Fig. 4 is the concentration of gushing out of 3 inorganic substance is measured in expression respectively to the material of embodiment and comparative example in the embodiments of the invention 1 the figure of mean value.
As shown in Figure 4, can confirm to compare from the material that contains the active substance that constitutes by loess, blast-furnace slag, water purification mud and eggshell, gush out 2 times at least, 4 times or more each element at most with the material that only contains loess.
These each elements are the main effect of performance when the biological treating processes of down water and waste water, not only owing to the growth that is easy to supply with microorganism improves activity degree, and improves biomembranous formation owing to the external microbial at carrier adheres to efficiently.
＜phosphorus is removed efficient experiment-experimental example 2 〉
Comparative evaluation phosphorus is removed efficient in this experiment.
Experimental technique is: make phosphoric acid salt (PO 4 3--P) concentration is the solution of 25mg/L, in Erlenmeyer flask, add with in above-mentioned experimental example 1 the identical embodiment of the material that uses and the material of comparative example, speed with 200rpm stirred 72 hours on one side, filtering through taking out supernatant liquor after the specified time on one side, (Ion chromatography) analyzes phosphatic residual concentration with ion chromatography.
Fig. 5 be expression in this experimental example 2 through the time the figure that changes of phosphate concn.
As shown in Figure 5, the material of embodiment demonstrates the trend that experiment beginning back phosphate concn reduces constantly.The phosphatic concentration of 72 hours post analysis is shown 3.28mg/L, and measuring it, to remove efficient be 86.9%.This is the cause that reduces concentration from the active substance of the material of embodiment because divalent such as the aluminium of gushing out, calcium, iron, magnesium or 3 valency cationic substances combine with phosphoric acid salt in the water.
On the other hand, only ochreous comparative example also demonstrates the trend that phosphate concn reduces, but compares with embodiment, and its degree is faint.That is, during for the simple loess of comparative example, the phosphate concn of 72 hours post analysis is shown 15.6mg/L, and measuring it, to remove efficient be 37.6%, and this is to compare with the active substance of embodiment to reduce about numerical value of about 50%.
In a word, can obtain as drawing a conclusion: though also contain in the loess as aluminium, calcium, iron, magnesium etc. can with phosphoric acid salt bonded positively charged ion, compare with active substance of the present invention, the amount of gushing out is few, it is not high that it removes efficient.Therefore, can confirm that active substance of the present invention and the carrier that includes it are very effective for the phosphoric acid salt of removing in the treating water.
＜processing efficiency determination experiment-embodiment 3 〉
In this experiment, measure the processing efficiency of the carrier that contains active substance of the present invention.
For this reason, the interconnective air filter in space that is formed in the inside and outside is with the carrier that contains the active substance identical with used material in above-mentioned these experimental examples in the sponge.Reactor (" R-2 ") that is incorporated with the carrier that includes above-mentioned active substance and the reactor (" R-1 ") that sponge carrier only is housed are worked under the same conditions.It is the cylindric of 250mm, the high 550mm of being that above-mentioned reactor has diameter, and by the acryhic material manufacturing, total useful volume is about 13L.On the other hand, hydraulic residence time (HRT) and solid matter residence time (SRT) were made as respectively 6 hours and 25 days in this experiment, and such working conditions is all equally suitable for each reactive tank.The bottom of reactor is made as anaerobism/oxygen-free atmosphere condition, and the useful volume of this part reaches the about 35% of the total useful volume of reactive tank, keeps aerobic condition while top utilizes pneumatic pump to inject air, and this part accounts for 65% of the total useful volume of reactive tank.On the other hand, except biological reaction tank, settling bath is set induces after the solid-liquid separation of mud, treating water is discharged.At this moment, utilization carrying pump makes the mud that has carried out solid-liquid separation flow into anaerobism/anaerobic part of biological reaction tank lower end from the bottom of settling bath, and carrying rate and inflow water ratio reach 100%.
Table 1～3 are represented respectively: be respectively charged among the embodiment 3 that works in the reactive tank after about 150 days at sponge carrier the active substance implicit typing carrier of the foregoing description and comparative example, analyze wherein inflow water and the result of the water quality gained of the treating water of each reactor.
[table 1]
Figure C20061011155800151
[table 2]
Figure C20061011155800152
[table 3]
By table 1～3 as can be known, be incorporated with the water quality for the treatment of water of the R-2 reactor of the sponge carrier that includes active substance of the present invention, compare with the water quality of the treating water of the R-1 reactor that is incorporated with sponge carrier separately, in all water quality analysis projects, demonstrate the efficient of removing of raising.
That is, if be benchmark with the concentration of the pollution substance in the treating water, then the concentration of the solid matter of R-1 treating water (SS) is about 100%, and the concentration of dissolved organic matter matter (Soluble COD) is about 50%, ammonium-nitrogen (NH 3-N) concentration is about 50%, and the concentration of total nitrogen (TN) is about about 25%, and analytical results is than R-2 treating water height.
The cause of the raising of such processing efficiency is, owing to the active substance that includes in sponge carrier improves the activity degree of all microfloras to the necessary nutrient substance of the microorganism supply trace relevant with removing pollution substance constantly.
On the other hand, if see the situation of total phosphorus (TP), the efficient of removing that shows with respect to the R-2 treating water is 89.4%, and the R-1 treating water demonstrates 52.2% low-down value.This is and the resulting similar numerical value of efficient of removing of conventional actived sludge, and described conventional actived sludge is to utilize generally as the biological height treatment process of phosphorus and inapplicable emitting and excess ingestion mechanism.
In addition, if be that benchmark is observed with the TP concentration in the treating water as can be known, the analytical results of R-2 treating water is average 0.58mg/L, compares with the 2.62mg/L of R-1 treating water, is handled very efficiently.This is because positively charged ions such as the aluminium of gushing out constantly from active substance, calcium, iron, magnesium combine with phosphoric acid salt and precipitate, the final cause that is removed with the abolishment of excess sludge.
Like this, can positively confirm: active substance of the present invention and contain its carrier, in the treating processes of following water and waste water, not only improve the efficient of removing of pollution substance by direct raising microbic activity degree, and as mentioned above, by positively charged ion and phosphatic Chemical bond and increase the efficient of removing of total phosphorus epoch-makingly.
Include the carrier of active substance of the present invention, the iron of gushing out from active substance, potassium, magnesium, calcium, sodium, manganese, silicon, aluminium etc. must pass on the microbial film that is formed at carrier surface by nutrient substance, are very effective for the activity degree that improves microflora.Therefore, can handle down water and waste water efficiently with biological method.
And then positively charged ions such as the aluminium of gushing out from active substance of the present invention, calcium, iron, magnesium can make the total phosphorus concentration of final treating water reduce effectively owing to combine with phosphoric acid salt in the treating water.
In addition, active substance of the present invention does not have 2 pollution problems, except the loess of natural materials, by applying flexibly the waste as shells such as blast-furnace slag, water purification field mud, eggshell, shellfish or oyster, can bring into play following effect: starting material self are cheap and also very economical aspect recirculation, and are particularly affine with environment.

Claims (14)

1, is used for the active substance of biological down water and wastewater treatment, it is characterized in that, contain any one or two kinds or more kinds of and loess in blast-furnace slag, water purification field mud, eggshell or the shell.
2, be used for the microbe carrier of biological down water and wastewater treatment, it is characterized in that, contain in the active substance of any one or two kinds in blast-furnace slag, water purification field mud, eggshell or the shell or more kinds of and loess and be contained in the carrier.
3, the making method that is used for the microbe carrier of biological water down and wastewater treatment, it is characterized in that, comprise the steps: to provide any one or two kinds in blast-furnace slag, water purification field mud, eggshell or the shell as the active substance raw material or the step S1 of more kinds of and loess; Step S1-1 with described blast-furnace slag and eggshell pulverizing; Step S1-2 with described water purification field drying sludge; From described active substance raw material, select step S2 with the separated powder particle; Cooperate described powder particle, mix with water and make the step S4 of mixture; Described mixture is configured as desirable shape and manufactures the step S5 of body; Calcine described molding and make the step S6 of sintered compact; And make and be contained in the step S7 that makes microbe carrier in the carrier in the described sintered compact.
4, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3 is characterized in that, in described S2 step, selects the powder particle of 425 μ m.
5, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3, it is characterized in that described method further comprises and will carry out exsiccant step S3 after the described powder particle washing except the mud of described water purification field.
6, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 5 is characterized in that, in described drying step, carries out drying 12 hours under 105 ℃ or the longer time.
7, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3, it is characterized in that, in described S4 step, when containing described loess, blast-furnace slag, water purification field mud and eggshell, 40～60%, 15～25%, 15～25% and 5～15% the mode of reaching respectively with its weight ratio cooperates.
8, the making method that is used for the microbe carrier of biological down water and wastewater treatment according to claim 7 is characterized in that, described eggshell cooperates to reach 10% mode.
9, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3 is characterized in that, in described S4 step, with respect to the powder particle of described cooperation, mixes 5～20% water by weight.
10, the making method that is used for the microbe carrier of biological down water and wastewater treatment according to claim 3 is characterized in that, in described S5 step, is configured as when described shaping and has the spherical of 10～20mm particle diameter.
11, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3 is characterized in that, in described S6 step, calcines under 900～1100 ℃.
12, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3, it is characterized in that, in described S7 step, a plurality of described sintered compacies of packing in the visible object of regulation, the outside of the visible object of the sintered compact of will having packed into covers with filamentary material and makes microbe carrier.
13, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 12 is characterized in that described filamentary material is a non-woven fabrics.
14, the making method that is used for the microbe carrier of biological water down and wastewater treatment according to claim 3, it is characterized in that, in described S7 step, the microbe carrier that a plurality of described sintered compact manufacturings of packing in sponge include described sintered compact.
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