CN103979732B - The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof - Google Patents
The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof Download PDFInfo
- Publication number
- CN103979732B CN103979732B CN201410195422.9A CN201410195422A CN103979732B CN 103979732 B CN103979732 B CN 103979732B CN 201410195422 A CN201410195422 A CN 201410195422A CN 103979732 B CN103979732 B CN 103979732B
- Authority
- CN
- China
- Prior art keywords
- methane
- gas
- container
- flow
- liquid
- 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.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The present invention relates to film biological treating equipment and the method thereof of methane and sulfur-bearing nitrogenous effluent associated treatment.Equipment of the present invention be by inside, the gaseous jet simulation container of multiple gas film assembly, the filler adhered to for accommodating methane-oxidizing bacteria and sulphate reducing bacteria and the circulation type oxidation container of suspension are installed, flow lifting type regeneration container, solid-liquid separation device and the gas flow guiding container for the accommodating aaerosol solution containing thiobacillus denitrificans form.Oxidized at circulation type oxidation container methane, vitriol is reduced; The centrifugation of gas film assembly, making the methane of not oxidation in time be back to circulation type oxidation container continues oxidized, make sulfate reduction product hydrogen sulfide enter flow lifting type regeneration container and be oxidized to vitriol by nitrate, become the oxygenant of regeneration, simultaneously nitrate is reduced to nitrogen, realizes methane waste product and sulfur-bearing nitrogenous effluent and works in coordination with two biochemical reaction zones and effectively process.Compact equipment of the present invention, energy consumption are low, simple to operate.
Description
Technical field
The invention belongs to the equipment utilizing bio-reactor associated treatment waste gas, waste water, particularly a kind of built-up type contains film biological treating equipment and the method thereof of methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
Background technology
In anerobic sowage process, sludge condensation and digestion and garbage loading embeading process, while producing with repugnant substance, also has a large amount of methane generation.No matter be physico-chemical process or biological process, mainly remove the pollution substances such as hydrogen sulfide, ammonia and the VFA in foul gas at present, very micro-to the removal effect of methane.Methane concentration in foul gas is usually not high, utilizes uneconomical economically as energy recovery, normally the gas still containing methane after process is passed through Dilution air high altitude discharge.But methane belongs to greenhouse gases, its Greenhouse effect are 26 times of carbonic acid gas.And methane or hazardous gas, very easily blast when its aerial concentration is 5%-15%.Therefore, study the Collaborative Control technology of cost-effective methane and repugnant substance, for eliminating safe hidden trouble, environment protection has great importance.
Under anaerobic, methane-oxidizing bacteria utilizes vitriol to be carbonic acid gas by methane oxidation, and reaction formula is such as formula (1).Containing a large amount of vitriol in food medicine factory effluent, trade effluent and mine wastewater.Vitriol enters water body, can cause the problem such as water acidification, soil compaction.Utilizing the waste gas of wastewater treatment containing methane of containing sulfate, is an effective way of methane and vitriol associated treatment.But while methane is oxidized to carbonic acid gas, vitriol is reduced to sulfonium ion (S
2-).When having H in solution
+when existing, S
2-with H
+in conjunction with generation hydrogen sulfide, reaction formula is such as formula (2).Hydrogen sulfide very easily spills in air from solution, forms odor pollution.Research finds, under the effect of thiobacillus denitrificans, the anaerobic oxidation of hydrogen sulfide can carry out with the denitrification of nitrate simultaneously, and nitrate is reduced to nitrogen, and hydrogen sulfide is oxidized to vitriol, and reaction formula is such as formula (3).The product sulfur hydrochlorate can be back to the anaerobic oxidation of methane as oxygenant.The process discharge such as the organic and fuel production of chemical fertilizer manufacture, Iron and Steel Production, gunpowder manufacture, livestock beverage field, production of electronic components, oxidation contain the waste water of NO3-N and NO2-N.In water, nitrogen element too much can cause body eutrophication, deteriorating water quality, the existence of harm aquatic animals and plants.Like this, methane oxidation-sulfate reduction is combined with Oxidation of Hydrogen Sulfide-nitrate denitrification two process, utilizing sulfate wastewater oxidizing of methylene, utilize nitrate wastewater to regenerate methane oxidation agent---vitriol, can realize containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
CH
4+SO
4 2-→CO
2+S
2-+2H
2O (1)
S
2-+2H
+→H
2S↑ (2)
H
2S+NO
3-→N
2↑+SO
4 2-+H
2O (3)
But methane oxidation-sulfate-reducing process completes under the effect of methane-oxidizing bacteria and sulphate reducing bacteria.Oxidation of Hydrogen Sulfide-nitrate denitrification is then carry out under the effect of thiobacillus denitrificans.Methane-oxidizing bacteria, sulphate reducing bacteria are different from the growing environment of thiobacillus denitrificans methane, are difficult to grow in a reaction zone.Existing patent arranges the reaction zone of above-mentioned two processes generally relatively independently, as ZL200510126217.8 discloses a kind of waste water treating apparatus with circulating membrane bioreactor and method of wastewater treatment, CN201310193077.0 discloses " a kind of apparatus and method based on intermittent membrane bioreactor gathering denitrifying type dependent anaerobic methane oxidation bacteria ", this device comprises SMBR reactor, inlet chest, automatic control system, water tank, methane gas-holder, argon gas gas-holder, achieves the fast enriching of anaerobic methane bacterium; CN201310589503.2 discloses " application anaerobic membrane bioreactor processes the method for denitrogenating with desulfurization to sewage ", treatment sewage containing nitrate and/or nitrite and sulfide to be introduced in anaerobic reactor and to contact with thiobacillus denitrificans, can high-efficiency desulfurization denitrogenation.In addition, the oxidation rate of methane is comparatively slow, makes except hydrogen sulfide, carbonic acid gas in the gaseous product of methane oxidation-sulfate-reducing process, usually also containing a certain amount of not oxidized methane.This part methane, as do not removed in time, not only reduces methane oxidation decontamination effect improving, also can affect Oxidation of Hydrogen Sulfide-nitrate denilrification procedure, cause the problem can not working in coordination with biological treatment containing methane waste product and sulfur-bearing nitrogenous effluent.
Membrane bioreactor is a kind of water technology being replaced secondary sedimentation basins and sand filter in conventional biochemical treatment technology by membrane filtration.The appearance of membrane bioreactor improves mud-water separation efficiency.Utilize the centrifugation of film, the contaminant degradation bacterium in water is trapped in reactor, improve the concentration of degradation bacteria, thus increase the removal ability of bio-reactor.CN01123900.X discloses " detachable membrane bioreactor and water treatment method ", and the biofilm reactor addressed comprises screen cloth, equalizing tank, bio-reactor and membrane filtration pond, and the mode adopting shoaling layer to heave is carried out film and rinsed effectively to reduce energy consumption.CN201210505701.1 discloses " integration air-float-membrane bioreactor ", this reactor shell is made up of two single ponds, wherein the top in single pond, left side is gas-floating chamber, bottom is chitosan fluid dressing, membrane module is placed in single pond in right side, and arranges backflow pressurizing vessel device effectively to remove the algae in water in hull outside.CN201310068691.4 discloses " a kind of membrane bioreactor ", comprise oxidation ditch, vacuum unit, through liquid pool and permeate pipeline, wherein be provided with multiple film case in oxidation ditch, be provided with multiple hyperfiltration membrane assembly or microfiltration membrane membrane module in each film case, reach good mud-water separation effect.CN201110435627.6 discloses " a kind of VT-MBR bio-reactor ", be made up of VTBR device, membrane separation unit, Buffer Pool, recycle pump and venting port, utilize the crown_interception of film, extend the macromole residence time of hardly degraded organic substance in reactor, and the biphase gas and liquid flow of different fluidised form can be formed in tubular membrane component internal membrane surface, increase the shearing force on film surface, improve the permeability rate of film.But no matter early stage detachable membrane bioreactor or existing integral type film biological reactor, be all obtain filtered liquid by vacuum pump or other type of pump, thus energy consumption is high.
Gas separation membrane is the very fast new technology of development in recent years.The transmitance of different polymeric membranes to different types of gas molecule is different with selectivity, thus can select to be separated and certain gas of enrichment from gaseous mixture.As ZL200310117133.9 discloses a kind of air film-bioreactor waste gas processing equipment.
Summary of the invention
The object of the invention is to solve the problem can not working in coordination with biological treatment containing methane waste product and sulfur-bearing nitrogenous effluent, utilize gas separation membrane to select divided gas flow and membrane module to retain the characteristic of degradation bacteria, methane oxidation-sulfate reduction is combined with Oxidation of Hydrogen Sulfide-nitrate denitrification two reaction process.
Another object of the present invention is to provide the method that the film biological treating equipment utilizing built-up type to contain methane waste product and sulfur-bearing nitrogenous effluent associated treatment carries out containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme: the film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment, comprises circulation type oxidation container, gas film selects separation vessel, flow lifting type regeneration container, solid-liquid separation device and gas flow guiding container.
The inside of described circulation type oxidation container is provided with dividing plate and circulation type oxidation container is divided into fixed reaction zone and floated reaction zone, fixed reaction zone is connected with second liquid flow-guiding mouth by the first liquid flow-guiding mouth being arranged on dividing plate two ends with floated reaction zone, liquid flows downward in fixed reaction zone, in floated reaction zone on flowing; Described inside, fixed reaction zone is provided with the gas distribution grid with multiple hole, gas distribution grid is filled with filler, and filler is between first liquid flow-guiding mouth and second liquid flow-guiding mouth; The top of fixed reaction zone has the first air outlet, and bottom has the first mud discharging mouth; Outer side wall upper end, fixed reaction zone has the first water-in, and lower end has the first inlet mouth, and the first water-in is higher than first liquid flow-guiding mouth, and the first inlet mouth is higher than second liquid flow-guiding mouth; Second liquid flow-guiding mouth is higher than the first mud discharging mouth; The bottom of described floated reaction zone has water port.
Described gas film selects the bottom of separation vessel to arrange the second air outlet, and a sidewall is arranged the second inlet mouth, another sidewall is arranged the 3rd air outlet, described second inlet mouth is connected with the first air outlet; Gas film selects the inside of separation vessel to be provided with multiple gas separation membrane module, be connected by pipeline between multiple gas separation membrane module, and the bottom of each gas film assembly is connected with a total pipeline by respective pipeline, one end of multiple gas film assembly is communicated with the second inlet mouth by pipeline, and the other end is connected with the 3rd air outlet by pipeline; Total pipeline is connected with the second air outlet, and the second air outlet is communicated with the first inlet mouth, and arranges the first vacuum pump between the second air outlet and the first inlet mouth.
Membrane module is equipped with in described solid-liquid separation device inside, and a sidewall upper sets out the mouth of a river, and lower end arranges the 3rd inlet mouth, and described water outlet is communicated with the first water-in by pipeline and recycle pump, and the 3rd inlet mouth is connected with the 3rd air outlet; And be provided with the second vacuum pump between the 3rd inlet mouth and the 3rd air outlet.
The bottom of described flow lifting type regeneration container is provided with the second mud discharging mouth, and top is provided with venting port, and the upper end of a sidewall is provided with the second water-in; Another side wall lower ends is connected with solid-liquid separation device by connected entrance, liquid in described flow lifting type regeneration container on flowing.
Described gas flow guiding container is between flow lifting type regeneration container and solid-liquid separation device, and the upper end of gas flow guiding container one sidewall is provided with the first gas flow guiding hole and is connected with solid-liquid separation device; The lower end of another sidewall is provided with the second gas flow guiding hole and is connected with described flow lifting type regeneration container.
Described connected entrance is lower than the second described gas flow guiding hole.
The aperture in the hole on described gas distribution grid is 3 ~ 50mm.
The first described inlet mouth lower than gas distribution grid, and higher than second liquid flow-guiding mouth.
Described first water-in is higher than first liquid flow-guiding mouth.
Described gas separation membrane module is at least 2.
The filler of the fixed reaction zone of described circulation type oxidation container is attached with methane-oxidizing bacteria and sulphate reducing bacteria, and in floated reaction zone, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution; The aqueous suspension containing thiobacillus denitrificans is mounted with in flow lifting type regeneration container; The waste water of containing sulfate enters the fixed reaction zone circulation type oxidation container continuously from the first water-in and flows downward, through described filler, enter floated reaction zone through second liquid flow-guiding mouth and upwards flow, be back to fixed reaction zone by first liquid flow-guiding mouth again, thus make circulation flowing in the two reaction zones of liquid in circulation type oxidation container; Meanwhile, sulfate reduction is S by the sulphate reducing bacteria being attached on described filler or be suspended in the solution of floated reaction zone
2-; Methane enters circulation type oxidation container from the first inlet mouth and also upwards flows, and the methane-oxidizing bacteria be attached on described filler utilizes the vitriol in solution to be carbonic acid gas by methane oxidation; Part methane enters the floated reaction zone described circulation type oxidation container from the second liquid flow-guiding mouth of bottom and upwards flows, and the liquid promoted in floated reaction zone is oxidized by the methane-oxidizing bacteria suspended while promoting circulation flowing; Reduzate hydrogen sulfide and the not oxidized in time methane of vitriol are discharged from the first air outlet, enter in gas separation membrane module through the second inlet mouth, be difficult to methane through gas separation membrane as oozing residual air, by be communicated with the second air outlet total pipeline eluting gas film select separation vessel, and by vacuum pump from first inlet mouth backflow enter continue circulation type oxidation container oxidized; Be easy to through the hydrogen sulfide of gas separation membrane module, carbonic acid gas as the gas separation membrane oozed described in vapor transmission, entered in solid-liquid separation device by the 3rd air outlet and the 3rd inlet mouth and also upwards flow, to be entered in gas flow guiding container by the first gas flow guiding hole and flow downward, enter flow lifting type regeneration container through the second gas flow guiding hole and upwards flow; Entering described flow lifting type regeneration container from the second water-in containing the waste water of nitrate and flow downward, the thiobacillus denitrificans be suspended in described flow lifting type regeneration container utilizes nitrate to be vitriol by Oxidation of Hydrogen Sulfide, and meanwhile, nitrate is reduced to nitrogen; Nitrogen and carbonic acid gas are discharged from the venting port at the top of flow lifting type regeneration container; Unnecessary mud is discharged from the second mud discharging mouth; Oxidation products vitriol containing hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device from the connected entrance of bottom; Liquid containing vitriol is separated with thiobacillus denitrificans by the membrane module arranged in solid-liquid separation device; The liquid of containing sulfate inputs the fixed reaction zone of circulation type oxidation container in through recycle pump from the first water-in from the water outlet of solid-liquid separation device, and the oxygenant as regeneration continues oxidizing of methylene; Water after process is discharged from water port.
Described flow lifting type regeneration container is higher than solid-liquid separation device, and the film water outlet of solid-liquid separation device drives continuous effluent by the gravity head above membrane module, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device; Enter the sulfide hydrogen of solid-liquid separation device from the 3rd inlet mouth, the infiltration gas of carbonic acid gas washes away film surface on the one hand, make mud or thiobacillus denitrificans can not be attached to film surface, prevent fouling membrane, promote current on the other hand, make the liquid containing thiobacillus denitrificans be back to flow lifting type breeding blanket by the first gas flow guiding hole and the second gas flow guiding hole, avoid the loss of thiobacillus denitrificans.
Gas separation membrane in described gas separation membrane module is rolled film, hollow-fibre membrane or flat sheet membrane, and mould material is polyimide, polysulfones or polydimethylsiloxane.
The membrane module of described solid-liquid separation device is hollow-fibre membrane or flat sheet membrane, and mould material is polypropylene or polysulfones.
Described filler is light porous natural materials or synthetic materials; As the mixing that mineral filler is volcanics, perlite, gravel, haydite or gac wherein one or more; Or organic filler is the mixing of bark, wood chip, baton round or resin foam wherein one or more.
The content of the described methane-oxidizing bacteria contained in the aqueous suspension of methane-oxidizing bacteria and sulphate reducing bacteria is 5.0 × 10
3~ 1.0 × 10
11cFU/ml, the content of sulphate reducing bacteria is 5.0 × 10
5~ 1.0 × 10
11cFU/ml.
The described content containing the thiobacillus denitrificans in the aqueous suspension of thiobacillus denitrificans is 1.0 × 10
5~ 1.0 × 10
11cFU/ml.
Described is 10-2000mg/L containing nitrate concentration in the waste water of nitrate.
In the waste water of described containing sulfate, sulfate concentration is 100-2000mg/L.
Described methane concentration scope: 20-70%.
The described treatment time is 1 hour-2 days.
Beneficial effect:
Compact construction of the present invention, easy and simple to handle, energy consumption is lower; The built-up type that Recycling of oxidize utilizes contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, realizes containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.Methane is carbonic acid gas in oxidation zone by oxide sulfate, and sulfate reduction product hydrogen sulfide is separated through the selection of multi-level gas separatory membrane, enters breeding blanket with after the methane separation be not degraded; Hydrogen sulfide is oxidized to vitriol in breeding blanket by nitrate, completes the regeneration of oxygenant; The oxygenant of regeneration is back to oxidation zone, for the oxidation of methane provides oxygenant, realizes the recycle of oxygenant; The effluent adopting membrane component filters of breeding blanket, prevents thiobacillus denitrificans run off and enter oxidation zone; Methane oxidation-sulfate reduction and Oxidation of Hydrogen Sulfide-nitrate denitrification two process all adopt anaerobic condition, do not need the oxygen outside supplementary quota, save energy consumption.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention
Wherein, 1. the first filler 4. circulation type oxidation container 5. first water-in 6. first air outlet 7., inlet mouth 2. fixed reaction zone 3. first liquid flow-guiding mouth 8. second liquid flow-guiding mouth 9. floated reaction zone 10. first mud discharging mouth 11. second inlet mouth 12. gas film selects gas flow guiding hole 25., vacuum pump 18. second vacuum pump 19. the 3rd inlet mouth 20. solid-liquid separation device 21. membrane module 22. water outlet 23. first gas flow guiding hole 24. second, air outlet 17. first, separation vessel 13. gas separation membrane module 14. total pipeline 15. second air outlet 16. the 3rd connected entrance 26. second mud discharging mouth 27. flow lifting type regeneration container 28. second water-in 29. venting port 30. gas flow guiding container 31. recycle pump 32. water port 33. gas distribution grid 34. dividing plate
Embodiment
Embodiment 1
Refer to Fig. 1.The built-up type that plastic plate is made contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, and its length is respectively 1.5m, 0.5m, 1.2m; Comprise and select separation vessel 12, flow lifting type regeneration container 27, solid-liquid separation device 20 and gas flow guiding container 30 for accommodating thiobacillus denitrificans aaerosol solution for the filler 3 of accommodating methane-oxidizing bacteria and sulphate reducing bacteria attachment and the circulation type oxidation container 4 of accommodating methane-oxidizing bacteria and sulphate reducing bacteria aaerosol solution, gas film.
The inside of described circulation type oxidation container 4 is provided with dividing plate 34 and circulation type oxidation container is divided into fixed reaction zone 2 and floated reaction zone 9, fixed reaction zone 2 is connected with second liquid flow-guiding mouth 8 by the first liquid flow-guiding mouth 7 being arranged on dividing plate 34 two ends with floated reaction zone 9, liquid fixed reaction zone 2 in flow downward, in floated reaction zone 9 on flowing; Described inside, fixed reaction zone 2 is provided with the gas distribution grid 33 with multiple hole, gas distribution grid 33 is filled with filler 3, and filler 3 is between first liquid flow-guiding mouth 7 and second liquid flow-guiding mouth 8; The top of fixed reaction zone 2 has the first air outlet 6, and bottom has the first mud discharging mouth 10; Outer side wall upper end, fixed reaction zone 2 has the first water-in 5, and lower end has the first inlet mouth 1, and the first water-in 5 higher than first liquid flow-guiding mouth 7, first inlet mouth 1 higher than second liquid flow-guiding mouth 8; Second liquid flow-guiding mouth 8 is higher than the first mud discharging mouth 10; The bottom of described floated reaction zone 9 has water port 32.
Described gas film is selected the bottom of separation vessel 12 to arrange on the second air outlet 15, sidewall and is arranged the second inlet mouth 11, and another sidewall is arranged the 3rd air outlet 16, described second inlet mouth 11 is connected with the first air outlet 6; Gas film selects the inside of separation vessel 12 to be provided with multiple gas separation membrane module 13, be connected by pipeline between multiple gas separation membrane module 13, and the bottom of each gas separation membrane module 13 is connected with a total pipeline 14 by respective pipeline, one end of multiple gas separation membrane module 13 is communicated with the second inlet mouth 11 by pipeline, and the other end is connected with the 3rd air outlet 16 by pipeline; Total pipeline 14 is connected with the second air outlet 15, and the second air outlet 15 is communicated with the first inlet mouth 1, and arranges the first vacuum pump 17 between the second air outlet 15 and the first inlet mouth 1.
Membrane module 21 is equipped with in described solid-liquid separation device 20 inside, one sidewall upper sets out the mouth of a river 22, lower end arranges the 3rd inlet mouth 19, and described water outlet 22 is communicated with the first water-in 5 by pipeline and recycle pump 31, and the 3rd inlet mouth 19 is connected with the 3rd air outlet 16; And be provided with the second vacuum pump 18 between the 3rd inlet mouth 19 and the 3rd air outlet 16.
The bottom of described flow lifting type regeneration container 27 is provided with the second mud discharging mouth 26, and top is provided with venting port 29, and the upper end of a sidewall is provided with the second water-in 28; Another side wall lower ends is connected with solid-liquid separation device 20 by connected entrance 25, liquid in described flow lifting type regeneration container 27 on flowing.
Described gas flow guiding container 30 is between flow lifting type regeneration container 27 and solid-liquid separation device 20, and the upper end of gas flow guiding container 30 1 sidewall is provided with the first gas flow guiding hole 23 and is connected with solid-liquid separation device 20; The lower end of another sidewall is provided with the second gas flow guiding hole 24 and is connected with described flow lifting type regeneration container 27.
The waste water of containing sulfate enters the fixed reaction zone 2 circulation type oxidation container 4 continuously from the first water-in 5 and flows downward, through described filler 3, enter floated reaction zone 9 through second liquid flow-guiding mouth 8 and upwards flow, be back to fixed reaction zone 2 by first liquid flow-guiding mouth 7 again, thus make circulation flowing in the two reaction zones of liquid in circulation type oxidation container 4; Meanwhile, be attached on described filler 3 or sulfate reduction is S by the sulphate reducing bacteria be suspended in the solution of floated reaction zone
2-; Methane enters circulation type oxidation container 4 from the first inlet mouth 1 and also upwards flows, and the methane-oxidizing bacteria be attached on described filler 3 utilizes the vitriol in solution to be carbonic acid gas by methane oxidation; Part methane enters the floated reaction zone 9 described circulation type oxidation container 4 from the second liquid flow-guiding mouth 8 of bottom and upwards flows, and the liquid promoted in floated reaction zone 9 is oxidized by the methane-oxidizing bacteria suspended while promoting circulation flowing; Reduzate hydrogen sulfide and the not oxidized in time methane of vitriol are discharged from the first air outlet 6, enter in gas separation membrane module 13 through the second inlet mouth 11, be difficult to methane through gas separation membrane as oozing residual air, by be communicated with the second air outlet 15 total pipeline 14 eluting gas film select separation vessel 12, and by the first vacuum pump 17 from first inlet mouth 5 backflow enter continue circulation type oxidation container 4 oxidized; Be easy to through the hydrogen sulfide of gas separation membrane module, carbonic acid gas as the gas separation membrane oozed described in vapor transmission, entered in solid-liquid separation device 20 by the 3rd air outlet 16 and the 3rd inlet mouth 19 and also upwards flow, to be entered in gas flow guiding container 30 by the first gas flow guiding hole 23 and flow downward, enter flow lifting type regeneration container 27 through the second gas flow guiding hole 24 and upwards flow; Nitrate to enter described flow lifting type regeneration container 27 from the second water-in 28 and flows downward, and the thiobacillus denitrificans be suspended in described flow lifting type regeneration container 27 utilizes nitrate to be vitriol by Oxidation of Hydrogen Sulfide, and meanwhile, nitrate is reduced to nitrogen; Nitrogen and carbonic acid gas are discharged from the venting port 29 at the top of flow lifting type regeneration container 27; Unnecessary mud is discharged from the second mud discharging mouth 26; Oxidation products vitriol containing hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device 20 from the connected entrance 25 of bottom; Liquid containing vitriol is separated with thiobacillus denitrificans by the membrane module 21 arranged in solid-liquid separation device 20; The liquid of containing sulfate inputs the fixed reaction zone 2 of circulation type oxidation container 4 in through recycle pump 31 from the first water-in 5 from the water outlet 22 of solid-liquid separation device 20, and the oxygenant as regeneration continues oxidizing of methylene; Water after process is discharged from water port 32.
Described flow lifting type regeneration container 27 is higher than solid-liquid separation device 20, and the film water outlet of solid-liquid separation device 20 drives continuous effluent by the gravity head above membrane module 21, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device 20; Enter the sulfide hydrogen of solid-liquid separation 20 from the 3rd inlet mouth 19, the infiltration gas of carbonic acid gas washes away film surface on the one hand, make mud or thiobacillus denitrificans can not be attached to film surface, prevent fouling membrane, promote current on the other hand, make the liquid containing thiobacillus denitrificans be back to flow lifting type regeneration container 27 by the first gas flow guiding hole 23 and the second gas flow guiding hole 24, avoid the loss of thiobacillus denitrificans.
Under room temperature condition, the film biological treating equipment utilizing aforesaid combination formula to contain methane waste product and sulfur-bearing nitrogenous effluent associated treatment carries out containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
The support filler installed in inside, the fixed reaction zone 2 of circulation type oxidation container 4 with on the gas distribution grid 33 in multiple hole, active carbon filler 3 is housed, and methane-oxidizing bacteria and sulphate reducing bacteria are attached on described filler; In the floated reaction zone of the circulation type oxidation zone be made up of the first container, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution, and the content of methane-oxidizing bacteria is 5.0 × 10
4cFU/ml, the content of sulphate reducing bacteria is 1.0 × 10
8cFU/ml; In flow lifting type regeneration container 27, be mounted with the aqueous suspension containing thiobacillus denitrificans, the content of thiobacillus denitrificans is 1.0 × 10
6cFU/ml.Gas film is selected to be provided with 2 gas separation membrane module 13 in separation vessel 12, and gas separation membrane is flat sheet membrane, and mould material is polyimide.Arrange membrane module 21 in solid-liquid separation device 20, membrane module is hollow-fibre membrane, and mould material is polypropylene.
Waste gas containing 31% methane, entering built-up type from the first inlet mouth 1 contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, waste water containing 267mg/L vitriol enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the first water-in 5, waste water containing 35mg/L nitrate enters built-up type from the second water-in 28 and contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, the residence time is 12 hours, in waste gas, the clearance of methane reaches 99%, the clearance 91% of vitriol in waste water, the clearance 80% of nitrate.
Embodiment 2.
Refer to Fig. 1.Built-up type contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, and its length is respectively 4.0m, 2.50m, 1.50m.Device structure and to the treatment process of waste gas, waste water with embodiment 1.
Under room temperature condition, utilize aforesaid device to containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.In the fixed reaction zone 2 of circulation type oxidation container 4, filler 3 is housed, filler 3 is bark, filler 3 is attached with methane-oxidizing bacteria and sulphate reducing bacteria, in the floated reaction zone 9 of circulation type oxidation container 4, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution, and the content of methane-oxidizing bacteria is 1.0 × 10
6cFU/ml, the content of sulphate reducing bacteria is 5.0 × 10
9cFU/ml; Be mounted with the aqueous suspension containing thiobacillus denitrificans in flow lifting type regeneration container, the content of thiobacillus denitrificans is 1.0 × 10
7cFU/ml.Gas film is selected to be provided with 3 gas separation membrane module 13 in separation vessel 12, and gas separation membrane is rolled film, and mould material is polysulfones.Arrange membrane module 21 in solid-liquid separation device 20, membrane module is flat sheet membrane, and mould material is polypropylene.
Waste gas containing 53% methane, entering built-up type from the first inlet mouth 1 contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, waste water containing 300mg/L vitriol enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the first water-in 5 continuously, waste water containing 125mg/L nitrate enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the second water-in 28, the residence time is 1 day, methane, the clearance of sulfate and nitrate reaches 90.2% respectively, 91% and 79.6%.
Embodiment 3.
Refer to Fig. 1.Built-up type contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, and its length is respectively 4.5m, 3.5m, 1.8m.Device structure and to waste gas processing method with embodiment 1.
Under room temperature condition, utilize aforesaid device to containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.In the fixed reaction zone 2 of circulation type oxidation container 4, filler 3 is housed, filler 3 is the mixture of resin foam and baton round, filler 3 is attached with methane-oxidizing bacteria and sulphate reducing bacteria, in the floated reaction zone 9 of circulation type oxidation container 4, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution, and the content of methane-oxidizing bacteria is 1.0 × 10
9cFU/ml, the content of sulphate reducing bacteria is 1.0 × 10
10cFU/ml; Be mounted with the aqueous suspension containing thiobacillus denitrificans in flow lifting type regeneration container, the content of thiobacillus denitrificans is 1.0 × 10
10cFU/ml.Gas separation membrane is selected to be provided with 3 gas separation membrane module 13 in separation vessel 12, and gas separation membrane is hollow-fibre membrane, and mould material is polyimide.Arrange membrane module 21 in solid-liquid separation device 20, membrane module is flat sheet membrane, and mould material is polysulfones.
Waste gas containing 60% methane, entering built-up type from the first inlet mouth 1 contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, waste water containing 1200mg/L vitriol enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the first water-in 5 continuously, waste water containing 800mg/L nitrate enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the second water-in 28, the residence time is 1.5 days, methane, the clearance of sulfate and nitrate reaches 82% respectively, 81% and 70%.
Embodiment 4.
Refer to Fig. 1.Built-up type contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, and its length is respectively 6.5m, 4.5m, 2.0m.Device structure and to waste gas processing method with embodiment 1.
Under room temperature condition, utilize aforesaid device to containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment.In the fixed reaction zone 2 of circulation type oxidation container 4, filler 3 is housed, filler 3 is the mixture of gravel and haydite, filler 3 is attached with methane-oxidizing bacteria and sulphate reducing bacteria, in the floated reaction zone 9 of circulation type oxidation container 4, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution, and the content of methane-oxidizing bacteria is 5.0 × 10
10cFU/ml, the content of sulphate reducing bacteria is 1.0 × 10
11cFU/ml; Be mounted with the aqueous suspension containing thiobacillus denitrificans in flow lifting type regeneration container, the content of thiobacillus denitrificans is 1.0 × 10
11cFU/ml.Gas film is selected to be provided with 4 gas film assemblies 13 in separation vessel 12, and the gas separation membrane of gas film assembly 13 is flat sheet membrane, and mould material is polydimethylsiloxane.Arrange membrane module 21 in solid-liquid separation device 20, membrane module is hollow-fibre membrane, and mould material is polypropylene.
Waste gas containing 65% methane, entering built-up type from the first inlet mouth 1 contains the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, waste water containing 1800mg/L vitriol enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the first water-in 5 continuously, waste water containing 1500mg/L nitrate enters built-up type carries out a biological disposal upon containing the film of methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the second water-in 28, the residence time is 2 days, methane, the clearance of sulfate and nitrate reaches 75% respectively, 80% and 70%.
Claims (9)
1. the film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment, comprises circulation type oxidation container, gas film selects separation vessel, flow lifting type regeneration container, solid-liquid separation device and gas flow guiding container; It is characterized in that,
The inside of described circulation type oxidation container is provided with dividing plate and circulation type oxidation container is divided into fixed reaction zone and floated reaction zone, fixed reaction zone is connected with second liquid flow-guiding mouth by the first liquid flow-guiding mouth being arranged on dividing plate two ends with floated reaction zone, liquid flows downward in fixed reaction zone, in floated reaction zone on flowing; Described inside, fixed reaction zone is provided with the gas distribution grid with multiple hole, gas distribution grid is filled with filler, and filler is between first liquid flow-guiding mouth and second liquid flow-guiding mouth; The top of fixed reaction zone has the first air outlet, and bottom has the first mud discharging mouth; Outer side wall upper end, fixed reaction zone has the first water-in, and lower end has the first inlet mouth, and the first water-in is higher than first liquid flow-guiding mouth, and the first inlet mouth is higher than second liquid flow-guiding mouth; Second liquid flow-guiding mouth is higher than the first mud discharging mouth; The bottom of described floated reaction zone has water port;
Described gas film selects the bottom of separation vessel to arrange the second air outlet, and a sidewall is arranged the second inlet mouth, another sidewall is arranged the 3rd air outlet, described second inlet mouth is connected with the first air outlet; Gas film selects the inside of separation vessel to be provided with multiple gas separation membrane module, be connected by pipeline between multiple gas separation membrane module, and the bottom of each gas separation membrane module is connected with a total pipeline by respective pipeline, one end of multiple gas separation membrane module is communicated with the second inlet mouth by pipeline, and the other end is connected with the 3rd air outlet by pipeline; Total pipeline is connected with the second air outlet, and the second air outlet is communicated with the first inlet mouth, and arranges the first vacuum pump between the second air outlet and the first inlet mouth;
Membrane module is equipped with in described solid-liquid separation device inside, and solid-liquid separation device one sidewall upper sets out the mouth of a river, and lower end arranges the 3rd inlet mouth, and described water outlet is communicated with the first water-in by pipeline and recycle pump, and the 3rd inlet mouth is connected with the 3rd air outlet; And be provided with the second vacuum pump between the 3rd inlet mouth and the 3rd air outlet;
The bottom of described flow lifting type regeneration container is provided with the second mud discharging mouth, and top is provided with venting port, and the upper end of a sidewall is provided with the second water-in; Another side wall lower ends is connected with solid-liquid separation device by connected entrance, liquid in described flow lifting type regeneration container on flowing;
Described gas flow guiding container is between flow lifting type regeneration container and solid-liquid separation device, and the upper end of gas flow guiding container one sidewall is provided with the first gas flow guiding hole and is connected with solid-liquid separation device; The lower end of another sidewall is provided with the second gas flow guiding hole and is connected with described flow lifting type regeneration container.
2. the film biological treating equipment of methane according to claim 1 and sulfur-bearing nitrogenous effluent associated treatment, is characterized in that: the first described inlet mouth lower than gas distribution grid, and higher than second liquid flow-guiding mouth.
3. the film biological treating equipment of methane according to claim 1 and sulfur-bearing nitrogenous effluent associated treatment, is characterized in that: connected entrance is lower than the second gas flow guiding hole.
4. utilize the film biological treating equipment of the methane in claim 1 ~ 3 described in any one and sulfur-bearing nitrogenous effluent associated treatment to carry out containing the method for methane waste product and sulfur-bearing nitrogenous effluent associated treatment: to it is characterized in that: the filler of the fixed reaction zone of circulation type oxidation container is attached with methane-oxidizing bacteria and a sulphate reducing bacteria, in floated reaction zone, methane-oxidizing bacteria and sulphate reducing bacteria suspend in the solution; The aqueous suspension containing thiobacillus denitrificans is mounted with in flow lifting type regeneration container;
The waste water of containing sulfate enters the fixed reaction zone circulation type oxidation container from the first water-in and flows downward, through described filler, enter floated reaction zone through second liquid flow-guiding mouth and upwards flow, be back to fixed reaction zone by first liquid flow-guiding mouth again, thus make circulation flowing in the two reaction zones of liquid in circulation type oxidation container; Meanwhile, sulfate reduction is S by the sulphate reducing bacteria being attached on described filler or be suspended in the solution of floated reaction zone
2-; Methane enters circulation type oxidation container from the first inlet mouth and also upwards flows, and the methane-oxidizing bacteria be attached on described filler utilizes the vitriol in solution to be carbonic acid gas by methane oxidation; Part methane enters the floated reaction zone described circulation type oxidation container from the second liquid flow-guiding mouth of bottom and upwards flows, and the liquid promoted in floated reaction zone is oxidized by the methane-oxidizing bacteria suspended while promoting circulation flowing; Reduzate hydrogen sulfide and the not oxidized in time methane of vitriol are discharged from the first air outlet, enter in gas separation membrane module through the second inlet mouth, be difficult to methane through gas separation membrane as oozing residual air, by be communicated with the second air outlet total pipeline eluting gas film select separation vessel, and by the first vacuum pump from first inlet mouth backflow enter continue circulation type oxidation container oxidized; Be easy to through the hydrogen sulfide of gas separation membrane module, carbonic acid gas as the gas separation membrane oozed described in vapor transmission, entered in solid-liquid separation device by the 3rd air outlet and the 3rd inlet mouth and also upwards flow, to be entered in gas flow guiding container by the first gas flow guiding hole and flow downward, enter flow lifting type regeneration container through the second gas flow guiding hole and upwards flow; Nitrate wastewater to enter described flow lifting type regeneration container from the second water-in and flows downward, and the thiobacillus denitrificans be suspended in described flow lifting type regeneration container utilizes nitrate to be vitriol by Oxidation of Hydrogen Sulfide, and meanwhile, nitrate is reduced to nitrogen; Nitrogen and carbonic acid gas are discharged from the venting port at the top of flow lifting type regeneration container; Unnecessary mud is discharged from the second mud discharging mouth; Oxidation products vitriol containing hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device from the connected entrance of bottom; Liquid containing vitriol is separated with thiobacillus denitrificans by the membrane module arranged in solid-liquid separation device; The liquid of containing sulfate inputs the fixed reaction zone of circulation type oxidation container in through recycle pump from the first water-in from the water outlet of solid-liquid separation device, and the oxygenant as regeneration continues oxidizing of methylene; Water after process is discharged from water port.
5. method according to claim 4: it is characterized in that: described flow lifting type regeneration container is higher than solid-liquid separation device, and the film water outlet of solid-liquid separation device drives continuous effluent by the gravity head above membrane module, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device; The hydrogen sulfide containing infiltration gas entering solid-liquid separation device from the 3rd inlet mouth washes away film surface on the one hand, make mud or thiobacillus denitrificans can not be attached to film surface, prevent fouling membrane, promote current on the other hand, make the liquid containing thiobacillus denitrificans be back to flow lifting type regeneration container by the first gas flow guiding hole and the second gas flow guiding hole, avoid the loss of thiobacillus denitrificans.
6. method according to claim 4: it is characterized in that: described gas selects the gas separation membrane in separating film module to be rolled film, and hollow-fibre membrane or flat sheet membrane, mould material is polyimide, polysulfones or polydimethylsiloxane.
7. method according to claim 4: it is characterized in that: described filler is light porous natural materials or synthetic materials.
8. method according to claim 4: it is characterized in that: the content of the described methane-oxidizing bacteria contained in the aqueous suspension of methane-oxidizing bacteria and sulphate reducing bacteria is 5.0 × 10
3~ 1.0 × 10
11cFU/ml, the content of sulphate reducing bacteria is 5.0 × 10
5~ 1.0 × 10
11cFU/ml.
9. method according to claim 4: it is characterized in that: the described content containing the thiobacillus denitrificans in the aqueous suspension of thiobacillus denitrificans is 1.0 × 10
5~ 1.0 × 10
11cFU/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195422.9A CN103979732B (en) | 2014-05-09 | 2014-05-09 | The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410195422.9A CN103979732B (en) | 2014-05-09 | 2014-05-09 | The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103979732A CN103979732A (en) | 2014-08-13 |
| CN103979732B true CN103979732B (en) | 2015-10-07 |
Family
ID=51271937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410195422.9A Active CN103979732B (en) | 2014-05-09 | 2014-05-09 | The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103979732B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107224853A (en) * | 2016-03-25 | 2017-10-03 | 陈晓林 | A kind of method of riser self-loopa depriving hydrogen sulphide |
| CN107285503B (en) * | 2016-04-11 | 2020-02-18 | 中国石油化工股份有限公司 | Method for discharging high-sulfur-content wastewater of oil and gas field after injection reduction and reaching standards |
| CN111099784A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Treatment method of desulfurization wastewater |
| CN109943377B (en) * | 2019-04-17 | 2021-08-06 | 哈尔滨工业大学 | Method for synchronously purifying and enhancing sewage denitrification by using nitrite as electron acceptor |
| CN110407418A (en) * | 2019-08-19 | 2019-11-05 | 海南大学 | A kind of the native rubber processing waste water deep denitrogenation device and method of containing sulfate |
| CN111111422B (en) * | 2019-12-05 | 2023-10-20 | 中国科学院生态环境研究中心 | Method for cooperatively treating volatile organic compounds and nitrogenous and sulphurous malodorous substances |
| CN112624326A (en) * | 2020-12-08 | 2021-04-09 | 香港科技大学深圳研究院 | Control method for membrane pollution in membrane bioreactor and sewage treatment system |
| CN112479506B (en) * | 2020-12-11 | 2022-01-28 | 中国科学院生态环境研究中心 | Coupled biological-membrane-electrochemical waste gas and wastewater co-treatment method |
| CN113736717B (en) * | 2021-11-03 | 2022-02-11 | 广东省科学院生态环境与土壤研究所 | Methane oxidizing bacterium with denitrification function and anoxia resistance and application thereof |
| CN114163079A (en) * | 2021-12-09 | 2022-03-11 | 苏州金渠环保科技有限公司 | Black and odorous river water treatment process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3089297B2 (en) * | 1998-03-18 | 2000-09-18 | 農林水産省畜産試験場長 | Post-treatment equipment for anaerobic sewage treatment |
| CN101036856A (en) * | 2006-03-15 | 2007-09-19 | 中国科学院生态环境研究中心 | Combined type biodegradation-absorbing and separating waste gas processing device and the operation method |
| CN103537188B (en) * | 2012-07-10 | 2015-05-27 | 中国科学院生态环境研究中心 | Integrated equipment and method for coprocessing methane and malodorous substances |
-
2014
- 2014-05-09 CN CN201410195422.9A patent/CN103979732B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103979732A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103979732B (en) | The film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment and method thereof | |
| CN101302058B (en) | Method for removing sulphur and nitrogen in inorganic waste water synchronously | |
| KR101303525B1 (en) | A livestock wastewater treatment system using constructed wetlands | |
| CN101205109B (en) | Apparatus for treating chemical fiber waste water by anaerobic method | |
| CN105693014A (en) | Sewage treatment system and sewage treatment method | |
| CN102126814B (en) | Combination advanced treatment method for oil extraction wastewater | |
| CN203307175U (en) | Deep coking wastewater treatment device by using advanced oxidation process combined with membrane bioreactor | |
| CN102963981B (en) | Method for deep denitrification of integrated biological aerated filter | |
| CN103112991A (en) | Coking wastewater treatment system and coking wastewater treatment method | |
| CN101481197B (en) | Advanced treatment process for sewerage of oilfield heavy crude recovery | |
| CN204550325U (en) | Sewage from oil refinery treatment system | |
| KR100839891B1 (en) | Apparatus for treatment bank filtered water including nitrate nitrogen | |
| CN105776760A (en) | Advanced treatment system and method for crushed coal pressurized gasification waste water | |
| CN204211537U (en) | The double oxygen MBR membrane bioreactor of integration | |
| CN208562075U (en) | Ozone oxidation-BAC filtering-composite catalytic oxidation advanced treatment on coking wastewater system | |
| CN102964039A (en) | Method for treating refractory organic sewage with high salt content | |
| CN113264586A (en) | MBR (membrane bioreactor) process for treating nitrate wastewater | |
| CN211620257U (en) | Ozone catalytic oxidation coupling microalgae method wastewater treatment system | |
| CN201354342Y (en) | Sewage depth treatment device of thick oil recovery of oil field | |
| CN202063766U (en) | Top end gradation particle sludge purification bed | |
| CN104150686A (en) | Landfill leachate treatment method based on microporous aeration ultrafiltration and efficient adsorption | |
| CN201276438Y (en) | Intelligent ultrasonic vibration membrane biological reaction sewage treatment and reclaimed water recycling apparatu | |
| CN203768185U (en) | Coking wastewater treatment system | |
| CN202038946U (en) | Wastewater treatment device in acrylic production process | |
| CN205590517U (en) | Ozone - membrane bioreactor coking wastewater advanced treatment unit that pH control was adjusted |
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 |