CN103979732A - Membrane biological treatment device and method for cooperative treatment of methane and sulfur and nitrogen-containing wastewater - Google Patents
Membrane biological treatment device and method for cooperative treatment of methane and sulfur and nitrogen-containing wastewater Download PDFInfo
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- CN103979732A CN103979732A CN201410195422.9A CN201410195422A CN103979732A CN 103979732 A CN103979732 A CN 103979732A CN 201410195422 A CN201410195422 A CN 201410195422A CN 103979732 A CN103979732 A CN 103979732A
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Abstract
The invention relates to a membrane biological treatment device and method for cooperative treatment of methane and sulfur and nitrogen-containing wastewater. The device provided by the invention comprises a gas membrane separation container provided inside with a plurality of gas membrane modules, a circulation type oxidation container for holding a filling material adhered with methane-oxidizing bacteria and sulfate reducing bacteria, and a suspension, an upflow-type regeneration container for holding a supernatant solution containing Thiobacillus denitrificans, a solid-liquid separation container and a gas guiding container. Methane is oxidized and sulfate is reduced in the circulation type oxidation container; separation effect of gas membrane modules make unoxidized methane return to the circulation type oxidation container for continuous oxidization, and make the sulfate reducing product hydrogen sulfide enter into the upflow-type regeneration container and be oxidized by nitrate into sulfate, as a regeneration oxidant; and at the same time, nitrate is reduced into nitrogen, so as to realize cooperative effective treatment of methane exhaust gas and sulfur and nitrogen-containing wastewater in two biochemical reaction zones. The device provided by the invention has the advanategs of compact structure, low energy consumption and simple operation.
Description
Technical field
The invention belongs to the equipment that utilizes bio-reactor associated treatment waste gas, waste water, particularly a kind of built-up type is containing film biological treating equipment and the method thereof of methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
Background technology
At anerobic sowage, process, mud is concentrated with digestion and garbage loading embeading process in, when following repugnant substance to produce, also have a large amount of methane to generate.No matter be physico-chemical process or biological process, be mainly at present the pollution substances such as hydrogen sulfide, ammonia and VFA of removing in foul gas, very micro-to the removal effect of methane.Methane concentration in foul gas is conventionally not high, uneconomical economically as energy recovery utilization, normally the gas that still contains methane after processing is passed through to 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, when being 5%-15%, its aerial concentration very easily blasts.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, it is carbonic acid gas by methane oxidation that methane-oxidizing bacteria utilizes vitriol, and reaction formula is suc as formula (1).In food medicine factory effluent, trade effluent and mine wastewater, contain a large amount of vitriol.Vitriol enters water body, can cause the problems such as water acidification, soil compaction.Utilizing the wastewater treatment of containing sulfate containing the waste gas of methane, is an effective way of methane and vitriol associated treatment.But when methane is oxidized to carbonic acid gas, vitriol is reduced to sulfonium ion (S
2-).In solution, there is H
+while existing, S
2-with H
+in conjunction with generating hydrogen sulfide, reaction formula is suc as formula (2).Hydrogen sulfide very easily spills in air from solution, forms odor pollution.Research discovery, 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 suc as formula (3).The product sulfur hydrochlorate can be used as the anaerobic oxidation that oxygenant is back to methane.Chemical fertilizer manufacture, Iron and Steel Production, gunpowder manufacture, livestock beverage field, production of electronic components, the waste water that oxidation is organic and the discharge of the process such as fuel production contains nitrate and nitrite.In water, nitrogen element too much can cause body eutrophication, deteriorating water quality, the existence of harm aquatic animals and plants.Like this, two processes of methane oxidation-sulfate reduction and Oxidation of Hydrogen Sulfide-nitrate denitrification are combined, utilize sulfate wastewater oxidizing of methylene, utilize nitrate wastewater regeneration 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 is to complete under the effect of methane-oxidizing bacteria and sulphate reducing bacteria.Oxidation of Hydrogen Sulfide-nitrate denitrification is to 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 generally arranges the reaction zone of above-mentioned two processes 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 methane anaerobic oxidized bacterium ", this device comprises SMBR reactor, inlet chest, automatic control system, water tank, methane gas-holder, argon gas gas-holder, has realized the fast enriching of anaerobic methane bacterium; CN201310589503.2 discloses " application anaerobic membrane bioreactor is processed the method for denitrogenating with desulfurization to sewage ", the treatment sewage that contains nitrate and/or nitrite and sulfide is introduced in anaerobic reactor and contacted with thiobacillus denitrificans, can high-efficiency desulfurization denitrogenation.In addition, the oxidation rate of methane is slower, makes in the gaseous product of methane oxidation-sulfate-reducing process, except hydrogen sulfide, carbonic acid gas, conventionally also to contain 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, causes the problem that can not work in coordination with biological treatment containing methane waste product and sulfur-bearing nitrogenous effluent.
Membrane bioreactor is a kind ofly by membrane filtration, to replace the water technology of secondary sedimentation basins and sand filter in traditional biochemical processing.The appearance of membrane bioreactor has improved 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, thereby increase the removal ability of bio-reactor.CN01123900.X discloses " detachable membrane bioreactor and water treatment method ", and the biofilm reactor of addressing comprises screen cloth, equalizing tank, bio-reactor and membrane filtration pond, and the mode that adopts shoaling layer to heave is carried out film flushing effectively to reduce energy consumption.CN201210505701.1 discloses " integration air-float-membrane bioreactor ", this reactor shell is comprised of two single ponds, wherein the top in single pond, left side is that gas-floating chamber, bottom are biological filtering layer, membrane module is placed in single pond in right side, and backflow pressurizing vessel device is set effectively to remove the algae in water in hull outside.CN201310068691.4 discloses " a kind of membrane bioreactor ", comprise oxidation ditch, vacuum unit, see through liquid pool and see through liquid pipeline, wherein in oxidation ditch, be provided with a plurality of film casees, in each film case, be provided with a plurality of hyperfiltration membrane assemblies or microfiltration membrane membrane module, reach good mud-water separation effect.CN201110435627.6 discloses " a kind of VT-MBR bio-reactor ", by VTBR device, membrane separation unit, Buffer Pool, recycle pump and venting port, formed, utilize the crown_interception of film, extend the residence time of macromole hardly degraded organic substance in reactor, and can form in tubular membrane component internal membrane surface the biphase gas and liquid flow of different fluidised forms, increase the shearing force on film surface, improved the permeability rate of film.Yet no matter early stage detachable membrane bioreactor or existing integral type film biological reactor, be all to obtain filtered liquid by vacuum pump or other type of pump, thereby energy consumption is high.
Gas separation membrane is a very fast new technology of development in recent years.Different polymeric membranes is different with selectivity to the transmitance of different types of gas molecule, thereby can from gaseous mixture, select separated and certain gas of enrichment.As ZL200310117133.9 has announced a kind of air film-bioreactor waste gas processing equipment.
Summary of the invention
The object of the invention is to solution and can not work in coordination with the problem of biological treatment containing methane waste product and sulfur-bearing nitrogenous effluent, utilize gas separation membrane to select divided gas flow and membrane module to hold back the characteristic of degradation bacteria, two reaction process of methane oxidation-sulfate reduction and Oxidation of Hydrogen Sulfide-nitrate denitrification are combined.
Another object of the present invention is to provide the method that the film biological treating equipment that utilizes built-up type to contain methane waste product and sulfur-bearing nitrogenous effluent associated treatment contains 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 selection 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 circulation type oxidation container is divided into fixed reaction zone and floated reaction zone, fixed reaction zone is connected by being arranged on first liquid flow-guiding mouth and the second liquid flow-guiding mouth at dividing plate two ends with floated reaction zone, liquid flows downward in fixed reaction zone, in floated reaction zone on flow; Described inside, fixed reaction zone is provided with the gas distribution grid with a plurality of holes, is filled with filler on gas distribution grid, 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 that the second air outlet is set, and the second inlet mouth is set on a sidewall, and the 3rd air outlet is set on another sidewall, and described the second inlet mouth is connected with the first air outlet; Gas film selects the inside of separation vessel that a plurality of gas delivery membrane modules are installed, between a plurality of gas delivery membrane modules, by pipeline, be connected, and the bottom of each gas film assembly is connected with a total pipeline by pipeline separately, one end of a plurality of gas film assemblies 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 between the second air outlet and the first inlet mouth, the first vacuum pump is set.
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 flow.
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 is lower than gas distribution grid, and higher than second liquid flow-guiding mouth.
Described the first water-in is higher than first liquid flow-guiding mouth.
Described gas delivery membrane module is at least 2.
On the filler of the fixed reaction zone of described circulation type oxidation container, be attached with methane-oxidizing bacteria and sulphate reducing bacteria, in floated reaction zone, methane-oxidizing bacteria and sulphate reducing bacteria are suspended in solution; In flow lifting type regeneration container, be mounted with the aqueous suspension that contains thiobacillus denitrificans; The waste water of containing sulfate enters continuously the fixed reaction zone circulation type oxidation container and flows downward from the first water-in, through described filler, through second liquid flow-guiding mouth, enter floated reaction zone and upwards flow, by first liquid flow-guiding mouth, be back to fixed reaction zone again, thereby circulation in two reaction zones of liquid in circulation type oxidation container is flowed; Meanwhile, be attached on described filler or the sulphate reducing bacteria being suspended in the solution of floated reaction zone is S by sulfate reduction
2-; Methane enters circulation type oxidation container and upwards and flows from the first inlet mouth, and it is carbonic acid gas by methane oxidation that the methane-oxidizing bacteria on the filler described in being attached to utilizes the vitriol in solution; Part methane enters the floated reaction zone described circulation type oxidation container and upwards flows from the second liquid flow-guiding mouth of bottom, promotes the methane-oxidizing bacteria that the liquid in floated reaction zone promotes circulation to be suspended in the time of mobile and is oxidized; The reduzate hydrogen sulfide of vitriol is discharged from the first air outlet with in time not oxidized methane, in the second inlet mouth enters gas delivery membrane module, the methane that is difficult to see through gas separation membrane is as oozing residual air, by being communicated with the total pipeline eluting gas film of the second air outlet, select separation vessel, and by vacuum pump from the first inlet mouth reflux enter circulation type oxidation container, continue oxidized; The hydrogen sulfide, the carbonic acid gas that are easy to see through gas delivery membrane module see through described gas separation membrane as infiltration gas, by the 3rd air outlet and the 3rd inlet mouth, enter in solid-liquid separation device and upwards and flow, by the first gas flow guiding hole, enter in gas flow guiding container and flow downward, through the second gas flow guiding hole, enter flow lifting type regeneration container and upwards flow; Waste water containing nitrate enters described flow lifting type regeneration container and flows downward from the second water-in, and it is vitriol by Oxidation of Hydrogen Sulfide that the thiobacillus denitrificans in the flow lifting type regeneration container described in being suspended in utilizes nitrate, 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; The oxidation products vitriol that contains hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device from the connected entrance of bottom; The membrane module arranging in solid-liquid separation device is separated with thiobacillus denitrificans by the liquid that contains vitriol; The liquid of containing sulfate is inputted from the first water-in through recycle pump in the fixed reaction zone of circulation type oxidation container from the water outlet of solid-liquid separation device, as the oxygenant continuation oxidizing of methylene of regeneration; Water after processing 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 of membrane module top, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device; From the 3rd inlet mouth, enter the sulfide hydrogen of solid-liquid separation device, 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 that film from polluting, promote on the other hand current, make by the first gas flow guiding hole and the second gas flow guiding hole, to be back to flow lifting type breeding blanket containing the liquid of thiobacillus denitrificans, avoid the loss of thiobacillus denitrificans.
Gas separation membrane in described gas delivery 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; If mineral filler is the mixing of volcanics, perlite, gravel, haydite or wherein one or more of gac; Or organic filler is the mixing of bark, wood chip, baton round or wherein one or more of resin foam.
The content of methane-oxidizing bacteria in the described aqueous suspension that contains 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 content of the thiobacillus denitrificans in the described aqueous suspension that contains 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, containing the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment, is realized 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 multistage gas separation membrane, and enters breeding blanket after the methane separation not being 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 module of breeding blanket filters, and prevents that thiobacillus denitrificans runs off and enters oxidation zone; Methane oxidation-sulfate reduction and two processes of Oxidation of Hydrogen Sulfide-nitrate denitrification 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 fixed reaction zone of the inlet mouth 2. 3. filler 4. circulation type oxidation container 5. first water-in 6. first air outlet 7. first liquid flow-guiding mouth 8. floated reaction zone of second liquid flow-guiding mouth 9. 10. first mud discharging mouth 11. second inlet mouth 12. gas films are selected separation vessel 13. gas delivery membrane module 14. total pipeline 15. second air outlet 16. the 3rd air outlet 17. first 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 gas flow guiding hole 25. 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 plates
Embodiment
Embodiment 1
Refer to Fig. 1.The built-up type that plastic plate is made is containing 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 that the filler 3 that adheres to for accommodating methane-oxidizing bacteria and sulphate reducing bacteria and circulation type oxidation container 4, the gas film of accommodating methane-oxidizing bacteria and sulphate reducing bacteria aaerosol solution 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.
The inside of described circulation type oxidation container 4 is provided with dividing plate 34 circulation type oxidation container is divided into fixed reaction zone 2 and floated reaction zone 9, fixed reaction zone 2 is connected by being arranged on first liquid flow-guiding mouth 7 and the second liquid flow-guiding mouth 8 at dividing plate 34 two ends with floated reaction zone 9, liquid fixed reaction zone 2 in flow downward, floated reaction zone 9 interior on flow; Described 2 inside, fixed reaction zone are provided with the gas distribution grid 33 with a plurality of holes, are filled with filler 3 on gas distribution grid 33, 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; 2 outer side wall upper ends, fixed reaction zone have 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, the first inlet mouths 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, one sidewalls the second inlet mouth 11 is set, and the 3rd air outlet 16 is set on another sidewall, and described the second inlet mouth 11 is connected with the first air outlet 6; Gas film selects the inside of separation vessel 12 that a plurality of gas delivery membrane modules 13 are installed, between a plurality of gas delivery membrane modules 13, by pipeline, be connected, and the bottom of each gas delivery membrane module 13 is connected with a total pipeline 14 by pipeline separately, one end of a plurality of gas delivery membrane modules 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 between the second air outlet 15 and the first inlet mouth 1, the first vacuum pump 17 is set.
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 the upper end that top is provided with venting port 29, one sidewalls 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 described flow lifting type regeneration container 27 interior on flow.
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 sidewalls 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 continuously the fixed reaction zone 2 circulation type oxidation container 4 and flows downward from the first water-in 5, through described filler 3, through second liquid flow-guiding mouth 8, enter floated reaction zone 9 and upwards flow, by first liquid flow-guiding mouth 7, be back to fixed reaction zone 2 again, thereby circulation in two reaction zones of liquid in circulation type oxidation container 4 is flowed; Meanwhile, be attached on described filler 3 or the sulphate reducing bacteria being suspended in the solution of floated reaction zone is S by sulfate reduction
2-; Methane enters circulation type oxidation container 4 and upwards and flows from the first inlet mouth 1, and it is carbonic acid gas by methane oxidation that the methane-oxidizing bacteria on the filler 3 described in being attached to utilizes the vitriol in solution; Part methane enters the floated reaction zone 9 described circulation type oxidation container 4 and upwards flows from the second liquid flow-guiding mouth 8 of bottom, promotes the methane-oxidizing bacteria that the liquid in floated reaction zone 9 promotes circulation to be suspended in the time of mobile and is oxidized; The reduzate hydrogen sulfide of vitriol is discharged from the first air outlet 6 with in time not oxidized methane, through the second inlet mouth 11, enter in gas delivery membrane module 13, the methane that is difficult to see through gas separation membrane is as oozing residual air, by being communicated with the total pipeline 14 eluting gas films of the second air outlet 15, select separation vessels 12, and by the first vacuum pump 17 from the first inlet mouth 5 reflux enter circulation type oxidation container 4, continue oxidized; The hydrogen sulfide, the carbonic acid gas that are easy to see through gas delivery membrane module see through described gas separation membrane as infiltration gas, by the 3rd air outlet 16 and the 3rd inlet mouth 19, enter in solid-liquid separation device 20 and upwards and flow, by the first gas flow guiding hole 23, enter in gas flow guiding container 30 and flow downward, through the second gas flow guiding hole 24, enter flow lifting type regeneration container 27 and upwards flow; Nitrate enters described flow lifting type regeneration container 27 and flows downward from the second water-in 28, and it is vitriol by Oxidation of Hydrogen Sulfide that the thiobacillus denitrificans in the flow lifting type regeneration container 27 described in being suspended in utilizes nitrate, 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; The oxidation products vitriol that contains hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device 20 from the connected entrance 25 of bottom; The membrane module 21 of solid-liquid separation device 20 interior settings is separated with thiobacillus denitrificans by the liquid that contains vitriol; The liquid of containing sulfate is inputted in the fixed reaction zone 2 of circulation type oxidation container 4 from the first water-in 5 through recycle pump 31 from the water outlet 22 of solid-liquid separation device 20, as the oxygenant continuation oxidizing of methylene of regeneration; Water after processing 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 of membrane module 21 tops, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device 20; From the 3rd inlet mouth 19, enter the sulfide hydrogen of solid-liquid separation 20, 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 that film from polluting, promote on the other hand current, make by the first gas flow guiding hole 23 and the second gas flow guiding hole 24, to be back to flow lifting type regeneration container 27 containing the liquid of thiobacillus denitrificans, avoid the loss of thiobacillus denitrificans.
Under room temperature condition, utilize aforesaid combination formula to contain methane waste product and sulfur-bearing nitrogenous effluent associated treatment containing the film biological treating equipment of methane waste product and sulfur-bearing nitrogenous effluent associated treatment.
On the gas distribution grid 33 with a plurality of holes of the inner support fillers of installing in the fixed reaction zone 2 of circulation type oxidation container 4, 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 consisting of the first container, methane-oxidizing bacteria and sulphate reducing bacteria are suspended in 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 that contains thiobacillus denitrificans, the content of thiobacillus denitrificans is 1.0 * 10
6cFU/ml.Gas film is selected, in separation vessel 12,2 gas delivery membrane modules 13 are installed, and gas separation membrane is flat sheet membrane, and mould material is polyimide.The interior membrane module 21 that arranges of solid-liquid separation device 20, membrane module is hollow-fibre membrane, mould material is polypropylene.
The waste gas that contains 31% methane, from the first inlet mouth 1, enter the film biological treating equipment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment, the waste water that contains 267mg/L vitriol enters the film biological treatment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the first water-in 5, the waste water that contains 35mg/L nitrate enters the film biological treating equipment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment from the second water-in 28, 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 is containing 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, on filler 3, be attached with methane-oxidizing bacteria and sulphate reducing bacteria, the interior methane-oxidizing bacteria in the floated reaction zone 9 of circulation type oxidation container 4 and sulphate reducing bacteria, be suspended in solution, the content of methane-oxidizing bacteria is 1.0 * 10
6cFU/ml, the content of sulphate reducing bacteria is 5.0 * 10
9cFU/ml; In flow lifting type regeneration container, be mounted with the aqueous suspension that contains thiobacillus denitrificans, the content of thiobacillus denitrificans is 1.0 * 10
7cFU/ml.Gas film is selected, in separation vessel 12,3 gas delivery membrane modules 13 are installed, and gas separation membrane is rolled film, and mould material is polysulfones.The interior membrane module 21 that arranges of solid-liquid separation device 20, membrane module is flat sheet membrane, mould material is polypropylene.
The waste gas that contains 53% methane, from the first inlet mouth 1, enter the film biological treating equipment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment, the waste water that contains 300mg/L vitriol enters the film biological treatment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment continuously from the first water-in 5, the waste water that contains 125mg/L nitrate enters the film biological treatment of built-up type containing 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 respectively 90.2%, 91% and 79.6%.
Embodiment 3.
Refer to Fig. 1.Built-up type is containing 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, on filler 3, be attached with methane-oxidizing bacteria and sulphate reducing bacteria, the interior methane-oxidizing bacteria in the floated reaction zone 9 of circulation type oxidation container 4 and sulphate reducing bacteria, be suspended in solution, the content of methane-oxidizing bacteria is 1.0 * 10
9cFU/ml, the content of sulphate reducing bacteria is 1.0 * 10
10cFU/ml; In flow lifting type regeneration container, be mounted with the aqueous suspension that contains thiobacillus denitrificans, the content of thiobacillus denitrificans is 1.0 * 10
10cFU/ml.Gas separation membrane is selected, in separation vessel 12,3 gas delivery membrane modules 13 are installed, and gas separation membrane is hollow-fibre membrane, and mould material is polyimide.The interior membrane module 21 that arranges of solid-liquid separation device 20, membrane module is flat sheet membrane, mould material is polysulfones.
The waste gas that contains 60% methane, from the first inlet mouth 1, enter the film biological treating equipment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment, the waste water that contains 1200mg/L vitriol enters the film biological treatment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment continuously from the first water-in 5, the waste water that contains 800mg/L nitrate enters the film biological treatment of built-up type containing 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 respectively 82%, 81% and 70%.
Embodiment 4.
Refer to Fig. 1.Built-up type is containing 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, on filler 3, be attached with methane-oxidizing bacteria and sulphate reducing bacteria, the interior methane-oxidizing bacteria in the floated reaction zone 9 of circulation type oxidation container 4 and sulphate reducing bacteria, be suspended in solution, the content of methane-oxidizing bacteria is 5.0 * 10
10cFU/ml, the content of sulphate reducing bacteria is 1.0 * 10
11cFU/ml; In flow lifting type regeneration container, be mounted with the aqueous suspension that contains thiobacillus denitrificans, the content of thiobacillus denitrificans is 1.0 * 10
11cFU/ml.Gas film is selected, in separation vessel 12,4 gas film assemblies 13 are installed, and the gas separation membrane of gas film assembly 13 is flat sheet membrane, and mould material is polydimethylsiloxane.The interior membrane module 21 that arranges of solid-liquid separation device 20, membrane module is hollow-fibre membrane, mould material is polypropylene.
The waste gas that contains 65% methane, from the first inlet mouth 1, enter the film biological treating equipment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment, the waste water that contains 1800mg/L vitriol enters the film biological treatment of built-up type containing methane waste product and sulfur-bearing nitrogenous effluent associated treatment continuously from the first water-in 5, the waste water that contains 1500mg/L nitrate enters the film biological treatment of built-up type containing 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 respectively 75%, 80% and 70%.
Claims (10)
1. the film biological treating equipment of methane and sulfur-bearing nitrogenous effluent associated treatment, comprises circulation type oxidation container, gas film selection 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 circulation type oxidation container is divided into fixed reaction zone and floated reaction zone, fixed reaction zone is connected by being arranged on first liquid flow-guiding mouth and the second liquid flow-guiding mouth at dividing plate two ends with floated reaction zone, liquid flows downward in fixed reaction zone, in floated reaction zone on flow; Described inside, fixed reaction zone is provided with the gas distribution grid with a plurality of holes, is filled with filler on gas distribution grid, 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 that the second air outlet is set, and the second inlet mouth is set on a sidewall, and the 3rd air outlet is set on another sidewall, and described the second inlet mouth is connected with the first air outlet; Gas film selects the inside of separation vessel that a plurality of gas delivery membrane modules are installed, between a plurality of gas delivery membrane modules, by pipeline, be connected, and the bottom of each gas delivery membrane module is connected with a total pipeline by pipeline separately, one end of a plurality of gas delivery membrane modules 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 between the second air outlet and the first inlet mouth, the first vacuum pump is set;
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 flow;
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 is 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: described the first water-in is higher than first liquid flow-guiding mouth.
4. 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.
5. utilize the film biological treating equipment of the methane described in any one and sulfur-bearing nitrogenous effluent associated treatment in claim 1～4 to contain the method for methane waste product and sulfur-bearing nitrogenous effluent associated treatment: to it is characterized in that: on the filler of the fixed reaction zone of circulation type oxidation container, be attached with methane-oxidizing bacteria and a sulphate reducing bacteria, in floated reaction zone, methane-oxidizing bacteria and sulphate reducing bacteria are suspended in solution; In flow lifting type regeneration container, be mounted with the aqueous suspension that contains thiobacillus denitrificans;
The waste water of containing sulfate enters the fixed reaction zone circulation type oxidation container and flows downward from the first water-in, through described filler, through second liquid flow-guiding mouth, enter floated reaction zone and upwards flow, by first liquid flow-guiding mouth, be back to fixed reaction zone again, thereby circulation in two reaction zones of liquid in circulation type oxidation container is flowed; Meanwhile, be attached on described filler or the sulphate reducing bacteria being suspended in the solution of floated reaction zone is S by sulfate reduction
2-; Methane enters circulation type oxidation container and upwards and flows from the first inlet mouth, and it is carbonic acid gas by methane oxidation that the methane-oxidizing bacteria on the filler described in being attached to utilizes the vitriol in solution; Part methane enters the floated reaction zone described circulation type oxidation container and upwards flows from the second liquid flow-guiding mouth of bottom, promotes the methane-oxidizing bacteria that the liquid in floated reaction zone promotes circulation to be suspended in the time of mobile and is oxidized; The reduzate hydrogen sulfide of vitriol is discharged from the first air outlet with in time not oxidized methane, in the second inlet mouth enters gas delivery membrane module, the methane that is difficult to see through gas separation membrane is as oozing residual air, by being communicated with the total pipeline eluting gas film of the second air outlet, select separation vessel, and by the first vacuum pump from the first inlet mouth reflux enter circulation type oxidation container, continue oxidized; The hydrogen sulfide, the carbonic acid gas that are easy to see through gas delivery membrane module see through described gas separation membrane as infiltration gas, by the 3rd air outlet and the 3rd inlet mouth, enter in solid-liquid separation device and upwards and flow, by the first gas flow guiding hole, enter in gas flow guiding container and flow downward, through the second gas flow guiding hole, enter flow lifting type regeneration container and upwards flow; Nitrate wastewater enters described flow lifting type regeneration container and flows downward from the second water-in, and it is vitriol by Oxidation of Hydrogen Sulfide that the thiobacillus denitrificans in the flow lifting type regeneration container described in being suspended in utilizes nitrate, 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; The oxidation products vitriol that contains hydrogen sulfide and the liquid of thiobacillus denitrificans enter described solid-liquid separation device from the connected entrance of bottom; The membrane module arranging in solid-liquid separation device is separated with thiobacillus denitrificans by the liquid that contains vitriol; The liquid of containing sulfate is inputted from the first water-in through recycle pump in the fixed reaction zone of circulation type oxidation container from the water outlet of solid-liquid separation device, as the oxygenant continuation oxidizing of methylene of regeneration; Water after processing is discharged from water port.
6. method according to claim 5: 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 of membrane module top, reduces operation energy consumption; Thiobacillus denitrificans is trapped within solid-liquid separation device; The hydrogen sulfide containing infiltration gas that enters 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 that film from polluting, promote on the other hand current, make by the first gas flow guiding hole and the second gas flow guiding hole, to be back to flow lifting type regeneration container containing the liquid of thiobacillus denitrificans, avoid the loss of thiobacillus denitrificans.
7. method according to claim 5: it is characterized in that: it is rolled film that described gas is selected the gas separation membrane in separating film module, hollow-fibre membrane or flat sheet membrane, mould material is polyimide, polysulfones or polydimethylsiloxane.
8. method according to claim 5: it is characterized in that: described filler is light porous natural materials or synthetic materials.
9. method according to claim 5: it is characterized in that: the content of the methane-oxidizing bacteria in the described aqueous suspension that contains 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.
10. method according to claim 5: it is characterized in that: the content of the thiobacillus denitrificans in the described aqueous suspension that contains thiobacillus denitrificans is 1.0 * 10
5～1.0 * 10
11cFU/ml.
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| CN107224853A (en) * | 2016-03-25 | 2017-10-03 | 陈晓林 | A kind of method of riser self-loopa depriving hydrogen sulphide |
| CN107285503A (en) * | 2016-04-11 | 2017-10-24 | 中国石油化工股份有限公司 | Oil gas field wastewater with high concentration of sulfide reduces standard discharge method |
| CN109943377A (en) * | 2019-04-17 | 2019-06-28 | 哈尔滨工业大学 | A method of using nitrite as the synchronous strengthening sewage denitrification of the marsh gas purifying of 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 |
| 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 |
| CN111111422A (en) * | 2019-12-05 | 2020-05-08 | 中国科学院生态环境研究中心 | Method for cooperatively treating volatile organic compounds and nitrogen-sulfur-containing malodorous substances |
| CN112479506A (en) * | 2020-12-11 | 2021-03-12 | 中国科学院生态环境研究中心 | Coupled biological-membrane-electrochemical waste gas and wastewater co-treatment method |
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| CN113736717A (en) * | 2021-11-03 | 2021-12-03 | 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 |
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| CN107224853A (en) * | 2016-03-25 | 2017-10-03 | 陈晓林 | A kind of method of riser self-loopa depriving hydrogen sulphide |
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| 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 |
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| 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 |
| CN109943377A (en) * | 2019-04-17 | 2019-06-28 | 哈尔滨工业大学 | A method of using nitrite as the synchronous strengthening sewage denitrification of the marsh gas purifying of electron acceptor |
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| 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 |
| CN112479506A (en) * | 2020-12-11 | 2021-03-12 | 中国科学院生态环境研究中心 | Coupled biological-membrane-electrochemical waste gas and wastewater co-treatment method |
| CN113736717A (en) * | 2021-11-03 | 2021-12-03 | 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 |
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