CN102173509B - Plate-frame immobilized cell membrane bioreactor and application thereof - Google Patents
Plate-frame immobilized cell membrane bioreactor and application thereof Download PDFInfo
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- CN102173509B CN102173509B CN201110062809A CN201110062809A CN102173509B CN 102173509 B CN102173509 B CN 102173509B CN 201110062809 A CN201110062809 A CN 201110062809A CN 201110062809 A CN201110062809 A CN 201110062809A CN 102173509 B CN102173509 B CN 102173509B
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Abstract
The invention discloses a plate-frame immobilized cell membrane bioreactor. The bioreactor is characterized in that cover plates are arranged on the outmost layers; the middle part is formed by successively arranging and assembling frames and flat-shaped immobilized cells; the frames include W frames and a C frame; the W frames represent the frames for the underground water to flow; the C frame represents the frame for the ethanol water to flow; the arrangement sequence of the cover plates, the frames and the flat-shaped immobilized cells is as follows: one cover plate, one W frame, one flat-shaped immobilized cell, the C frame, the other flat-shaped immobilized cell, the other W frame and the other cover plate; the lower and upper ends of the W frames and the C frame are respectively provided with inlets and outlets; and bolt holes are arranged around the cover plates and the frames. The bioreactor has the following advantages: the oxygen in the air is avoided from being dissolved in the underground water and ethanol water in the reactor, thus reducing the adverse effects of the dissolved oxygen on denitrification; at the same time, the effective reaction area of the immobilized cell in unit volume and the treatment capability in unit volume are obviously improved; and besides, recycling of the carbon source of denitrification is also realized, thus reducing waste of the carbon source of denitrification.
Description
Technical field
The present invention relates to drinking water safety safeguards technique field, specifically, relate to a kind of plate and frame immobilized cell membrane bioreactor and the application in underground water biological denitrification denitride technology thereof.
Background technology
Underground water is the main drinking water source of many countries and regions, as the U.S. surpass half the population with underground water as tap water; Holland's tap water 2/3 comes from underground water.China shows that to the statistics of 21 provinces and cities and 27 main cities it is main water source with underground water that city over half is arranged.Yet,, cause the nitrate concentration in the underground water to continue to rise owing to reasons such as irrational use chemical fertilizer, sewage irrigation and effluent seepages.Nitrate salt is ingested behind the human body, in stomach, is reduced to nitrite, and the latter can be the Fe in the oxyphorase
2+Be oxidized to Fe
3+, reduce the oxygen carrier capacity of blood, thereby have the danger that causes various diseases, like methemoglobinemia, hepatic injury and cancer etc.
For preventing be detrimental to health by the underground water of azotate pollution, many in the world countries and international organization have all set ceiling value to the content of nitrate salt in the tap water.The tap water nitrate salt limit value of in " drinking-water quality criterion " (the 3rd edition) of publishing in 2004, recommending like The World Health Organization (WHO) is 50mg NO
3 -/ L; U.S. EPA and Canadian environmental organization have stipulated that the upper limit (UL) value of nitrate nitrogen concentration is 10mgNO in the tap water
3 --N/L.European Union has proposed that the nitrate salt maximum permissible concentration is 50 mgNO in the tap water
3 -/ L, the horizontal 5.6mgNO of permission of recommendation nitrate nitrogen
3 --N/L.The nitrate salt limit value that China's " drinking water sanitary standard " (GB5749-2006) stipulates is that 10mg/L is (with NO
3 --N meter).
The method of reducing to nitrate in groundwater concentration below the standard value mainly contains IX, r-o-and biological denitrification etc.IX has similar shortcoming with r-o-, and the both understands the by-product strong brine, needs further to handle or dispose.Biological denitrification is relatively inexpensive denitrogenation method, promptly under anoxic or anaerobic environment, denitrifying bacterium with organism as the oxygen in electron donor, the nitrate salt molecule as final electron acceptor(EA), become nitrogen to nitrate reduction.The biological denitrification process can by-product salt solution.
In decades recently, the biological denitrification technology is obtaining broad research aspect the underground water denitration, but practical applications that should technology seldom, and reason is that conventional biological denitrification can't be avoided the pollution to treating water of mikrobe and electron donor.Therefore, correlative study focuses on the membrane bioreactor (MBR) that bioprocess combines with membrane separation technique and forms.MBR can avoid underground water to receive microbial contamination fully, but still can't solve residual electron donor to phreatic pollution problem.
Chinese patent (CN101786763A) discloses a kind of batch-type groundwater denitrifying method; Promptly organically combine immobilized cell technique and membrane separation technique; Made up a kind of new membrane bio-reactor of periodical operation; Utilize this new membrane bio-reactor to carry out groundwater denitrifying, can overcome the shortcoming that exists in conventional biological denitrification and the common MBR denitrification denitrogenation process.But, when operation, need underground water and the aqueous ethanolic solution in the continuous stirred reactor because this new membrane bio-reactor is a kind of unlimited system, particularly this reactor drum, thereby eliminate the influence of external diffusion anti-nitration reaction.But, the stirring that continues also makes the surface of underground water and aqueous ethanolic solution bring in constant renewal in, and this has just increased the dissolving of oxygen in underground water and aqueous ethanolic solution in the atmosphere inevitably.The increase of dissolved oxygen in underground water and the aqueous ethanolic solution; Can improve the speed that dissolved oxygen spreads again from the liquid of both sides in shaped immobilized cell; Make the top layer zone dissolved oxygen concentration higher (be in oxygen condition) of shaped immobilized cell near underground water or aqueous ethanolic solution; On the thickness of whole shaped immobilized cell, have only region intermediate to be in hold concurrently oxygen or anaerobic state in other words, satisfy the condition of biological denitrification.That is to say; The denitrification zone of shaped immobilized cell has been dwindled in the increase of dissolved oxygen, and therefore, the denitrogenation speed of this batch-type groundwater denitrifying method is slow; The practical applications that is unfavorable for this groundwater denitrifying method; And airborne oxygen constantly dissolves in the aqueous ethanolic solution, also can promote mikrobe that alcoholic acid is degraded, and increases alcoholic acid consumption.In addition, the useful area of membranaceous immobilized cell is smaller in this batch-type groundwater denitrifying technology unit reactor volume, compares with general MBR, reaches the required reactor volume of same treatment ability and is so great that many.If thoroughly do not change the structure of reactor drum, be difficult to improve the processing power of unit reactor volume.
Summary of the invention
The object of the present invention is to provide a kind of continuous, airtight, plate and frame immobilized cell membrane bioreactor.
Second purpose of the present invention is to provide a kind of method of underground water continous way denitrification denitrogenation, and realizes the recycle of electron donor denitrifying carbon source.
For realizing above purpose, the present invention discloses following technical scheme: a kind of plate and frame immobilized cell membrane bioreactor is characterized in that; Outermost layer is two cover plates; Middle portion is arranged in order by frame and tabular immobilized cell and assembles, and said tabular immobilized cell is made by the denitrifying bacterium and the polyvinyl alcohol solution blend of enrichment culture, and said frame is rectangle; Comprise W frame and C frame; W frame representative supplies the frame of underground water circulation, and the representative of C frame supplies the frame of aqueous ethanolic solution circulation, and said middle portion comprises two tabular immobilized cells, two W frames and a slice C frame at least; Its cover plate, frame and tabular immobilized cell put in order for; Cover plate-W frame-tabular immobilized cell-C frame-tabular immobilized cell-W frame-cover plate, wherein W frame and C frame lower end and upper end are offered entrance and exit respectively, all have bolt hole around cover plate and the frame.
This reactor simulation underground water passes through the W frame successively with series system; Aqueous ethanolic solution then passes through the C frame with series system successively.First W frame upper end is exported under second W frame and connects through conduit between the end entrance, and the connection between more W frames by that analogy; In like manner, first C frame upper end is exported under second C frame and connects through conduit between the end entrance, and the connection between more C frames by that analogy.Briefly, couple together the outlet and the inlet of two W frames or C frame with a pipe exactly.
As a preferred version, also be coated with millipore filtration towards the tabular fixation cell cellular surface of W frame, be used for preventing the microbial contamination underground water that splits away off from the tabular immobilized cell.
For realizing above second purpose; The present invention discloses following technical scheme, and a kind of method of underground water continous way denitrification denitrogenation is characterized in that; Be delivered to underground water from its storage tank the inlet of first W frame lower end of above-mentioned plate and frame immobilized cell membrane bioreactor; Underground water in the W frame on flow, flow into the inlet of next W frame lower end from the outlet of this W frame opposite side upper end through conduit, the underground water of handling is discharged from the outlet of last W frame upper end; Be transported to aqueous ethanolic solution from its storage tank the inlet of first C frame lower end simultaneously; Aqueous ethanolic solution in the C frame on flow; Flow into the inlet of next C frame lower end through conduit from this C frame opposite side upper end outlet; And return the aqueous ethanolic solution storage tank from the outlet of last C frame upper end, recycle.
When underground water in the W frame on when flowing; Nitrate salt diffuses into the tabular immobilized cell from water; Be fixed in wherein denitrifying bacteria utilization and from opposite side C frame, spread the ethanol that comes and become nitrogen to nitrate reduction, realize the purpose of denitrification denitrogenation as electron donor.
The invention has the advantages that: (1) plate and frame immobilized cell membrane bioreactor is continuous, an airtight reactor drum; Underground water and aqueous ethanolic solution continuous flow in different frames; Control suitable flow velocity; Can make the frame inner fluid reach higher level of disruption, thereby eliminate the influence of external diffusion plate and frame membrane bioreactor denitrification denitrogenation process; (2) can avoid airborne oxygen constantly to dissolve in the underground water and aqueous ethanolic solution in the reactor drum, reduce the disadvantageous effect that dissolved oxygen produces denitrification denitrogenation; (3) because the thickness of frame is much littler than teeter column in the intermittence stirred reactor; Therefore plate and frame immobilized cell membrane bioreactor unit volume internal fixing born of the same parents' effecting reaction area is much bigger, thereby has improved the processing power of unit reactor volume greatly; (4) plate and frame immobilized cell membrane bioreactor can be realized recycling of denitrifying carbon source aqueous ethanolic solution, has reduced the waste of denitrifying carbon source.
Description of drawings
Fig. 1 is plate and frame immobilized cell membrane bioreactor and denitrification denitrogenation schematic flow sheet thereof.
Fig. 2 is cover plate, frame, the millipore filtration in the plate and frame immobilized cell membrane bioreactor, the structural representation of tabular immobilized cell.
Fig. 3 is the continuous denitrification denitrogenation effect of plate and frame immobilized cell membrane bioreactor.
Fig. 4 is water inlet nitrate nitrogen load and water outlet COD in the continuous operational process of plate and frame immobilized cell membrane bioreactor
MnVariation.
Wherein, the label among Fig. 1, Fig. 2 is respectively: 1. underground water storage tank; 2. carry phreatic pump; 3. aqueous ethanolic solution storage tank; 4. carry the pump of aqueous ethanolic solution; 5. cover plate; 6. supply the frame (being called for short the W frame) of underground water circulation; 7. millipore filtration; 8. tabular immobilized cell; 9. supply the frame (being called for short the C frame) of aqueous ethanolic solution circulation; 10. bolt hole; 11. the inlet of W frame; 12. the outlet of W frame; 13. the inlet of C frame; 14. the outlet of C frame.
Embodiment
Below in conjunction with accompanying drawing the present invention is elaborated, the effect of embodiment only is to explain and non-limiting the present invention.
Embodiment one: the structure of plate and frame immobilized cell membrane bioreactor.
(1) enrichment culture of denitrifying bacterium: in every liter of zero(ppm) water, add saltpetre 2000mg/L respectively; Ethanol 1500mg/L, calcium chloride 350mg/L, sal epsom 300mg/L; The 0.2mol/L phosphate buffered saline buffer 0.5mL of pH 7.2 constitutes denitrifying bacterium enrichment culture liquid.Join the active sludge of taking from city domestic sewage treatment plant in the denitrifying bacterium nutrient solution, carry out the denitrifying bacterium enrichment culture.Cultivate the reactor drum stirring reaction every day 20h of denitrifying bacterium, quiescent setting 4h discharges supernatant with siphonage, and then adds fresh denitrifying bacterium nutrient solution and carry out the next round operation, and continuous service 70d obtains denitrifying bacterium suspension-s.
(2) Z 150PH (PVA) solution preparation: PVA places the 1000mL beaker the 90g solid, adds 580mL zero(ppm) water, beaker is placed on the boiling water bath heat then; Heat while stirring to PVA and dissolve fully; Stop the heating, naturally cool to room temperature after, add an amount of zero(ppm) water; Be settled to 600mL to PVA solution, then the concentration of gained PVA solution is 15% (w/v).In gained PVA solution, add 24mL glycerine at last again, the back that stirs is subsequent use.
(3) preparation of tabular fixed cell: with the denitrifying bacterium suspension-s of step (1) gained at 3000rmin
-1Following centrifugal 15min; Abandoning supernatant with saline water washing also centrifugal 2 times, takes by weighing 12.0g then and concentrates thalline; It is joined in the PVA solution that step (2) prepared; Be tiled in after stirring in the plate and frame model of 4 350mm * 100mm * 4mm, place-20 ± 1 ℃ refrigerator and cooled to freeze 16h, 4h then at room temperature thaws.Repeated freezing-thaw 4 times with zero(ppm) water thorough washing film surface, promptly gets the tabular fixed cell.
(4) structure of plate and frame immobilized cell membrane bioreactor: cover plate, W frame, millipore filtration, tabular immobilized cell, C frame, tabular immobilized cell, millipore filtration, W frame, millipore filtration, tabular immobilized cell, C frame, tabular immobilized cell, millipore filtration, W frame, cover plate precedence are arranged; Inserting bolt in the bolt hole around plate and frame; Tighten the nut of two side cover plate outside surfaces then; Tighten together plate and frame, promptly get plate and frame immobilized cell membrane bioreactor.The useful volume of W frame and C frame is 60 mL (30 cm * 2 cm * 1 cm), and the aperture of millipore filtration is 0.45 μ m.
Among Fig. 1, first W frame upper end is exported under second W frame has single line between the end entrance, and this line is just represented two linking conduits between the W frame; In like manner, first C frame upper end is exported under second C frame has single line between the end entrance, and this line is just represented two linking conduits between the C frame.Briefly, couple together the outlet and the inlet of two W frames or C frame with a pipe exactly.
Embodiment two: underground water continous way denitrification denitrogenation.
The use pump is nitrate nitrogen concentration the underground water of 16 ~ 100mg/L is transported to first W frame lower end of plate and frame immobilized cell membrane bioreactor shown in Figure 1 from the underground water storage tank with the flow of 50mL/h a inlet; Underground water in the W frame on flow; Flow into the inlet of next W frame lower end through conduit from the outlet of this W frame opposite side upper end; Connection between more W frames by that analogy, the underground water of handling is discharged from the outlet of last W frame upper end; Using pump simultaneously is ethanol content the aqueous ethanolic solution of 130 ~ 1725mg/L is transported to first C frame lower end from the aqueous ethanolic solution storage tank with the flow of 500mL/min inlet; Aqueous ethanolic solution in the C frame on flow; Flow into the inlet of next C frame lower end through conduit from this C frame opposite side upper end outlet; Connection between more C frames and is returned the aqueous ethanolic solution storage tank from the outlet of last C frame upper end by that analogy, recycles.
Every separated 24h is respectively from underground water storage tank, treating water relief outlet, aqueous ethanolic solution storage tank sampling and measuring water inlet nitrate nitrogen concentration, water outlet nitrate nitrogen, nitrite nitrogen and COD
MnConcentration, and concentration of ethanol in the aqueous ethanolic solution, and in the aqueous ethanolic solution storage tank, replenish used up ethanol in the denitrification process according to the variation of alcohol concn.Test-results is shown in accompanying drawing 3 and 4.
Can find out that by Fig. 3 when water inlet nitrate nitrogen concentration rises to the process of 100 mg/L from 16mg/L gradually, the running status of reactor drum can receive impact to a certain degree, but tends towards stability soon.After the operation of reactor drum got into stable state, water outlet nitrate nitrogen concentration was all below 3 mg/L.And, under steady state conditions, the accumulation of nitrite nitrogen does not appear in the water outlet, and the nitrite nitrogen concentration is less than 0.1mg/L.
Can find out by Fig. 4, in reactor load less than 3.5g NO
3 --N/m
2During d (corresponding aqueous ethanolic solution concentration is less than 1250mg/L), water outlet COD
MnContent is less than 3mg/L.And, even alcohol concn up to 1725mg/L, water outlet COD
MnContent does not surpass 5mg/L yet.
Synthesizing map 3 and result shown in Figure 4 are not difficult to find out, handle the underground water that receives azotate pollution continuously with plate and frame immobilized cell membrane bioreactor, when the running status of reactor drum reach stablize after, water outlet nitrate nitrogen, nitrite nitrogen and COD
MnAll meet " drinking water sanitary standard " requirement (GB5749-2006) etc. index.Show that it is fully feasible handling the underground water that receives azotate pollution continuously with method of the present invention.
In addition, it can also be seen that the maximum load of plate and frame immobilized cell membrane bioreactor is 5.0g NO nearly by Fig. 4
3 --N/m
2D; Suitable (the Ergas S J of common MBR denitrification denitrogenation load with bibliographical information; Rheinheimer D E. Drinking water denitrification using a membrane bioreactor. Water Research; 2004,38 (14-15): 3225 – 3232), be equivalent to 3 times of publication CN101786763A report.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (3)
1. a plate and frame immobilized cell membrane bioreactor is characterized in that, outermost layer is two cover plates; Middle portion is arranged in order by frame and tabular immobilized cell and assembles, and said tabular immobilized cell is made by the denitrifying bacterium and the polyvinyl alcohol solution blend of enrichment culture, and said frame is rectangle; Comprise W frame and C frame; W frame representative supplies the frame of underground water circulation, and the representative of C frame supplies the frame of aqueous ethanolic solution circulation, and said middle portion comprises two tabular immobilized cells, two W frames and a slice C frame at least; Its cover plate, frame and tabular immobilized cell put in order for; Cover plate-W frame-tabular immobilized cell-C frame-tabular immobilized cell-W frame-cover plate, wherein W frame and C frame lower end and upper end are offered entrance and exit respectively, all have bolt hole around cover plate and the frame; First W frame upper end is exported under second W frame and connects through conduit between the end entrance, and the connection between more W frames by that analogy; In like manner, first C frame upper end is exported under second C frame and connects through conduit between the end entrance, and the connection between more C frames by that analogy.
2. plate and frame immobilized cell membrane bioreactor according to claim 1 is characterized in that, towards the tabular immobilized cell surface coverage of W frame millipore filtration is arranged.
3. method of utilizing claim 1 or 2 described plate and frame immobilized cell membrane bioreactors underground water to be implemented the continous way denitrification denitrogenation; It is characterized in that; Be delivered to underground water from its storage tank the inlet of first W frame lower end; Underground water in the W frame on flow, flow into the inlet of next W frame lower end from the outlet of this W frame opposite side upper end through conduit, the underground water of handling is discharged from the outlet of last W frame upper end; Be transported to aqueous ethanolic solution from its storage tank the inlet of first C frame lower end simultaneously; Aqueous ethanolic solution in the C frame on flow; Export the inlet that flows into next C frame lower end through conduit from this C frame opposite side upper end, and return the aqueous ethanolic solution storage tank from the outlet of last C frame upper end.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480400A2 (en) * | 1990-10-11 | 1992-04-15 | Endotronics, Inc. | Process and apparatus for improving mass transfer in a membrane bioreactor and providing a more homogeneous culture environment |
| CN101786763A (en) * | 2010-01-26 | 2010-07-28 | 华东理工大学 | Batch-type groundwater denitrifying method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480400A2 (en) * | 1990-10-11 | 1992-04-15 | Endotronics, Inc. | Process and apparatus for improving mass transfer in a membrane bioreactor and providing a more homogeneous culture environment |
| CN101786763A (en) * | 2010-01-26 | 2010-07-28 | 华东理工大学 | Batch-type groundwater denitrifying method |
Non-Patent Citations (1)
| Title |
|---|
| 曹国民等.新型固定化细胞膜反应器脱氮研究.《环境科学学报》.2001,第21卷(第2期), * |
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