CN103347824A - Anaerobic processing method and device - Google Patents

Anaerobic processing method and device Download PDF

Info

Publication number
CN103347824A
CN103347824A CN2011800596438A CN201180059643A CN103347824A CN 103347824 A CN103347824 A CN 103347824A CN 2011800596438 A CN2011800596438 A CN 2011800596438A CN 201180059643 A CN201180059643 A CN 201180059643A CN 103347824 A CN103347824 A CN 103347824A
Authority
CN
China
Prior art keywords
mud
anaerobism
sludge
digested sludge
flocculation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800596438A
Other languages
Chinese (zh)
Other versions
CN103347824B (en
Inventor
片冈直明
萩野隆生
西胁正人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swing Corp
Original Assignee
Swing Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swing Corp filed Critical Swing Corp
Publication of CN103347824A publication Critical patent/CN103347824A/en
Application granted granted Critical
Publication of CN103347824B publication Critical patent/CN103347824B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/02—Biological treatment
    • C02F11/04—Anaerobic treatment; Production of methane by such processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Treatment Of Sludge (AREA)
  • Processing Of Solid Wastes (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The purpose of the present invention is to provide an anaerobic processing method and a device, whereby: an anaerobic digestion device can be made more compact; the generation of phosphorous, siloxane, and other precipitates is reduced; sludge generated at wastewater processing facilities, etc., is stably and efficiently anaerobically digested; biogas (especially methane gas) can be efficiently recovered; digested sludge can be efficiently dewatered; and cost is reduced. Provided is an anaerobic processing method that includes: a preprocessing step that solid/liquid separates a coagulated sludge, which is prepared by adding a coagulant to sludge, into a sludge concentrate with a sludge concentration of 4-12% and a separated liquid; an anaerobic digestion step that anaerobically digests the sludge concentrate and also recovers biogas; a step for preparing a digested sludge coagulant by mixing a coagulant and at least one of either the separated liquid and water, with the anaerobically digested sludge prepared in the anaerobic digestion step; and a step for dewatering a digested sludge concentrate obtained by solid/liquid separating the digested sludge coagulant. Also provided is a device for implementing said processing method.

Description

Anaerobism treatment process and device
Technical field
The present invention relates to anaerobism treatment process and the device of mud.
Background technology
Compare with the aerobism processing, the mud generation of the anaerobism digestion process of mud is few, pathogenic micro-organism, parasitic ovum can promptly be killed and stabilization, do not need the supply of oxygen, power consumption is few, can obtain with the methane gas is the biogas of principal constituent, therefore is the technology of just using as energy-conservation treatment process since ancient times.On the other hand, anaerobism digestive shelf equipment must be big capacity, and chemical is costly in the processing of digested sludge, and mud is difficult dehydration property, and the dewatered sludge water ratio is not easy to reduce, and also is the more technology of problem therefore.
Therefore, as existing method for sludge treatment, not with sludge anaerobic digestion, but or dehydration back landfill, or the example of dehydration back burning disposal is also a lot.For example, handle as the anaerobism of existing mud, can list the processing shown in the feel flow draw of block shown in Fig. 6.This flow process below is described.
Mud 1 is transported in the storage facility 2, then, mud 1 is transported in the equipment for separating liquid from solid 6, solid-liquid separation is mud enriched material 7 and parting liquid 8, mud enriched material 7 is transported in the anaerobism slaking apparatus 9, anaerobism digestion by mud, generate biogas 10 and anaerobism digested sludge 11, biogas 10 is transported in the biological gas tank 101, then, biogas 10 is transported to gas and for example utilizes equipment 102(, gas turbine, biogas boiler, gaslight, drying machine thermal source etc.) or residual gas combustion unit 103 in.Anaerobism digested sludge 11 is transported in the digested sludge throw out preparation facilities 12, when isolating parting liquid 14, preparation digested sludge throw out 15, digested sludge throw out 15 is transported in the dewatering unit 16, prepares dewatered cake 18 when isolating parting liquid 17.Parting liquid 8, parting liquid 14 and parting liquid 17 are transported in sewage treatment equipment 104 etc.In digested sludge throw out preparation facilities 12, add flocculation agent mostly.
On the other hand, the treatment process of a kind of fecaluria, food waste, mud has been proposed in the patent documentation 1, by this treatment process, with mud, fecalurias such as the mud of organic wastewater treatment facility, purification tank mud, contain the food waste energy-efficient treatment of plant and animal residue, simultaneously, non-wholesomeness screening reject wholesomeness composting or Solid fuelization with in fecaluria, the purification tank mud the treating method comprises following operation: the pretreatment process that (a) will mix the fecaluria solid-liquid separation of mud; (b) solid substance that separates in the treatment process is not dewatered and the anaerobism digestion operation of direct anaerobism digestion; (c) will contain the anaerobism digestion operation of the food waste anaerobism digestion of plant and animal residue and solid substance; (d) anaerobism being digested the dehydration of operation effluent liquid is separated into solid substance and divides dried up dehydration procedure; (e) branch of pretreatment process is dried up, the separation water biology oxidation from dehydration procedure, the biologic treatment process of denitrogenation.
A kind of method for sludge treatment and system thereof have been proposed in the patent documentation 2, by this treatment process, primary sludge and two kinds of mud of excess sludge concentration in a system that will be produced by wastewater treatment, concentrate by follow-up dehydration procedure simultaneously, be maintained until the suitableeest sludge concentration, thereby bring into play concentrating of these wastewater sludges to greatest extent, the total efficiency of dewatering process, the treating method comprises: the excess sludge that the primary sludge that will be produced by the initial settling tank of sewage treatment equipment and final tank produce mixes, store, in this mixing sludge, add flocculation agent, carry out flocculation treatment one time, then, the mixing sludge concentration of a flocculation treatment will have been finished, make its sludge concentration reach 6～8%, then, add flocculation agent in the mixing sludge after concentration, carry out the secondary flocculation treatment, further the mixing sludge that has carried out the secondary flocculation treatment is implemented processed.
In addition, in the patent documentation 3, propose a kind of transport capacity that improves equipment for separating liquid from solid, and increased the slit type thickner of extruding squeezing effect.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 10-216785 communique
Patent documentation 2: TOHKEMY 2007-264758 communique
Patent documentation 3: TOHKEMY 2003-211293 communique
Summary of the invention
The problem that invention will solve
In the anaerobism digestion process of the mud that produces in the sewage treatment equipment etc., usually because the HRT(hydraulic detention time: be 20～30 days Hydraulic retention time), therefore, needing jumbo anaerobism digestive shelf is maximum problem.For example, at mud TS(Total Solids) concentration 3wt%, treatment capacity 100m 3In the sludge treatment in/sky, need the common 2000～3000m of design 3Large-scale anaerobism digestive shelf.In addition, in digested sludge is handled, have the mud flocculation, the required chemical expense of processed increases, and mud becomes difficult dehydration property, moisture percentage in sewage sludge also is not easy the problem that reduces.This be because, in the digestion of the anaerobism of mud, because protein is decomposed, generate ammonia-state nitrogen, it is about 3 that M basicity (reaching the acid consumption of pH4.8) also is increased to, 000mg CaCO 3More than/the L, departed from the slightly acidic zone of the optimal pH condition that is considered to the mud flocculation.In addition, the problem of existence is, because sludge digestion, the thick seston (fibre composition) in the mud is decomposed together, and therefore, the thick seston content of the dehydration when going far towards sludge dewatering descends, and the dewatered cake water ratio increases.In addition, also there is the problem that precipitates such as phosphorus, calcium take place in anaerobism digestive shelf, the pipe arrangement etc.In addition, the silicon that contains in the draining normally is derived from the form of the siloxanes of the silicon compounds such as silicone oil that contain in shampoo, hair conditioner, the makeup etc.Siloxanes refers to that main framing is the organic compound with silicon-oxygen key that alkyl is arranged on Si-O-, the side chain.As siloxanes, for example can list Siliciumatom and be 2～6, alkyl is wire or the annular siloxane of methyl etc.Because the solubleness of siloxanes in water is low, when the sewage sludge anaerobism is digested, distribute and move in the biogas, therefore, when generating utilizes biogas, in generating sets such as gas engine, peripherals, form dirt and separate out, known have manyly cause that generating efficiency reduces, maintenance of the equipment produces dysgenic example, it prevents that countermeasure from becoming important.
The present invention makes in view of the above problems, its objective is provides a kind of anaerobism treatment process and device of realizing cost degradation, it makes the miniaturization of anaerobism slaking apparatus, and the generation of the precipitate that comprises phosphorus, calcium, siloxanes (silicon compound with siloxane bond) etc. is reduced, stable and the anaerobism digestion effectively with middle mud that produces such as sewage treatment equipments, and can reclaim biogas (especially methane gas) effectively, and can effectively digested sludge be dewatered.
For the scheme of dealing with problems
According to the present invention, provide following anaerobism treatment process and anaerobism treatment unit.
1) a kind of anaerobism treatment process, it comprises: the flocculation mud solid-liquid separation that interpolation flocculation agent in mud is prepared is the mud enriched material of sludge concentration 4～12wt% and the pretreatment process of parting liquid; Anaerobism digestion operation with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism digestion operation and flocculation agent and be selected from described parting liquid and the water any mixes at least, prepare the operation of digested sludge throw out; And the operation that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
2) a kind of anaerobism treatment unit, it comprises: add flocculation agent and prepare the flocculation groove of the mud that flocculates in mud; With mud enriched material and the parting liquid that this flocculation mud solid-liquid separation is sludge concentration 4～12wt%, prepare the pre-treatment sludge concentration device of mud enriched material; Anaerobism slaking apparatus with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism slaking apparatus and flocculation agent and be selected from described parting liquid and water any mixes and prepares the digested sludge flocculation plant of digested sludge throw out at least; And the dewatering unit that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
In treatment process of the present invention, solid-liquid separation in pretreatment process and the mud enriched material for preparing contain 4～12wt%, be the mud of the high density more than 1.5～2 times of existing method.For with this mud enriched material anaerobism digestion process, anaerobism digested sludge of the present invention has M basicity and the ammonia concentration higher than the anaerobism digested sludge of existing method.Therefore, want in anaerobism digested sludge directly to add flocculation agent and during the throw out (floc) that obtains to dewater, need a large amount of flocculation agents.Therefore, in the present invention, for the digested sludge throw out that obtains to dewater, with the parting liquid that obtains in the pretreatment process or water any mixes with anaerobism digested sludge at least, anaerobism digested sludge is diluted, the mud flocculation reaction of the flocculation agent by anaerobism digested sludge and interpolation and generate the digested sludge throw out reposefully, thus realize the reduction of flocculent agent injection rate.In addition, in pretreatment process of the present invention, for the flocculation mud that will add flocculation agent and prepare is separated into mud enriched material and parting liquid, water-soluble or hydrophilic useful resources such as phosphorus contains in parting liquid, can reclaim useful resources effectively.In addition, because can reclaim the pretreatment process of useful resources carried out before anaerobism digestion operation, be transported to reductions such as phosphorus in the mud enriched material of anaerobism digestion operation, siloxanes, and because sludge concentration is high density, therefore can reduce the generation of the precipitate that contains phosphorus, siloxanes etc. in the anaerobism digestive shelf.
In the present invention, unless otherwise prescribed, " % " refers to " quality % ".Anaerobism treatment unit of the present invention can have aptly for the unit of carrying mud between above-mentioned each intrinsic device, for example pipe arrangement, pump, valve etc.
The effect of invention
According to the present invention, by the anaerobism digestion of the mud in the waste water processing station etc., organism is decomposed, and can reclaim biogas (especially methane gas) effectively, thus, can improve energy recovery efficiency significantly.Especially, at in the existing treatment process greatly capacity anaerobism digestion facility, costly and mud is the technical task that difficult dehydration property, dewatered sludge water ratio are difficult to reduce for the chemical of digested sludge processing, in the present invention, can in the concentrating unit of low operating cost, mud height be concentrated, and can significantly cut down anaerobism digestion capacity, in addition, the dehydration operation that can also carry out the anaerobism digested sludge of difficult dehydration property improves, thus can realize can be effectively with the Digestive tract of anaerobism cheaply of digested sludge processed.In addition, the present invention the introducing amount of the phosphorus in the anaerobism digestive shelf, calcium, siloxanes etc. can be reduced in the past roughly half, and then can reduce the generation of the precipitate that contains phosphorus, calcium, siloxanes etc. in the anaerobism digestive shelf, help the reduction of the keeping of anaerobism digestive shelf and pipe arrangement etc., overhead charges, can reclaim useful resources such as phosphorus simultaneously effectively.
Description of drawings
Figure 1 shows that the explanatory view of formation of the treatment unit of embodiments of the present invention.
Figure 2 shows that the explanatory view of formation of the treatment unit of embodiments of the present invention.
Figure 3 shows that the explanatory view of formation of the treatment unit of embodiments of the present invention.
Figure 4 shows that the explanatory view of formation of the treatment unit of embodiments of the present invention.
Figure 5 shows that the explanatory view of formation of the treatment unit of embodiments of the present invention.
Figure 6 shows that the explanatory view of the formation of existing treatment unit.
Embodiment
Below suitably be described in more detail the present invention with reference to accompanying drawing.
Anaerobism treatment process of the present invention comprises: the flocculation mud solid-liquid separation that interpolation flocculation agent in mud is prepared is the mud enriched material of sludge concentration 4～12wt% and the pretreatment process of parting liquid; Anaerobism digestion operation with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism digestion operation and flocculation agent and be selected from described parting liquid and the water any mixes at least, prepare the operation of digested sludge throw out; And the operation that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
In the present invention, " mud " refers at the mud of disposing of sewage, discharging in the operation of organic system material such as fecaluria, food waste.
As the mud of handling among the present invention, preferably be selected from primary sludge that the initial settling tank by sewage treatment equipment produces and the excess sludge that produced by final tank at least a, be more preferably the mixing sludge from both.This mud preferably is stored in the storagetank, carries out gravity and concentrates.
In the mud of being discharged by storagetank, add flocculation agent, preparation flocculation mud.The addition of flocculation agent is with respect to the SS(Suspended Solids of mud, suspended particle) be preferably 0.2～1.0wt%, more preferably 0.3～0.6wt%.
As flocculation agent, can use flocculation agent commonly used with being not particularly limited.For example, can list inorganic based flocculating agent such as bodied ferric sulfate or PAC, Tai-Ace S 150 etc. and organic polymer coargulator (below be also referred to as polymeric flocculant) etc., can be used alone or in combination separately, preferably contain polymeric flocculant at least.As polymeric flocculant, can list positively charged ion system, negatively charged ion system, both sexes system etc., for example, can list amidine based flocculating agent, acrylamide based flocculating agent, acrylic acid series flocculation agent etc.
Below according to operation anaerobism treatment process of the present invention is described.
＜pretreatment process 〉
This pretreatment process is that the flocculation mud solid-liquid separation of will add flocculation agent and prepare in mud is the mud enriched material of sludge concentration 4～12wt% and the mud enrichment process of parting liquid.In existing treatment process, owing to add polymeric flocculant mud is concentrated, therefore, be concentrated into 3～4wt%, the sludge concentration about 4～5wt% is the limit at the most.In the present invention, the high densityization that reaches sludge concentration 4～12wt% is possible.On the other hand, contain phosphorus, calcium, siloxanes etc. in the parting liquid.
＜anaerobism digestion operation 〉
Then, above-mentioned mud enriched material is transported in the anaerobism digestion operation, is recovered in the produced simultaneously biogas of anaerobism digestion.Preferably, the digestion of mud enriched material is preferably carried out in 30～40 ℃ mesophilic digestion zone or 50～60 ℃ thermophilic digestion zone at 30～60 ℃.Suitable pH during anaerobism digestion is pH6～8.5, most preferably is pH6.5～8.0.
In the time of will containing the following organic waste liquid of many lubricant components or waste mixture slaking, when temperature was high, the dispersiveness of neutral fat, higher fatty acid increased, therefore the preferential thermophilic digestion method of selecting 50～60 ℃.On the other hand, the ammonia that generates in the digestion of the anaerobism of mud dissociates in high pH and high-temperature zone easily, therefore, should be noted that to be subjected to this point that ammonia hinders easily in thermophilic digestion.As NH in the Digestive system 4 +-N concentration is more than 3, the 500mg/L in mesophilic digestion, is 2,000mg/L when above in thermophilic digestion, and the methane formation reaction is hindered.These operational conditions consider that sludge concentration, sludge character, the water yield when anaerobism digests of thickened sludge change, target processing water quality is determined.
Anaerobism digestion operation more preferably comprises: at 30～60 ℃ for the treatment of temps, HRT(hydraulic detention time: Hydraulic retention time) under 1～3 day the condition described mud enriched material is carried out dissolving the leading portion digestion operation of handling with acid-fermentation, and methane fermentation is carried out in the digested sludge of handling in this leading portion digestion operation handle, the methane fermentation operation of preparation anaerobism digested sludge.
This leading portion digestion operation has the function that the anaerobism of the methane fermentation operation that promotes back segment is handled, for reducing the HRT of methane fermentation operation, the recovery effectuation that makes biogas and stabilization, stably keep high thick seston containing ratio, reduce fermentation broth viscosity.In addition, can digest the adjustment of carrying out SS concentration in the operation at leading portion.
The methane fermentation operation is preferably carried out under the condition of 30～60 ℃ for the treatment of temps and HRT12～20 day, and is preferred so that be that 3～20% mode prepares anaerobism digested sludge with respect to the thick seston containing ratio of SS.The thick seston of above-mentioned thick seston containing ratio refers to fibrous material, particulate matters etc. such as Mierocrystalline cellulose.This HRT more preferably 12～15 days, thick seston containing ratio more preferably 5～18%.By thick seston containing ratio is set at above-mentioned scope, can improve the dehydration property of digested sludge enriched material, realize that the water ratio of dewatered cake reduces.
In addition, in the anaerobism of the present invention digestion operation, can be with from the outside, namely organic waste liquid or the waste transported of the system outside of the waste water processing station of implementing among the present invention handled with mud.Organic waste liquid or waste from the outside contain the organic compound of discharging from the equipment of factory, sewage work etc. at least, can contain mud, draft class etc.Organic waste liquid or waste from the outside can be input in any one of pretreatment process, leading portion digestion operation and methane fermentation operation.When digesting with the mud anaerobism from the organic waste liquid of outside or waste, preferably with the slurry TS(Total Solids of this organic waste liquid or waste) concentration is adjusted to 1～15%(more preferably 3～10%), add reaching under the mixing condition of slurry TS ratio that TS with respect to the mud enriched material is (more preferably 5～100%) below 120%.Wherein, slurry TS concentration refers to the TS concentration in the slurry, and slurry TS is than the TS ratio of the input material that refers to contain in the slurry.Slurry TS concentration considers that kind, concentration, state, the incoming frequency of organic waste liquid or waste wait to determine.In addition, when the organic waste liquid of importing from the outside or waste are incorporated into the anaerobism digestion operation as required after carrying out physical property, chemical, biological disaggregating treatment, can make the digestion reaction stabilization, thereby be preferred.An example as processing mode can list wet type fragmentation, dry type pulverizing, thermal treatment, high temperature high pressure process, acid or alkaline purification, biosolubleization or acid-fermentation processing etc. aptly.
＜digested sludge throw out preparation section 〉
Then, anaerobism digested the anaerobism digested sludge for preparing in the operation and flocculation agent and be selected from the parting liquid of pretreatment process and water any mixes at least, preparation digested sludge throw out.
As the flocculation agent that adds in anaerobism digested sludge, polymeric flocculant etc. are preferred.In addition, bodied ferric sulfate or PAC etc. are inorganic is the clarity that also can be effective to improve parting liquid sometimes that is used in combination of flocculant aid and polymeric flocculant.As polymeric flocculant, can use less expensive cationic polymers based flocculating agent for example acrylic ester, methacrylate ester, both sexes based flocculating agent that cationic degree is higher than negatively charged ion degree etc., but also can use the amidine based flocculating agent of high price.As acrylic ester, molecular weight 300～6,000,000 are owing to obtained the high digested sludge throw out of settlement separate property but preferred.
The addition of flocculation agent changes according to the proterties of anaerobism digested sludge, and in order to improve the settlement separate property of digested sludge throw out, preferably the flocculation particle diameter of throw out reaches the addition of several millimeter.Particularly, with respect to the SS in the anaerobism digested sludge to be 1.0～2.5% scope, preferred 1.5～2.0% scope is added flocculation agent, makes that the flocculation particle diameter of throw out is the scope of 5～20mm, is preferably the scope of 10～20mm.
The parting liquid that uses in the digested sludge throw out preparation section or water (being also referred to as " dilution water ") have the function of dilution anaerobism digested sludge.The dilution of the thickened sludge by utilizing parting liquid or water is adjusted to the specific conductivity of mud below the 1200mS/m, below the preferred 750mS/m, the M basicity of mud is adjusted to below the 4000mg/l, below the preferred 2500mg/l, the temperature of mud is adjusted to more than 35 ℃ preferred 50～75 ℃.The temperature of the mud of dilution can be adjusted by the parting liquid or the water that add the said temperature scope, perhaps can add post-heating.The parting liquid that dilution water obtains, the common tap water etc., be dissolved into that the concentration of grading is less to be waited condition of water quality (electric conductivity is that 500mg/L is following, M basicity is that 1500mg/L is following, SS is that 1500mg/L is following, COD so long as satisfy in pretreatment process CrBelow 15000mg/L) water, can use any process water in the processing plant.In addition, can also use biological treatment of water such as active sludge treatment water, biological deodorizing device waste liquid.
Gained digested sludge throw out is carried out solid-liquid separation, preparation digested sludge enriched material and parting liquid.The concentration rate of digested sludge enriched material is preferably about 2.5～8 times.Herein, concentration rate refers to the value that the volume with the digested sludge throw out obtains divided by the volume of digested sludge enriched material.
In the digested sludge enriched material that solid-liquid separation is crossed, add flocculation agent and dilution water as required again, preparation reconcentration flocculation mud.Flocculation agent and the dilution water that use this moment can be flocculation agent and the dilution waters that uses in the digested sludge throw out preparation section.(the TS concentration that concentrates flocculation mud was the scope of 4～15wt%, is preferably 6～10wt%), is transported in the dehydration procedure as final digested sludge throw out when reconcentration flocculation mud had sufficient dehydration property.Yet, when this reconcentration flocculation mud does not have sufficient dehydration property, perhaps be considered as in case of necessity (when the TS concentration that concentrates flocculation mud is lower than 4wt%) etc. originally in the design, for example can repeat that above-mentioned flocculation agent reinjects and follow-up solid-liquid separation or only repeat solid-liquid separation.Be used for the reflooded flocculation agent of flocculation agent and can use the identical flocculation agent of flocculation agent that uses with digested sludge throw out preparation section, also can use different flocculation agents.
Even final digested sludge throw out preferably has after the shearing force in the dehydration procedure that stands back segment the also throw out of the intensity of residual a little degree of its granular throw out shape.The flocculation agent that is used for this digested sludge throw out of acquisition is not particularly limited, preferably polymeric flocculant.As polymeric flocculant, can list the polymeric flocculant for above-mentioned flocculation mud preparation section, can be identical with the flocculation agent of pretreatment process, also can be different.
＜dehydration procedure 〉
Then, with the dehydration of digested sludge throw out, solid-liquid separation is dewatered cake and parting liquid.In the present invention, the concentration rate of dewatered cake is preferably about 4～10 times.Herein, concentration rate refers to the value that the volume with the digested sludge throw out obtains divided by the volume of dewatered cake.Therefore the parting liquid that separates in the dewatered cake preparation section is suitable as the dilution water that uses in the operation of preparation digested sludge throw out owing to have little SS concentration, M basicity and specific conductivity.Dewatered cake is owing to be hyposaline and low-water-content, but therefore renewable resources also is suitable for secondary processing such as composting, carbonization, turning sludge into fuel etc.
＜phosphorus and siloxanes reclaim 〉
Contain phosphorus, calcium, siloxanes etc. in the parting liquid that obtains in the pretreatment process.Among the present invention, all or part of of parting liquid that contains them can be transported to reclaim or the operation except dephosphorization, calcium, siloxanes etc. in.The recovery of phosphorus can be used the contact dephosphorization method of using hydroxyapatite, the MAP method of using ammonium magnesium phosphate etc.
In the MAP method, can list following method: for example be pre-charged with the crystal seed of MAP in the upward flow groove at reactive tank, in addition, as required, in parting liquid, add the medicament that is used for replenishing not enough MAP composition, for example MgCl 2, Mg (OH) 2Deng, further, as required, the pH of parting liquid is adjusted to 7.8～8.5, parting liquid is passed in the reactive tank according to upward flow, the particle diameter of MAP is increased, this is had the MAP that increases particle diameter suitably discharge from reactive tank, separate, reclaim.The fine MAP that generates in the reactive tank reclaims from groove top, turns back in the reactive tank.
The recovery of siloxanes can be carried out parting liquid by utilizing sorbent materials such as gac, silica gel, zeolite, polymkeric substance (for example styrene diethylene benzene copoly mer etc.) as gas and even spray form absorption or the method for directly adsorbing under liquid state.In addition, as required, nitrogen is suitably heated, in being adsorbed with the sorbent material of siloxanes, pass through, thereby siloxanes can be broken away from, reclaims.For following biogas, can use with above-mentioned same sorbent material and handle siloxanes, using the same method breaks away from siloxanes, reclaim.
The present invention is as mentioned above owing to have the operation that solid-liquid separation is parting liquid and mud enriched material, so import volumes in the anaerobism slaking apparatus such as phosphorus, siloxanes that reduced compared with the past, and then be reduced in the generation of the precipitate that comprises phosphorus, siloxanes etc. in this device, have the effect that helps to reduce the keeping of this device or pipe arrangement etc., overhead charges.
＜anaerobism treatment unit 〉
Anaerobism treatment unit of the present invention comprises: add flocculation agent and prepare the flocculation groove of the mud that flocculates in mud; Solid-liquid separation is the mud enriched material of sludge concentration 4～12wt% and the pre-treatment sludge concentration device of parting liquid; Anaerobism slaking apparatus with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism slaking apparatus and flocculation agent and be selected from described parting liquid and water any mixes and prepares the digested sludge flocculation plant of digested sludge throw out at least; And the device that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
The flocculation groove can be normally used flocculation groove.
The pre-treatment sludge concentration device can be to be the solid-liquid separation tank of mud enriched material and parting liquid with flocculation mud solid-liquid separation.Solid-liquid separation tank is not particularly limited, can lists the simple groove of application of weight method of enrichment, the separating centrifuge of using centrifugal method of enrichment, the separating machine of using the flotation method of enrichment, the separating machine that uses screen cloth, slit type thickner etc.Wherein, the slit type thickner is preferred, for example, can list the physical construction as record in the above-mentioned TOHKEMY 2003-211293 communique (patent documentation 3): handled thing is caught with slit plate (slit plate), be formed with on the slit plate of a plurality of slits, make the outstanding a plurality of plectanes of side face utilize the axial rotary handled thing to discharge the eccentric rotation of direction, handled thing is transferred to discharging side on slit plate, in this process, liquid component in the slit and plectane between the gap fall and be filtered, the separated capture of solids component in the handled thing further arranges that upper surface with slit plate approaches and in the discharge direction rotation of handled thing at above-mentioned slit plate, capture thing on the slit plate is squeezed, take off the band transfer roller of liquid.When using the slit type thickner, can be stable and realize the high densityization of 4～12wt% reliably with cheap running cost.
The anaerobism slaking apparatus comprises the anaerobism digestive shelf at least.The anaerobism digestive shelf is not particularly limited the complete mixed type digestive shelf of advantageous applications.The anaerobism digestive shelf is in order to realize the homogenization of the homogenizing of liquid in the groove, temperature distribution, prevent the generation of scum silica frost simultaneously, stirring is essential, in the present invention, the mechanical stirring mode is the most effective, but according to facility environment, treatment condition, attached pump alr mode, gas stirring mode also are effective.In addition, so long as possess the watertight of these important documents and the digestive shelf of airtight construction gets final product, can be any of skeleton construction or steel plate system, also can and upgrade existing anaerobism digestive shelf and use according to the treatment condition transformation.In addition, the anaerobism slaking apparatus preferably includes: the mud enriched material is carried out dissolving the methane fermentation groove of handling with dissolving of handling of acid-fermentation and acid-fermentation treatment trough and the digested sludge methane fermentation that will handle in this groove.The anaerobism slaking apparatus preferably includes: store from the organic waste liquid of outside or the external biogas storage facility of waste; And will import to from the biogas that this external biogas storage facility is discharged and be selected from by described storage facility, carry out to dissolve and device that acid-fermentation is handled and mechanism and the pipe arrangement in any device at least the methane fermentation device.
The digested sludge flocculation plant comprises digested sludge flocculation groove, introduce the suitable mud of dilution unit, flocculation agent adding device, agitating unit, heating unit, flocculation mud draw unit etc.In addition, can have for mixing device in the pipe arrangement of dilution.
Anaerobism treatment unit of the present invention preferably has the device that is prepared the digested sludge enriched material by the digested sludge throw out.
The device of preparation digested sludge enriched material preferably has and prepares the flocculation mud that concentrates flocculation mud by the mud flocculation treatment device of flocculation agent preparation flocculation mud, with this flocculation mud solid-liquid separation and separate concentrating unit, concentrate interpolation flocculation agent in flocculation mud and prepare the device of reconcentration mud at this.
It is for concentrating the device of flocculation mud and parting liquid with flocculation mud solid-liquid separation that flocculation mud separates concentrating unit.The mud that flocculates is separated concentrating unit be not particularly limited, can list the separating machine of simple groove, the separating centrifuge of using centrifugal method of enrichment that uses the application of weight method of enrichment, the separating machine of using the flotation method of enrichment, use screen cloth etc.Wherein, the equipment for separating liquid from solid that preferably has screen cloth, for example, can list can be by a plurality of screen clothes of arranging according to parallel at certain interval and a plurality of disks that rotate between this adjacent screen cloth, the flocculation mud physical property in the gap between this adjacent screen cloth is got rid of, simultaneously separable for concentrating flocculation mud and dividing dried up equipment for separating liquid from solid.Wherein, less than the flocculation particle diameter of digested sludge throw out, be preferably 0.1～2.5mm on the wavelength width of a slit principle of screen cloth.
Reconcentration flocculation mud preparation facilities is suitable have concentrate that flocculation mud imports unit, flocculation agent adding device, agitating unit, reconcentration flocculation mud draw unit etc.
Be not particularly limited for the device with the dehydration of digested sludge enriched material, usually can use with the mud that flocculates and separate device identical on the concentrating unit principle, but separating concentrating unit with flocculation mud compares, generally higher for separating of the stress on the digested sludge throw out of dewatered cake, can adopt known unit.The dewatered cake preparation facilities is preferably by giving the means of stress at reconcentration flocculation mud and seeing through parting liquid, keep the filtration means of digested sludge throw out to constitute.As the means of giving stress at the digested sludge throw out, can list pressure, centrifugal etc.As the filtration means, can list opening diameter is screen cloth of 0.1～2.5mm etc.
Then further specify an example of the present invention with reference to accompanying drawing.
Figure 1 shows that the feel flow draw of block of first embodiment of the present invention, is the explanatory view of the formation of expression anaerobism treatment unit.
Mud 1 is transported in the storage facility 2.Then, mud 1 is discharged from storage facility 2, via pipe arrangement, is transported in the flocculation groove 3.In flocculation groove 3, flocculation agent 4 is added in the mud 1 to preparation flocculation mud 5.Flocculation mud 5 is transported in the pre-treatment mud thickener 6, and solid-liquid separation is mud enriched material 7 and the parting liquid 8 of sludge concentration 4～12%.Mud enriched material 7 is transported in the anaerobism slaking apparatus 9, and the anaerobism digestion by mud generates biogas 10 and anaerobism digested sludge 11.Biogas 10 is transported in the biological gas tank 101, and then, biogas 10 is transported to gas and utilizes equipment 102(for example gas turbine, biogas boiler, gaslight, drying machine thermal source etc.) or residual gas combustion unit 103 in.Anaerobism digested sludge 11 is transported in the digested sludge flocculation plant 12.The part of the parting liquid 8 that forms in pre-treatment mud thickener 6 is incorporated in the digested sludge flocculation plant 12.In digested sludge flocculation plant 12, parting liquid 8 and flocculation agent 13 are added in the anaerobism digested sludge 11, form digested sludge throw out 15 and parting liquid 14.Digested sludge throw out 15 from digested sludge flocculation plant 12 is transported in the dewatering unit 16, when isolating parting liquid 17, and preparation dewatered cake 18.The part of parting liquid 8, parting liquid 14 and parting liquid 17 are transported in sewage treatment equipments 104 such as phosphorus recovery etc.Wherein, before biological gas tank, can arrange that siloxanes is removed or retrieving arrangement.
Then, Figure 2 shows that the feel flow draw of block of second embodiment of the present invention, is the explanatory view of the formation of expression anaerobism treatment unit.In the leading portion of anaerobism digestion, carry out to dissolve with acid-fermentation and handle.
In the schema of Fig. 1, be transported to before the mud enriched material 7 that separates in pre-treatment mud thickener 6 is being transported in the anaerobism slaking apparatus 8 can dissolve with acid-fermentation treatment unit 9a in, generate and implemented to dissolve the digested sludge 7a that handles with acid-fermentation.Digested sludge 7a is transported in the anaerobism slaking apparatus 9, handles according to the flow process of Fig. 1 later.
Then, Figure 3 shows that the feel flow draw of block of the 3rd embodiment of the present invention, is the explanatory view of the formation of expression anaerobism treatment unit, and anaerobism digested sludge utilizes the mud flocculation treatment of flocculation agent to carry out at twice.
In this flow process, the part of anaerobism digested sludge 11 in Fig. 2 flow process and parting liquid 8 is transported in the digested sludge flocculation groove 12, and the flocculation agent 13 that passes through to add prepares the operation of digested sludge throw out 15 and carries out following change when isolating parting liquid 14.
The part of anaerobism digested sludge 11 and parting liquid 8 is transported among the mud flocculation treatment device 12a, the flocculation agent 13a that passes through to add, preparation flocculation mud 12c.Flocculation mud 12c is incorporated into flocculation mud to be separated among the concentrating unit 14A, and solid-liquid separation is parting liquid 14 and concentrates flocculation mud 12d.Then, concentrate flocculation mud 12d and be transported among the reconcentration flocculation mud preparation facilities 12b, the flocculation agent 13b that passes through to add prepares reconcentration flocculation mud, with this as final digested sludge throw out 15.
Then, Figure 4 shows that the feel flow draw of block of the 4th embodiment of the present invention, is the explanatory view of the formation of expression anaerobism treatment unit, in the flow process of Fig. 3 biological treatment of water 19 is added among the mud flocculation treatment device 12a, with the mud dilution, other processing is identical with Fig. 3.
As this biological treatment of water, can list active sludge treatment water, biological deodorizing processing water, nitrated denitrogenation processing water etc.Because the kind that contains composition of biological treatment of water and concentration affects thereof to kind or addition and then the expense of flocculation agent, therefore, are suitably determined according to processing intent.
Then, Figure 5 shows that the feel flow draw of block of the 5th embodiment of the present invention, being the explanatory view of the formation of expression anaerobism treatment unit, is that organic waste liquid or the waste of transporting from the outside in the flow process of Fig. 4 also carries out anaerobism consumption processing, and other processing is identical with Fig. 4.
In this flow process, organic waste liquid or waste 20 are stored in the biogas storage tank 21 as slurry, adjust as required from the slurry 22 of biogas storage tank 21 and to be incorporated into storagetank 2 after the TS concentration, can to dissolve and at least in any of acid-fermentation treatment unit 9a and anaerobism slaking apparatus 9, and implement to handle.
The anaerobism treatment unit of above-mentioned Fig. 1～5 can be controlled automatically, also can batch process, and also can be its combination.In addition, the control of the temperature of various mud can be automatization.
Embodiment
Embodiments of the invention below are described.Sewage sludge for producing from A sewage work carries out anaerobism Processing Test of the present invention.Need to prove that the present invention is not subjected to any restriction of this embodiment.
In test, in mud, add, mix 0.4%(with respect to the ratio of SS) cationic polymeric flocculant (molecular-weight average 3,000,000), carry out flocculation treatment, then, in the mechanical thickener that has the back pressure plate, solid-liquid separation is mud enriched material and parting liquid.The proterties of mud, mud enriched material, parting liquid has been shown in the table 1.
The anaerobism digestion trial condition of anaerobism slaking apparatus has been shown in the table 2.In the anaerobism Processing Test, use the complete mixed type digestion trial device (chuck warm water is circulating for cubic capacity 30L, useful volume 25L) of heat-resisting vinylchlorid system.In addition, can dissolve with the acid-fermentation device in, use the complete mixed type of Tokyo physics and chemistry apparatus (strain) fermentor tank MDL(processed cubic capacity 10L, turn round under the 4L depth of water).In test, anaerobism slaking apparatus (digestive shelf) is 37 ℃ of down runnings, can dissolve with acid-fermentation device (can dissolve groove) in 45 ℃ of runnings down.Wherein, in the comparative example 2, carry out 55 ℃ high temperature anaerobic Processing Test.Raw material comes into operation and manages pump RP-60 type (Tokyo Physico-chemical Apparatus Co., Ltd.'s system), divides every day and drops under timing register control for 4～8 times.
[embodiment 1]
Flow implementation according to Fig. 1.
[embodiment 2]
Flow implementation according to Fig. 2.Wherein, about the processed of anaerobism digested sludge, Fig. 3 and treatment process shown in Figure 4 are made up to carry out.
[comparative example]
Flow implementation according to Fig. 6.Wherein, digested sludge throw out 15 flocculates to prepare by the mud that utilizes polymeric flocculant.
[table 1]
The proterties of table 1 sewage sludge sample
? ? Mud The mud enriched material Parting liquid
pH - 5.2 5.3 5.2
M basicity (mg/L presses CaCO 3Meter) 600 950 530
TS (g/L) 29.5 72.7 -
VTS (%) 86 87 -
SS (g/L) 24.0 71.8 307※
VSS (%) 88 88 -
Thick seston (%, SS ratio) 37 35 -
Kj-N (mg/L) 1,730 4,280 431
T-P (mg/L) 615 1,360 156
※ unit: mg/L
[table 2]
Table 2 anaerobism Processing Test condition
Wherein, analytical procedure is carried out according to following method.
TS(Total Solids, the total evaporation residue): 105 ℃ of evaporation residue weight (JIS K0102)
VTS(Volatile total solids, burning decrement): 600 ℃ of burning decrements (JIS K0102)
SS(Suspended solids, suspended particle): utilize centrifugal separation at rotating speed 3,000rpm, the weight of precipitate under 10 minutes (JIS K0102)
VSS(Volatile suspended solids, the volatility suspended particle): 600 ℃ of burning decrements (JIS K0102) of suspended particle
COD Cr(chemical oxygen consumption): potassium dichromate process (JIS K0102)
BOD(biological chemistry zmount of oxygen consumption): Winkler (Winkler) sodiumazide revised law (JIS K0102)
Protein: (Kai Shi (Kjeldahl) nitrogen-ammonium-nitrogen) * 6.25
VFA (VFA): high performance liquid chromatography (ERMA OPTICAL ERC-8710, detector RI, post Shodex RSpak KC-811,60 ℃ of column temperature, moving phase 0.1% phosphoric acid)
Methane gas, carbonic anhydride: gas chromatograph (GL Science GC-323, detector TCD, TCD current value 120A, separator column Active Carbon30/60,95 ℃ of column temperature, carrier gas He)
Siloxanes in the digestive gas: the circulation speed of digestive gas with 0.6L/ minute is passed in the hexane solution, captures after the siloxanes, concentrate, by gas chromatograph-mass spectrometer GC/MS quantitative analysis.Herein, be considered to decamethylcyclopentasiloxane (D5) concentration of the annular siloxane that content is maximum in the sewage sludge digestive gas by quantitative analysis evaluation.
Solvability fraction: filtrate GF/B(1 μ m)
M basicity: the hydrochloric acid soln with 0.1mol/L will utilize separating centrifuge at rotating speed 3, and the supernatant liquor titration of 000rpm, acquisition under 3 minutes is to pH4.8(sewage test method)
Thick seston: the thick seston with specified size 74 μ m sieves is analyzed (sewage test method)
[table 3]
Table 3 anaerobism result
1) calculated by the input mud of each composition and the difference of Digestive system
2) D: digestibility
D = ( 1 - VS 2 · A 1 VS 1 · A 2 ) × 100 VS 1: the organic composition (%) that drops into mud
VS 2: the organic composition of digested sludge (%)
A 1: the inorganic components (%) that drops into mud
A 2: the inorganic components of digested sludge (%)
Shown in the anaerobism Processing Test result of table 3, in the anaerobism of embodiment 1 and 2 is handled, obtained the performance of the TS rate of decomposition equal with prior art, VTS rate of decomposition, methane gas incidence.
In addition, when comparing the siloxanes D5 concentration in the digestive gas, in embodiment 1 and 2, its containing ratio reduces, it is believed that because silicone compounds is adsorbed in the digested sludge SS composition that keeps with high density, thus the siloxane concentrations step-down in the digestive gas.
In addition, during thicker seston, as can be seen, in embodiment 1 and 2, its containing ratio increases, and compares with existing digested sludge, has formed the mud condition more favourable to sludge dewatering.
Therefore wherein, in any digestive shelf of comparative example, embodiment, do not find the residual of VFA, think that the anaerobism processing reaction carries out no problemly.
Use the anaerobism digested sludge that obtains among above-mentioned comparative example 1 and 2, the embodiment 1 and 2, research sludge dewatering treatment performance.Cationic polymeric flocculant (molecular-weight average 3,000,000) is used in sludge dewatering.In addition, water extracter uses the press belt type water extracter, and the processed condition is carried out under 1.0m/ minute at filter cloth tension force 4.9kN/m, filter cloth speed.
At first, processed is carried out in the anaerobism digested sludge of comparative example 1 and 2, the result, polymeric flocculant input rate and dewatered cake water ratio are the result of table 4.
[table 4]
The processed result (1) of table 4 anaerobism digested sludge
Figure BDA00003331186100201
Then, the result of processed result, polymeric flocculant input rate and the dewatered cake water ratio of the anaerobism digested sludge that obtains among the embodiment 1 and 2 is the result of table 5.In any dewatering, be high performance with respect to existing method, wherein, as can be seen, the processing mode that flocculation agent shown in Figure 4 injects, is used in combination biological treatment of water at twice is the most effective.Wherein, the anaerobism digested sludge that obtains among the embodiment 1 need not divide dried up dilution, directly injects polymeric flocculant, and during with mud flocculation, processed, the polymeric flocculant input rate is that 3.8%(is with respect to SS), the dewatered cake water ratio is 83%.
[table 5]
The processed result (2) of table 5 anaerobism digested sludge
Figure BDA00003331186100211
In all tests of ※, anaerobism digested sludge: the liquid measure ratio of parting liquid is 1:0.5, and with the parting liquid diluted mixture, the M basicity during diluted mixture is 2500～3600mg/L in first time flocculation agent injection process
[embodiment 3]
Then, according to Fig. 5, illustrate and carry out the embodiment that sewage sludge and food mfg waste (waste saccharide liquid and dessert are waste prods) and rivers and creeks take up an area of the anaerobism processing of mowing.
＜treatment condition 〉
Sewage sludge amount (mixing sludge of primary sludge and excess sludge) 30m 3/ day (TS concentration 3.1%)
The food mfg waste amount of being transported into 1.35t/ days (TS concentration 9.9%)
The rivers and creeks takes up an area of the amount of being transported into 0.15t/ days (water ratio 70.0%) of mowing
Biogas storage tank 3m 2* 2 grooves
＜pre-treatment equipment for separating liquid from solid (the sewage mixing sludge is used 〉
Slit type thickner (screen cloth wavelength width of a slit 1.0mm has the back pressure plate)
Cationic polymeric flocculant (molecular-weight average 3,000,000) input rate 0.4%(is with respect to the ratio of SS)
Mud enriched material amount 12t/ days (TS concentration 7.9%)
Separate liquid measure 19.5m 3/ day (SS concentration 395mg/L)
The SS rate of recovery 97%
The mowing shredding unit
＜anaerobism digestion: can dissolve with the acid-fermentation device (vertical mechanical formula stirrer 〉
Food mfg waste, rivers and creeks take up an area of mow, the mixture of mud enriched material can dissolve with the acid-fermentation device in input amount 3m 3/ day (slurry TS concentration: 10%)
Food mfg waste and rivers and creeks take up an area of the TS of mowing with respect to the ratio 19% of the TS of mud enriched material
HRT2 days
Useful volume 6m 3
45 ℃ of water temperatures
＜anaerobism digestion: anaerobism slaking apparatus (vertical mechanical formula stirrer) 〉
Input amount 13.5m in the anaerobism slaking apparatus 3/ day
HRT14.8 days
Useful volume 200m 3
Water temperature: 37 ℃
The flocculation treatment operation of＜anaerobism digested sludge 〉
Slit type thickner (screen cloth wavelength width of a slit 1.0mm)
The combined amount 10.5m of mud parting liquid 3/ day (M basicity 690mg CaCO 3/ L)
The combined amount 3.5m of biological deodorizing device waste liquid 3/ day (M basicity 1250mg/L)
Cationic polymeric flocculant (molecular-weight average 3,000,000) input rate 1.7%(is with respect to the ratio of SS)
(input rate detail: the input rate 1.3% of leading portion flocculation groove, the input rate 0.4% of reflocculation groove)
＜water extracter 〉
Helical pressure type water extracter
＜generator 〉
The micro gas turbine generator
＜result 〉
Anaerobism digested sludge proterties (TS concentration 3.9%, VTS68%, SS concentration 3.0%, M basicity 8900mg CaCO 3/ L, thick seston containing ratio 16.7%(is with respect to the ratio of SS))
Biogas generation 570m 3/ day (NTP)
Methane gas generation 365m 3/ day (NTP)
Concentration of methane gas 64%
Methane gas production rate 0.37m 3/ input kg VTS(NTP)
Siloxanes D5 concentration 2.3mg/m in the biogas 3
Generated energy 686kwh/ days
Dewatered cake generation 2.1t/ days (water ratio 77%)
Wastewater flow rate 37.6m 3/ day
As mentioned above, as can be seen, according to the present invention, by the anaerobism slaking apparatus of remarkable miniaturization compared with the past, mud, organic waste anaerobism can be handled, stably produce the biogas of high-quality, can carry out the biogas generating.In the processing mode of HRT20～30 of existing method day, anaerobism digestive shelf 630～945m need be set 3, relative therewith, among the present invention, owing to be 206m 3The anaerobism slaking apparatus, therefore, can in anaerobism recess gauge mould is contracted to existing 1/3～1/4 system, carry out anaerobism and handle.In addition, the anaerobism digested sludge that produces can be by being easy to operation with low cost flocculation and dehydration, it is (with reference to table 4) of low-water-content that gained dewatered cake water ratio 77% is compared with existing about 82%, outward appearance and currently available products do not change, do not have undesirable smell, and be health.
[embodiment 4]
Similarly to Example 3, according to Fig. 5, in the sewage-farm, carry out the anaerobism of sewage sludge and food mfg waste (fruit juice citrus waste matter) and handle.Sewage sludge is the concentrated first heavy thickened sludge of gravity and the mixing sludge of excess sludge, implements mud and concentrates.Anaerobism digestion is implemented under the mixture ratio of basic equivalent in each solid substance amount of sewage sludge and citrus waste matter.
＜treatment condition 〉
Sewage sludge amount (mixing sludge of primary sludge and excess sludge) 35m 3/ day
(primary sludge: TS concentration 3.88%, excess sludge: TS concentration 0.93%, mixing sludge: TS concentration 1.39%)
The food mfg waste amount of being transported into 4.0t/ days (TS concentration 12.5%)
Biogas storage tank 3m 2* 2 grooves
＜pre-treatment equipment for separating liquid from solid (the sewage mixing sludge is used 〉
Slit type thickner (screen cloth wavelength width of a slit 1.0mm has the back pressure plate)
Cationic polymeric flocculant (molecular-weight average 3,000,000, strength of solution 2.0g/L) injection rate 0.95m 3/ day
Polymeric flocculant input rate 0.44%(is with respect to the ratio of SS)
Mud enriched material amount 6.2t/ days (TS concentration 7.5%)
Separate liquid measure 29.8m 3/ day (SS concentration 230mg/L)
The SS rate of recovery 98%
Dissolving and the acid-fermentation device of＜food mfg waste 〉
6.0m 3* 1 groove, vertical mechanical stirrer, 37 ℃ of heating
The TS of food mfg waste is with respect to the ratio 102% of the TS of mud enriched material
＜anaerobism slaking apparatus (vertical mechanical formula stirrer 〉
Input amount 10.2m in the anaerobism slaking apparatus 3/ day
HRT19.6 days
Useful volume 200m 3
37 ℃ of water temperatures
The flocculation treatment operation of＜anaerobism digested sludge 〉
Slit type thickner (screen cloth wavelength width of a slit 1.0mm)
The combined amount 2.0m of mud parting liquid 3/ day (M basicity 320mg CaCO 3/ L)
Cationic polymeric flocculant (molecular-weight average 3,000,000) input rate 1.6%(is with respect to the ratio of SS)
Flocculation agent injection process 1 time
＜water extracter 〉
Helical pressure type water extracter
＜generator 〉
The micro gas turbine generator
＜result 〉
(TS concentration 3.8%, VTS 70%, SS concentration 3.2%, M basicity 4490mg CaCO for anaerobism digested sludge proterties 3/ L, thick seston containing ratio 12.1%(is with respect to the ratio of SS))
Biogas generation 591m 3/ day (NTP)
Methane gas generation 349m 3/ day (NTP)
Concentration of methane gas 59%
Methane gas production rate 0.38m 3/ input kg VTS(NTP)
Siloxanes D5 concentration 1.2mg/m in the biogas 3
Generated energy 656kwh/ days
Dewatered cake generation 1.6t/ days (water ratio 78%)
Wastewater flow rate 41.5m 3/ day
As mentioned above, as can be seen, utilizing during sewage sludge of the present invention concentrates, the only first heavy thickened sludge that concentrates of gravity and the mixing sludge (TS concentration 1.39%) of excess sludge for there not being machinery to concentrate, effectively concentration is to about 5.4 times of TS concentration 7.5%(mud concentration rate), can omit the various mechanical thickening equipment of using mostly at present.And, in the present invention, in the anaerobism slaking apparatus of significantly miniaturization, even each solid substance amount of thickened sludge and citrus waste matter is carried out the anaerobism digestion process with the mixture ratio of basic equivalent, also can stably produce the biogas of high-quality.In addition, the anaerobism digested sludge that produces similarly to Example 3 can be by being easy to operation with low cost flocculation and dehydration, and gained dewatered cake water ratio 78% is compared with the past to be low-water-content.
[embodiment 5]
The waste liquid that produces among the research embodiment 3 and 4 and effective utilization of dewatered cake.The phosphorus that the parting liquid that will be produced by the solid-liquid separation of the sewage sludge that is equivalent to pretreatment process of the present invention and the dehydration parting liquid of dehydration procedure reclaim, the dewatered cake that is produced by the dehydration procedure of anaerobism digested sludge enriched material are carried out composting.
＜treatment condition 〉
(1) phosphorus of the solid-liquid separation waste liquid of mud reclaims (MAP method)
PH8.3 during reaction, Mg concentration is more than the 30mg/l
The single-channel type reactor (reacting part: diameter 35cm * height 2.2m, precipitation portion: diameter 80cm * height 1.8m is pre-charged with the crystal seed of the about 0.4～1.0mm of particle diameter)
Phosphorus volumetric loading 20kg-P/m 3My god
(2) composting of dewatered cake
Composting testing apparatus 15m 3(high rate composting vertical type fermentation groove)
The moisture adjustment of dewatered sludge is the mud mechanical drying, water ratio 45～55%
Do not add subsidiary material
Ventilation speed 0.15m during composting 3/ t minute
＜result 〉
[table 6]
Table 6 phosphorus reclaims
Figure BDA00003331186100271
[table 7]
Table 7 product compost proterties
Figure BDA00003331186100272
As can be seen from the above, in the present invention, the waste liquid that produces from embodiment 3 and 4 reclaims phosphorus, dewatered cake can composting, does not change basically with currently available products (listing as a comparative example, the compost proterties of food waste system mesophilic methane fermentation mud) on quality.The organic matter decomposition rate of composting is 24% in the mud of embodiment 3, is 28% in embodiment 4.Wherein, the gross calorific value of dewatered cake (Higher Heating Value) is 17MJ/kg-dry in the mud of embodiment 3, be 17.3MJ/kg-dry in the mud of embodiment 4, therefore, with this dewatered sludge mechanical drying, has the quality [quality standard of turning sludge into fuel thing (granulating and drying thing) is thermal value 4000kal/kg above (more than the 16.7MJ/kg)] that can be used as sludge fuel and effectively utilize.
Description of reference numerals
1 ... mud, 2 ... storagetank, 3 ... the flocculation groove, 4 ... flocculation agent, 5 ... flocculation mud, 6 ... pre-treatment mud thickener, 7 ... the mud enriched material, 7a ... digested sludge, 8 ... parting liquid, 9 ... the anaerobism digestive shelf, 9a ... can dissolve and acid-fermentation treatment trough, 10 ... biogas, 11 ... anaerobism digested sludge, 12 ... the digested sludge flocculation plant, 12a ... mud flocculation treatment groove, 12b ... reconcentration flocculation mud preparation facilities, 12c ... flocculation mud, 12d ... concentrate flocculation mud, 14A ... flocculation mud separates concentrating unit, 15 ... the digested sludge throw out, 13,13a, 13b ... flocculation agent, 14 ... parting liquid, 15 ... the digested sludge throw out, 16 ... dewatering unit, 17 ... parting liquid, 18 ... dewatered cake, 19 ... biological treatment of water, 20 ... organic waste liquid or waste, 21 ... the biogas storage tank, 101 ... biological gas tank, 102 ... gas utilizes equipment, 103 ... the residual gas combustion equipment, 104 ... sewage treatment equipment.

Claims (14)

1. anaerobism treatment process, it comprises: be the mud enriched material of sludge concentration 4～12wt% and the pretreatment process of parting liquid with the flocculation mud solid-liquid separation of adding flocculation agent and preparing in mud; Anaerobism digestion operation with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism digestion operation and flocculation agent and be selected from described parting liquid and the water any mixes at least, prepare the operation of digested sludge throw out; And the operation that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
2. anaerobism treatment process according to claim 1, wherein, described mud is to be selected from least a in the excess sludge that primary sludge that the initial settling tank by sewage treatment equipment produces and final tank produce.
3. anaerobism treatment process according to claim 1 and 2, wherein, described flocculation mud is that 0.2～1.0% flocculation agent prepares by using SS with respect to mud.
4. according to each described anaerobism treatment process of claim 1～3, wherein, described anaerobism digestion operation comprises: under the condition of 30～60 ℃ for the treatment of temps, HRT1～3 day described mud enriched material is carried out dissolving the leading portion digestion operation of handling with acid-fermentation; And methane fermentation is carried out in the digested sludge of handling in this leading portion digestion operation handle, prepare the methane fermentation operation of described anaerobism digested sludge.
5. anaerobism treatment process according to claim 4, wherein, described methane fermentation operation under the condition of 30～60 ℃ for the treatment of temps and HRT12～20 day so that be that 3～20% mode prepares anaerobism digested sludge with respect to the thick seston containing ratio of SS.
6. according to each described anaerobism treatment process of claim 1～5, wherein, the organic waste liquid that to transport from the outside or waste are adjusted to slurry TS concentration 1～15%, be transported in the described anaerobism digestion operation, carry out anaerobism under the mixing condition that TS with respect to described mud enriched material is the slurry TS ratio 120% below and digest reaching.
7. according to each described anaerobism treatment process of claim 1～6, wherein, described digested sludge enriched material prepares by carrying out 2 flocculation agent injection process at least at the in-process that is made of flocculation agent injection process and follow-up solid-liquid separation process.
8. anaerobism treatment unit, it comprises: add flocculation agent and prepare the flocculation groove of the mud that flocculates in mud; Solid-liquid separation is the mud enriched material of sludge concentration 4～12wt% and the pre-treatment sludge concentration device of parting liquid; Anaerobism slaking apparatus with this mud enriched material anaerobism digestion and recovery biogas; With the anaerobism digested sludge for preparing in this anaerobism slaking apparatus and flocculation agent and be selected from described parting liquid and water any mixes and prepares the digested sludge flocculation plant of digested sludge throw out at least; And the device that the digested sludge enriched material that this digested sludge throw out solid-liquid separation is obtained is dewatered.
9. anaerobism treatment unit according to claim 8, it possesses the mud storage facility of storing mud, and described mud is to be selected from least a in the excess sludge that primary sludge that the initial settling tank by sewage treatment equipment produces and final tank produce.
10. anaerobism treatment unit according to claim 9, it possess with flocculation agent supply to from the mud that described mud storage facility is discharged mechanism and for delivery of the pipe arrangement of mud.
11. according to claim 9 or 10 described anaerobism treatment unit, wherein, described anaerobism slaking apparatus comprises: described mud enriched material is carried out dissolving the device of handling with acid-fermentation and the device that the digested sludge of handling is carried out the methane fermentation processing in this device.
12. anaerobism treatment unit according to claim 11, wherein, the treatment temp of described acid-fermentation groove and described methane fermentation groove is 30～60 ℃.
13. the described anaerobism treatment unit of according to Claim 8～12 each, wherein, the device for preparing described digested sludge enriched material possesses: the mud flocculation treatment device by described flocculation agent preparation flocculation mud, prepare the device that concentrates flocculation mud, concentrate the mud that flocculates by flocculation agent by this and prepare the flocculate device of mud of reconcentration by the mud solid-liquid separation of will flocculate.
14. according to each described anaerobism treatment unit of claim 11～13, it possesses: the organic waste liquid that storage is transported from the outside or the external biogas storage facility of waste; And will import to from the biogas that this external biogas storage facility is discharged and be selected from by described mud storage facility, carry out to dissolve mechanism and pipe arrangement during any installs at least the group that the device handled with acid-fermentation and methane fermentation device form.
CN201180059643.8A 2010-12-10 2011-12-09 anaerobic treatment method and device Active CN103347824B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2010-276156 2010-12-10
JP2010276156 2010-12-10
PCT/JP2011/078531 WO2012077778A1 (en) 2010-12-10 2011-12-09 Anaerobic processing method and device

Publications (2)

Publication Number Publication Date
CN103347824A true CN103347824A (en) 2013-10-09
CN103347824B CN103347824B (en) 2016-01-13

Family

ID=46207260

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180059643.8A Active CN103347824B (en) 2010-12-10 2011-12-09 anaerobic treatment method and device

Country Status (5)

Country Link
JP (2) JP6121165B2 (en)
KR (1) KR101885070B1 (en)
CN (1) CN103347824B (en)
AU (1) AU2011339363B2 (en)
WO (1) WO2012077778A1 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103074134A (en) * 2013-01-05 2013-05-01 上海杲晟实业有限公司 Method for preparing biogas and carbonate by straw wastes
JP6211356B2 (en) * 2013-09-09 2017-10-11 水ｉｎｇ株式会社 Sludge treatment system and sludge treatment method
JP6432226B2 (en) * 2014-09-05 2018-12-05 栗田工業株式会社 Method and apparatus for anaerobic digestion of sewage treatment sludge
JP6715187B2 (en) * 2014-12-25 2020-07-01 水ｉｎｇ株式会社 Method and apparatus for treating oil-containing wastewater
JP6679503B2 (en) * 2015-01-09 2020-04-15 水ｉｎｇ株式会社 Method and apparatus for treating organic sludge
JP6666346B2 (en) * 2015-07-21 2020-03-13 水ｉｎｇ株式会社 Organic substance processing method and processing apparatus
WO2017178356A1 (en) * 2016-04-11 2017-10-19 Kemira Oyj Improving sludge dewaterability and energy balance of wastewater treatment
JP6639330B2 (en) * 2016-05-30 2020-02-05 水ｉｎｇ株式会社 Dehydration system and dehydration method
JP6635964B2 (en) * 2017-03-27 2020-01-29 三菱電機株式会社 Sludge treatment apparatus, water treatment system using the same, sludge treatment method and water treatment method
GB2561018B (en) * 2017-03-27 2021-09-08 Anaergia Inc Process for recovering organics from material recovery facility fines
JP2017209680A (en) * 2017-09-11 2017-11-30 水ｉｎｇ株式会社 Sludge treatment system and sludge treatment method
CN108996740A (en) * 2018-07-13 2018-12-14 武汉市政工程设计研究院有限责任公司 A kind of just rain processing system and method
JP7105136B2 (en) * 2018-08-21 2022-07-22 水ｉｎｇ株式会社 ORGANIC WASTE TREATMENT METHOD AND ORGANIC WASTE TREATMENT SYSTEM

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05123700A (en) * 1991-11-07 1993-05-21 Nishihara Environ Sanit Res Corp Method for treating sludge from organic waste water and apparatus therefor
JP2001104999A (en) * 1999-10-07 2001-04-17 Kurita Water Ind Ltd Treatment of organic waste
JP2001276880A (en) * 2000-03-31 2001-10-09 Ataka Construction & Engineering Co Ltd Waste treatment method and device therefor
JP2001334297A (en) * 2000-05-25 2001-12-04 Kurita Water Ind Ltd Method for dehydrating digested sludge and method for estimating dehydration properties of digested sludge
JP2002102828A (en) * 2000-09-28 2002-04-09 Japanese Research & Development Association For Environment-Friendly Processing In Food Industry Method for treating waste containing oil and fat
CN1631821A (en) * 2004-12-17 2005-06-29 清华大学 Urban sludge treatment method
CN101492231A (en) * 2008-05-28 2009-07-29 罗德春 Method for innocent treatment of bottom oil sludge, scruff and active sludge in petro-chemical industry
CN101696077A (en) * 2009-10-21 2010-04-21 黑旋风工程机械开发有限公司 Method for screening and dewatering urban sludge efficiently
CN101767922A (en) * 2010-01-21 2010-07-07 上海亚同环保实业股份有限公司 Sludge dehydration treatment technology

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54118649A (en) * 1978-03-08 1979-09-14 Hitachi Ltd Purifying water control system for sludge treatment
JPS56166997A (en) * 1980-05-26 1981-12-22 Hitachi Ltd Control method for sludge-digesting vessel
JPS5781899A (en) * 1980-11-10 1982-05-22 Toshiba Corp Treatment of organic sludge
JPS5794388A (en) * 1980-12-05 1982-06-11 Hitachi Ltd Sludge concentrating device
JPS57144098A (en) * 1981-02-28 1982-09-06 Hitachi Plant Eng & Constr Co Ltd Anaerobic digestive method for sewer sludge
JPH08206699A (en) * 1995-02-06 1996-08-13 Kurita Water Ind Ltd Dehydrating method for anaerobic digestion sludge
JP3533064B2 (en) 1997-02-07 2004-05-31 株式会社荏原製作所 Method and apparatus for treating night soil, kitchen waste and sludge
JP3389832B2 (en) * 1997-07-10 2003-03-24 栗田工業株式会社 How to treat human waste
JP3566547B2 (en) * 1998-04-21 2004-09-15 アタカ工業株式会社 Waste treatment equipment and pretreatment equipment for methane fermentation treatment
JP2938442B1 (en) * 1998-08-03 1999-08-23 三菱レイヨン株式会社 Sludge treatment method and treatment system
JP2000051900A (en) * 1998-08-17 2000-02-22 Kubota Corp Sludge conditioning and dehydration method
JP3974785B2 (en) 2002-01-17 2007-09-12 株式会社研電社 Solid-liquid separator
JP4117735B2 (en) * 2003-05-12 2008-07-16 株式会社荏原製作所 Methane fermentation treatment method and apparatus
JP2005246311A (en) * 2004-03-05 2005-09-15 Ngk Insulators Ltd Operation method of continuous sludge pressure dehydration machine
JP4298602B2 (en) * 2004-07-16 2009-07-22 株式会社荏原製作所 Method and apparatus for anaerobic digestion treatment of organic sludge
JP2006035166A (en) * 2004-07-29 2006-02-09 Kurita Water Ind Ltd Sludge treatment method and sludge treatment apparatus
JP2006305488A (en) * 2005-04-28 2006-11-09 Kobe Steel Ltd Method of treating organic sludge
JP4496489B2 (en) * 2005-11-18 2010-07-07 株式会社石垣 Method for controlling raw sludge supply amount of dehydrator and its control device
JP2007264758A (en) 2006-03-27 2007-10-11 Aiphone Co Ltd Light controller
JP4129479B1 (en) * 2007-10-10 2008-08-06 株式会社神鋼環境ソリューション Sludge treatment method and treatment system

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05123700A (en) * 1991-11-07 1993-05-21 Nishihara Environ Sanit Res Corp Method for treating sludge from organic waste water and apparatus therefor
JP2001104999A (en) * 1999-10-07 2001-04-17 Kurita Water Ind Ltd Treatment of organic waste
JP2001276880A (en) * 2000-03-31 2001-10-09 Ataka Construction & Engineering Co Ltd Waste treatment method and device therefor
JP2001334297A (en) * 2000-05-25 2001-12-04 Kurita Water Ind Ltd Method for dehydrating digested sludge and method for estimating dehydration properties of digested sludge
JP2002102828A (en) * 2000-09-28 2002-04-09 Japanese Research & Development Association For Environment-Friendly Processing In Food Industry Method for treating waste containing oil and fat
CN1631821A (en) * 2004-12-17 2005-06-29 清华大学 Urban sludge treatment method
CN101492231A (en) * 2008-05-28 2009-07-29 罗德春 Method for innocent treatment of bottom oil sludge, scruff and active sludge in petro-chemical industry
CN101696077A (en) * 2009-10-21 2010-04-21 黑旋风工程机械开发有限公司 Method for screening and dewatering urban sludge efficiently
CN101767922A (en) * 2010-01-21 2010-07-07 上海亚同环保实业股份有限公司 Sludge dehydration treatment technology

Also Published As

Publication number Publication date
KR101885070B1 (en) 2018-08-03
JP6121589B2 (en) 2017-04-26
AU2011339363A1 (en) 2013-09-05
CN103347824B (en) 2016-01-13
JP6121165B2 (en) 2017-04-26
WO2012077778A1 (en) 2012-06-14
AU2011339363B2 (en) 2017-06-01
JP2016117066A (en) 2016-06-30
JPWO2012077778A1 (en) 2014-05-22
KR20140032362A (en) 2014-03-14

Similar Documents

Publication Publication Date Title
CN103347824B (en) anaerobic treatment method and device
JP3452439B2 (en) Recovery and recycling of useful substances from organic waste
Wang et al. Enhancement of anaerobic digestion sludge dewatering performance using in-situ crystallization in combination with cationic organic polymers flocculation
Zhang et al. Enhanced dewatering of waste sludge with microbial flocculant TJ-F1 as a novel conditioner
Aziz et al. Extraction and application of starch-based coagulants from sago trunk for semi-aerobic landfill leachate treatment
CN105948436A (en) System and method for stabilizing and recycling excess sludge of sewage treatment plant
CN112777854A (en) Pig breeding wastewater treatment system and application method
JPH10216785A (en) Treatment of night soil, garbage and sludge
CN105621806A (en) Biological coagulation oxidation process for rapidly treating kitchen waste wastewater
CN109179760B (en) Recycling treatment process for kitchen sludge and rice residues
Hasan et al. Mechanistically understanding the dewatering fundamentals: impact of biological systems and thermal hydrolysis on cake total solids and polymer demand
AU2019385688B2 (en) Advanced phosphorous recovery process and plant
JPS6034799A (en) Treating apparatus for filthy water derived from night soil
Kataoka et al. Field test of methane fermentation system for treating swine wastes
CN221014924U (en) Biogas slurry high-efficiency solid-liquid separation system
CN213680324U (en) Sewage treatment sludge dewatering system
US12024454B2 (en) Advanced phosphorous recovery process and plant
Castillo Struvite formation and dewaterability of digested wastewater sludge from IVAR-SNJ
JPS6377600A (en) Anaerobic digestion method for organic sludge
CN117696611A (en) System and method for cooperatively treating household garbage and kitchen garbage
CN110698027A (en) Dehydration method of organic sludge
JP2022135001A (en) Methane fermentation method
JPH11277099A (en) Dephosphorizing method
Eliasson et al. Utilisation of fractions of digester sludge after thermal hydrolysis
Chauzy et al. First full-scale digestion-THP-digestion (DLD) plant at lille-France (620 000 PE): presentation of a success story

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant