CN102295352A - Method for removing nitrate nitrogen and device used in same - Google Patents
Method for removing nitrate nitrogen and device used in same Download PDFInfo
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- CN102295352A CN102295352A CN2010102182260A CN201010218226A CN102295352A CN 102295352 A CN102295352 A CN 102295352A CN 2010102182260 A CN2010102182260 A CN 2010102182260A CN 201010218226 A CN201010218226 A CN 201010218226A CN 102295352 A CN102295352 A CN 102295352A
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- draining
- nitrate nitrogen
- denitrogenation
- treatment trough
- sulfur
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Abstract
The invention relates to a method for removing nitrate nitrogen and a device used in the method and provides a method for removing nitrate nitrogen from drainage by using sulfur-oxidizing bacteria in the presence of a nitrogen removal material containing sulfur and calcium components. The method for removing nitrate nitrogen comprises the following steps: passing the drainage containing nitrate nitrogen through a filling layer made of the nitrogen removal material in a drainage treatment tank with the filling layer made of the nitrogen removal material; and circulating at least one part of treated drainage passing through the filling layer to the inlet side of the filling layer or the middle layer of the filling layer. In addition, the device for removing nitrate nitrogen is provided with a circulating pump which is used for circulating at least one part of drainage passing through the filling layer in the drainage treatment tank to the inlet side or middle layer of the filling layer. In the invention, the nitrogen removal material can be a material containing calcium carbonate and sulfur, and ferric oxide can also be coordinated in the nitrogen removal material.
Description
Technical field
The present invention relates to remove the method for nitrate nitrogen in the draining and be used for the device of described method with microorganism.
Background technology
In recent years, because the nitrate ion concentration problems is more and more serious in the draining, the various treatment systems of biological processes method have therefore been considered to use.Particularly, because superfluous in recent years fertilising state causes containing high concentration nitrate nitrogen in the draining of farmlands such as field, tea field, orchard, grassplot, become problem.In addition, contained nitrate nitrogen also is suggested as one of lakes and marhshes eutrophication problem in family's draining such as purification tank.
As corresponding treatment process, the known heterotrophism denitride technology that carries out denitrogenation with the organic carbon source in methyl alcohol or the mud as hydrogen donor, but not only the equal denitrification percent of matrix is low for this technology, also do not discharge to the outside for hydrogen donor superfluous after the denitrogenation, and need remove in addition, so need many treatment facilities or device.
At this problem, owing to use the nitrate nitrogen treatment system of sulphur oxidation process denitrification bacterium to need not to add methyl alcohol or organic carbon source, thus do not need to supply with 2 treatment facilities after necessary equipment or the denitrogenation yet, thereby receive publicity.
The prior art document
Patent documentation
[patent documentation 1] WO2000/18694A
[patent documentation 2] JPH11-285377A
[patent documentation 3] JP2001-104993A
[patent documentation 4] JP2001-93997A
[patent documentation 5] JP2004-174328A
[patent documentation 6] JP2004-237170A
[patent documentation 7] JP2004-255272A
[patent documentation 8] JP2004-322023A
[patent documentation 9] JP2004-298763A
[patent documentation 10] JP2004-167471A
[patent documentation 11] JP2006-015310A
[patent documentation 12] JP2006-015311A
[patent documentation 13] JP2006-015320A
[patent documentation 14] JP2006-142149A
[patent documentation 15] JP2006-142148A
[patent documentation 16] JP2006-255598A
[patent documentation 17] JP2006-272161A
[patent documentation 18] JP2001-347276A
[patent documentation 19] JP2003-071491A
Particularly open flat 11-285377 communique or the special 2001-104993 communique, spy opened opened the molten mixture of inorganic materials of sulfur-bearing in the 2001-93997 communique etc. and lime carbonate set member as solid nutrition with WO2000/18694 communique, spy, and nourish one's nature the method for sulfur-oxidizing bacteria owing to need not power supplys such as pump, whipping appts with independent battalion, so maintenance is demonstrating outstanding effect aspect the denitrogenation processing cost easily.
In addition, the applicant has developed the many denitride technologies that use the denitrogenation material of sulfur-bearing and lime carbonate set member, and it is disclosed in the above-mentioned patent documentation 5～19.
But above-mentioned technology is owing to utilize action of microorganisms, is difficult to follow the tracks of the variation of the temperature, the water yield, Pollutant levels etc. of draining.For example, general sulfur-oxidizing bacteria is active blunt in the low temperature below 15 ℃, with processing power generation change in season, the situation that can't carry out sufficient denitrogenation processing is arranged, and for fear of this situation, needs to import the treatment facility with surplus.In addition, if want denitrogenation to extremely low concentration, then denitrogenation speed reduces, even the problem of hydrogen sulfide etc. also occurs producing according to environment.
Summary of the invention
The technical task that the invention quasi-solution is determined
Therefore, what the purpose of this invention is to provide that the feature that makes the device that utilizes sulfur-oxidizing bacteria gets to the limit performance efficiently removes device, and the described feature of the device of sulfur-oxidizing bacteria of utilizing is always to demonstrate stable nitrogen removal performance; Near producing the draining scene, particularly need not propulsion source etc., safeguard easily.Other purposes of the present invention provide the nitrate nitrogen that can address the above problem a little and remove method.
Solve the technical scheme of problem
The present invention removes method for nitrate nitrogen, it is characterized in that, in the draining treatment trough of the packing layer of denitrogenation material with sulfur-bearing and calcium set member, make the draining that contains nitrate nitrogen packing layer by the denitrogenation material, use sulfur-oxidizing bacteria to remove nitrate nitrogen in the draining, make at least a portion of the processing draining by packing layer turn back to the middle layer of the inlet side or the packing layer of packing layer.
Secondly, the present invention removes device for nitrate nitrogen, it is in the draining treatment trough of the packing layer with the denitrogenation material of filling sulfur-bearing and calcium set member, use sulfur-oxidizing bacteria to remove the device of nitrate nitrogen, it is characterized in that having and make at least a portion of the draining by the packing layer in the described draining treatment trough be recycled to the inlet side of packing layer or the recycle pump in middle layer.
Moreover, the present invention is the denitrogenation material, it is to be used for using sulfur-oxidizing bacteria the nitrate nitrogen of water to be carried out the denitrogenation material of denitrogenation processing, it is characterized in that, described denitrogenation material is formed the coexisting body that comprises lime carbonate and sulphur and ferric oxide, and the iron oxide content of coexistence is that the specific surface area of 1～20wt% and described ferric oxide is 0.1m
2More than/the g, can suppress the generation of hydrogen sulfide.
The accompanying drawing summary
[Fig. 1] shows that nitrate nitrogen of the present invention removes the mode chart of device.
[Fig. 2] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
[Fig. 3] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
[Fig. 4] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
[Fig. 5] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
[Fig. 6] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
[Fig. 7] shows that the nitrate nitrogen of other embodiments of the present invention removes the mode chart of device.
The invention effect
By the present invention, can always demonstrate stable nitrogen removal performance, make effectively removing of nitrate nitrogen that the feature of the method for removing of utilizing sulfur-oxidizing bacteria brought into play to greatest extent.Nitrate nitrogen denitrogenation processing material of the present invention even when nitrate nitrogen is lower concentration in water, also can prevent loss, the death of sulfur-oxidizing bacteria, and can suppress the generation of incidental hydrogen sulfide when the nitrate nitrogen in the water and dissolved oxygen concentration are lower concentration.
Embodiment
Below, the present invention will be described in detail.
The draining that contains nitrate nitrogen is to contain at least a draining that is selected from nitrate ion and the nitrite ion, is called for short draining sometimes.Have in the draining: plant drainage, living drainage, agricultural drainage etc.In addition, the present invention has the situation of big-difference very effective for the temperature of draining, amount, Pollutant levels according to the time, season etc.For example, for have to the draining of the situation below 10 ℃ be effectively, related draining is multiple corresponding to the living drainage in winter, agricultural drainage etc.
The denitrogenation material of sulfur-bearing and calcium set member, can exemplify, as putting down in writing in the above-mentioned distribution publication, Paris white is distributed to the material that obtains in the molten sulfur, perhaps the material that has obtained to wherein having cooperated inorganic fibre or porous material or ion exchangeable material etc.
The calcium set member does not have specific restriction, but preferred lime carbonate.Secondly, the shared ratio of sulphur and calcium set member does not have specific restriction yet in the denitrogenation material, and still, preferred sulphur content is 30～90 weight %, more preferably 40～80 weight %, more preferably 50～70 weight %.When shared sulphur content was less than 30 weight % in the denitrogenation material, the crisp and easy damage of material was therefore impracticable, and surpassed 90 weight %, and then the pH value might become below 5 after the water treatment.
The manufacture method of denitrogenation material is restriction not, but preferably with calcium set members such as limestone powder and free sulfur with about 1: 2～2: 1 mixed, be heated make the sulphur fusion after, again with its cooling curing and integrated, and decide the method that granularity obtains by being crushed to.At this moment, can cooperate inorganic fibre, porous material etc. as required.Sulphur and lime carbonate set member and other add the ratio of material, when depending on these mixture fusion, cooled and solidified, can obtain having decide the integrated thing of intensity, the ratio of sulphur is big more, the intensity aspect has advantage, but the nutrition source of denitrifying bacteria will be unbalance, so will be in above-mentioned scope.Therefore, when cooperating inorganic fibre, porous material etc., cooperate for good in mode with the part of displacement lime carbonate set members such as inorganic fibre, porous material.When cooperating mineral fibre, for 1/10～1/2 scope of lime carbonate set member is good.In addition, as mineral fibre, preferably can exemplify: rock wool, slag wool, glass wool etc.
When using under being easy to generate the environment of hydrogen sulfide, the denitrogenation material is formed the coexisting body that comprises calcium set member, sulphur and ferric oxide, and the iron oxide content of coexistence is 1～20wt%, and the specific surface area of this ferric oxide is 0.1m
2More than/the g, be expected to suppress the generation of hydrogen sulfide.
Here used calcium set member and sulphur can be as hereinbefore.For the generation that prevents the hydrogen sulfide that nitric acid in the draining is easy to generate when being lower concentration and low dissolved axygen makes the ferric oxide coexistence.As ferric oxide, divalent iron and 3 valency iron or its mixture are arranged according to its form.Be specially: FeO, Fe
2O
3, Fe
3O
4, FeOOH (hydrous ferric oxide) etc., but can exemplify on using: naturally occurring iron ore (Fe
2O
3Or Fe
3O
4Be main component), crystallization such as the iron rust that from loess or mine drainage etc., produces or non-crystal hydrous ferric oxide, red iron oxide (Fe
2O
3), the converter ash (Fe that produces from steelworks
2O
3Be main component) etc.At this moment, owing to must catch the hydrogen sulfide of generation at once, the specific surface area of ferric oxide will be at 0.1m
2More than/the g, be preferably 1～100m
2/ g.The amount of the ferric oxide of coexistence is 1～20wt% of denitrogenation material, preferred 2～15wt%.
The above-mentioned denitrogenation material of ferric oxide that contains is owing to the coexisting body that comprises carbonate and sulphur and ferric oxide, so be present in separately in the same treatment unit, if and guarantee to carry out the appropriateness of the catching contact of denitrification reaction and hydrogen sulfide, and then need not to be present in the same particle, also can scatteredly exist.But consider from the capture rate aspect of denitrification reaction and hydrogen sulfide, preferably the particle of each composition integrated existence in same particle.When the denitrogenation material is filled with the independent particle form of each composition, the independent particle of the preferred about 0.5～50mm of diameter.When each composition is present in the same particle with integrated form, with these after micro mist is broken; Mixing, fusion or integrated by the press forming method are good with its particulate matter that further is a granulated into diameter 1～50mm.
Sulfur-oxidizing bacteria is under anaerobic, in the presence of above-mentioned denitrogenation material, and the microorganism that carries out denitrogenation.In order to allow denitrifier breeding around denitrogenation material internal or surface, can be by in the presence of the denitrogenation material, use the draining that contains nitrate nitrogen and denitrifier or soil disperse water to tame and reach.But, when processing contains the draining of nitrate nitrogen and denitrifier, because denitrifier breeding in handling, so not necessarily need domestication.Denitrifier is that main nutrition source carries out growing multiplication, nitrate nitrogen can be broken down into nitrogen with nitrate nitrogen and denitrogenation material.
As sulfur-oxidizing bacteria, sulfur-oxidizing bacteria-sulphur oxidation process denitrification bacterium (Thiobacillus denitrificans) etc. is nourished one's nature for good by the independent battalion that exists with common nature, so long as can carry out growing multiplication as the part of nutrition source with sulphur and carbonic acid part in the denitrogenation material, the sulfur-oxidizing bacteria that nitrate nitrogen is resolved into nitrogen just without limits.
Such sulfur-oxidizing bacteria activity in the low temperature below 15 ℃ that nature exists significantly reduces.Reduce here for anti-, sulfur-oxidizing bacteria is adhered to when being fixed in the denitrogenation material, sulfur-oxidizing bacteria that nature exists or the soil that contains sulfur-oxidizing bacteria are contacted in containing the substratum of nitrate nitrogen with the denitrogenation material, between cultivation institute under 1～10 ℃ the temperature is regular, preferably in denitrogenation material surface and space, cultivate, breed, adhere to fixedly bacterium.Also can there be other trace ingredients etc. in cultural method herein so long as contain and remain on said temperature in the substratum of nitrate nitrogen and get final product.At the incubation time under 1～10 ℃ so long as that bacterium can take place is just passable during adhering to fixed, more than 2 days, preferred more than 10 days, the more preferably incubation time about 1 month.Wherein the draining under cold condition is not used under the situation of denitrogenation material in handling, and can adopt about 15～40 ℃ culture temperature.In addition, in the cultivation, when the nitrate nitrogen concentration in the substratum reduces, add nitrate nitrogen, preferably keep the condition of low dissolved axygen.Because when dissolved oxygen was high, sulfur-oxidizing bacteria consumed dissolved oxygen and does not carry out denitrogenation, the therefore preferred anaerobic state that keeps.
The draining treatment trough is the groove that is filled with above-mentioned denitrogenation material, below can be called for short treatment trough.The shape of treatment trough is unqualified, but the form that flows through the packing layer of denitrogenation material with draining is favourable.Treatment trough can have a plurality of, but this moment configured in series, also can in parallel dispose.Drain treatment apparatus is made of 1 or 1 above treatment trough and pump and other equipment.
Draining is fed into treatment trough, when the packing layer by the denitrogenation material, is subjected to the effect of sulfur-oxidizing bacteria, carries out denitrogenation, and discharges.This moment, method of the present invention was at least a portion circulation that makes by the draining of packing layer in order to improve denitrification percent.Here,, following method is arranged:, then in by the draining before the packing layer, return at least a portion of the draining of passing through if packing layer is one deck as this circulation means; If treatment trough or packing layer have when a plurality of, then at least a portion of the draining in downstream side in being the draining of the above-mentioned upstream side more than 1 or 2, treatment trough or packing layer is returned.In addition, also pending draining can be mixed with processing draining by packing layer, be recycled to the packing layer inlet side again.Though internal circulating load changes with the proterties of draining, the water displacement of supply etc., be 2～500 times of supply water displacement, preferred 10～100 times.In addition, be 2～1500 times/hr of packing layer volume when a plurality of (be cubic capacity), preferred 2～1500 times/hr.With the circulation of such amount, the flow velocity of the draining by packing layer increases, and makes and do not finish denitrification reaction near the denitrogenation material surface, and also carry out denitrification reaction at the denitrogenation material internal that denitrification reaction is carried out, and as a result of, processing speed increases on a large scale.And if carry out denitrification reaction, then the denitrogenation material surface can adhere to bubble, and draining contacts with the denitrogenation material and becomes bad, if but the draining flow velocity is enough, just eliminate bubble easily, and as a result of, processing speed increases.On the other hand, its amount reduces owing to be filled in denitrogenation material slow consumption in the packing layer, if when therefore not appending the denitrogenation material, can reduce internal circulating load.Do not change packing layer and when using for a long time, be good with the internal circulating load that increases the initial stage.
Therefore, nitrate nitrogen of the present invention is removed device and is had the recycle pump of the draining of making at the groove internal recycle, the suction side of this recycle pump links to each other with the downstream side (by the current behind the packing layer) of draining current, discharges side and links to each other with the upstream side (by the middle layer of current before the packing layer or packing layer) of draining current.
It is following that the present invention will be described with reference to accompanying drawing.Among Fig. 1, nitrate nitrogen is removed device 1 and is made of treatment trough 11 and denitrogenation material packing layer 2, recycle pump 4 etc.Treatment trough 11 inside have denitrogenation material packing layer 2; There is upper strata water 9 in the top of packing layer 2, and there is lower floor's water 8 in the bottom.Draining imports treatment trough 11 from water-in 5, mixes with upper strata water 9, is sent to lower floor's water 8 by being disposed near water-in 5 recycle pumps 4 by managing 3.Lower floor's water 8 by packing layer 2, arrives upper strata water 9 again by its rising.Wherein, arrive near the draining of the upper strata water 9 the water outlet 6 be arranged on water-in 5 offsides, discharge from water outlet 6 as treating water.On the other hand, arrive near the draining of recycle pump 4 upper strata waters 9, deliver to lower floor's water 8 by recycle pump 4 once more, circulate.Wherein, packing layer 2 bottoms be have can make draining by but do not allow the structure of the porous plate 7 that the denitrogenation material passes through.
Fig. 2 shows another embodiment, is the example of water-in 5 in the bottom of filling slot 2.Fig. 3 shows another embodiment, though be the top of water-in 5 at filling slot 2, is provided with the example of dividing plate 10, and the packing layer 2 of draining by being separated by dividing plate 10 from water-in 5 is packed into by the packing layer 2 of water outlet 6 sides, arrives upper strata water 9 afterwards.Other symbols among Fig. 2,3 have the implication identical with Fig. 1.These examples have prevented not that the draining by filling slot 2 mixes with the draining of passing through and from the discharge of water outlet 6.
In addition, Fig. 4 shows an embodiment again, is the device that connects 2 treatment troughs.From the draining that the water-in 5 of first treatment trough 41 imports, the same with the example of Fig. 1, by pump 4 circulations, contact with packing layer, arrive upper strata water 9, from pipe connecting 43 outflows, be imported into second treatment trough 42 again.Be imported into the draining of second treatment trough 42, the same with first treatment trough 41, by pump 4 circulations, contact with packing layer, arrive upper strata water 9, discharge as treating water from water outlet 6 again.In Fig. 2～4, the symbol identical with Fig. 1 has identical meanings.
Fig. 5 shows that the nitrate nitrogen that is applicable to when the draining of packing into is low temperature removes the example of device.Nitrate nitrogen is removed device 1 and is constituted by being equipped with treatment trough 11 in the preparation groove 16.Draining is detained therein from the water-in 5 preparation groove 16 of packing into, by pump of constant delivery type 15 treatment trough 11 of packing into.Treatment trough 11 inside have the packing layer 2 of having filled the denitrogenation material, and the bottom links to each other with pump 15, and top is connecting water outlet 6.Wherein, the top of packing layer 2 take the draining by packing layer a part by pipe 3 and recycle pump 4 round-robin structure in preparation groove 16.In addition, treatment trough 11 is configured in the inside of preparation groove 16, draining 14 in store in the preparation groove 16.The arranged outside of preparation groove 16 has band heater 13, to remain on design temperature.Draining flows into preparation groove 16 from water-in 5, after being adjusted to institute's fixed temperature, import by the bottom of pump of constant delivery type 15 from treatment trough 11, contact with the packing layer 2 of denitrogenation material on one side on one side and rise, be subjected to being undertaken denitrogenation in this process by the effect of denitrifier, the gas that produces is 12 discharges from the air outlet, and treating water flows out from water outlet 6.In this device, in a single day draining enters preparation groove 16, just enters treatment trough 11 after fully reaching institute's fixed temperature therein, therefore can not occur in the problem of the active extreme reduction of denitrifier of the denitrogenation material internal of processing layer or periphery existence.Therefore, this device is that even the draining of packing into is the low temperature less than 10 ℃, the activity of denitrifier also can extremely not reduce, and therefore can keep high denitrification percent.
Wherein, treatment trough 11 can not be configured in the preparation groove 16 and independent the setting, but by being configured in the preparation groove 16, makes that treatment trough 11 is controlled to optimum temperuture becomes easy.In addition, the thermal medium of the draining of preparation in the groove as treatment trough heating usefulness can be able to be made the whole even heating of treatment trough, therefore, compare and use the band heater etc. can more excellent efficient heating.In addition, otherwise flow in preparing groove 16 in the time of can making the high warm water discharge of denitrifier death, the preparation groove can have refrigerating unit.
In addition, the preparation groove is owing to can be used as the conservation tank of draining, handle for the draining that for example has the intermittent type flow performance, also can make draining from preparing groove when the treatment trough 11 of having filled the denitrogenation material flows, by carry out continuous water flowing control with pump of constant delivery type, reach the quantitatively water flowing continuously of the influx in treatment trough.
Because the amount of draining essential denitrogenation material in handling depends on drain discharge, for example, even if average daily water displacement is identical, for the situation of continuous drainage on the 1st for the situation that is divided into draining for several times, the big change of flow in the latter's the situation unit time, when being conceived to certain time, the needs that a large amount of drainings are handled are carried out in generation, therefore, compare the situation of continuous and quantitative water flowing, need a large amount of denitrogenation materials, the shortcoming that generation device also becomes excessive.Therefore, above-mentioned preparation groove is irritated as deposit, and pass through pump of constant delivery type, with the logical method of handling draining of concentrated flow of a certain amount of continuous water-flowing amount to the denitrogenation material of having filled sulfur-bearing and calcium set member, the huge effect of performance aspect the miniaturization of equipment from the preparation groove.
In addition, the growing multiplication environment of denitrifier is different with the kind of denitrifier, source etc., but usually with about 30 ℃ for the suitableeest.Therefore, the temperature at discharging condensate that treatment trough is packed into is 10～50 ℃, preferred 15～40 ℃, and more preferably 20～40 ℃.Particularly, when the draining of inflow is less than 15 ℃ in preparing groove 16, preferably be adjusted to than its high temperature more than 10 ℃ the institute's fixed temperature between 15～40 ℃ with well heater 13.
The shape of treatment trough or preparation groove has no particular limits, but from the shape of practicality, preferably drum shape or cuboid.In addition, it is one that these grooves also need not, also can be according to processing intent or the processing power that is required, the groove of combination such as space more than 2 is set.For example, 1 preparation method that a plurality of treatment troughs are set in the groove also is an effective means.The size of preparation groove is 0.5～5 times of a treatment trough volumetrical, preferred 1～3 times.
In addition, making the draining circulation by recycle pump 4, necessarily also is effective for making the water temperature in preparation groove and the draining treatment trough.
Fig. 6 is shown in when denitrification percent reduces in the use, is suitable for making the device of its recovery, and the water-in 5 of circulation is set in the bottom of treatment trough 11, and top sets out the mouth of a river 6, has the packing layer of denitrogenation material in the groove.Import to the draining of packing layer bottom from water-in 5, arrive top by packing layer, a part is discharged from as treating water by water outlet 6, a part by manage 3 and pump 4 be recycled to the processing layer bottom.Treatment trough 11 links to each other by pipe arrangement 22 with the storage groove 21 of interim storage draining, and the monitoring device by being arranged at water port 6 23 is measured the nitrate nitrogen concentration for the treatment of water, simultaneously when the denitrification percent that calculates according to the nitrate nitrogen concentration of measuring reach decide then the switch of valve 24 and 25 and the running of pump 26 to be controlled when following.
In the treatment trough 11, nitrate ion changes into nitrogen often, is slowly accumulated between the denitrogenation material granule by the bubble of the nitrogen that produces.Because such bubble accumulates, hindered contacting of draining and denitrogenation material, and then the nitric efficiency reduction.Measure the nitrate nitrogen concentration of the draining after the processing of from treatment trough 1, discharging with monitoring device 23, when the denitrification percent for the treatment of water drops to set(ting)value when following, switched system (not shown) running of establishing in the monitoring device 23.This switched system valve-off 24 and stop draining and flow into is then opened valve 25, and the driving pump 26 and drainings in the treatment trough 11 are moved to storage groove 21 temporarily is in the emptying process groove 11.Utilize this operation to destroy the bubble that exists between the denitrogenation material granule, nitrogen is emitted.
Switched system does not just turn round during the nitrate nitrogen concentration more than reaching controlling valu, descends and also turns round 5～30% the time when surveying the denitrification percent (initial value) of periodic denitrification percent (measured value) when beginning than denitrogenation processing, also can remove bubble.Wherein, can improve the flow velocity of draining with the circulation of pump 4 generations, also can help the outflow of bubble, prevent that bubble from accumulating by packing layer by circulation.
Bubble is removed after processing finishes, and driving pump 26 and treatment trough 11 is returned in the draining that will preserve in the groove 21 is followed valve-off 25, opens valve 24, begins denitrogenation processing once more.In this operation,, remaining bubble will be washed away in case in the treatment trough 11 of emptying, send into draining.In addition, can expect that also mud that the denitrogenation material surface is adhered to etc. removes.
Monitoring device 23, but can use nitrate ion sensor determination, colorimeter measure, by the instrument of the simple measuring nitrate nitrogens such as gpc analysis of automatic draining sampling.
In addition,, be not limited to above-mentioned embodiment, also comprise following various embodiment as the method for removing bubble.
For example, be provided with valve, pump at drainage inlet and drain outlet, if the denitrification percent of measuring by monitoring device surpasses institute's definite value, the gate of then closing both sides drives recycle pump 4, makes whole circulation.By this operation, make the draining circulation in the treatment trough, remove the bubble of accumulating between the denitrogenation material granule.The circulation of draining can be that the draining current are equidirectional and increase flow velocity during with denitrogenation processing, or makes adverse current (with denitrogenation processing time draining current opposite), can efficiently remove bubble.
In addition, also can in treatment trough, apply vibrations, perhaps in treatment trough, be blown into air and remove bubble by to reducing pressure in the treatment trough by ultrasonic wave.
In addition, substitute above-mentioned monitoring device, also can use with the predetermined space running, stop the timing device that bubble is removed processing.Predetermined space is good with 7 days～6 months scope usually, is made as the short period of time when the nitrate nitrogen concentration of the draining of packing into is high, is made as long-time when nitrate nitrogen concentration is low.
When the denitrogenation of the draining that dissolved oxygen is high is carried out more efficiently, preferably near the inflow part of the high draining of dissolved oxygen, dissolved oxygen is set and reduces means, more preferably the part that treating water contacts with atmosphere in device is provided with dissolved oxygen reduction means.
Reduce means as dissolved oxygen, have: heating, with the oxygen-free gas degassing, add reductive agent, with aerobic-type microbiological treatment (for example with the processing of aerobic-type sulfur-oxidizing bacteria) etc.
Reduce means as dissolved oxygen, have: heating, the reductive agents such as sulphite, usefulness aerobic-type microbiological treatment etc. that carry out aeration, interpolation and dissolved oxygen reaction with the gas of oxygen-free gas such as nitrogen.As processing with the aerobic-type microorganism, use possess the aerobic-type sulfur-oxidizing bacteria, to reduce material with the dissolved oxygen of carbon source and draining neutralizing agent be favourable for free sulfur, sulfur-oxidizing bacteria.
Fig. 7 shows an example of the device that is suitable for handling the many drainings of dissolved oxygen, and it has dissolved oxygen and removes groove 62 and treatment trough 11.Draining enters dissolved oxygen from water-in 5 and removes groove 62, by having filled the packing layer 62 of denitrogenation material.The denitrogenation material of this packing layer 62 can be identical with the denitrogenation material of filling in the treatment trough 11, but preferably be attached with the aerobic-type sulfur-oxidizing bacteria.Like this, can reduce by the dissolved oxygen in the draining of this packing layer 62.The top of removing groove 61 by the draining of packing layer 62 from dissolved oxygen enters the bottom of treatment trough 11 through pipe connecting 63, by having filled the packing layer 2 of denitrogenation material, carries out denitrogenation with the anaerobic type sulfur-oxidizing bacteria.Draining by packing layer 2 is discharged from water outlet 6, but wherein a part through pump 4 and manage 3 bottoms that are recycled to treatment trough 11.
The nitrate nitrogen of Fig. 1～7 is removed device, even still can use under the situation that may produce hydrogen sulfide.At this moment, as the denitrogenation material, use the coexisting body that comprises carbonate salt and sulphur and ferric oxide, the iron oxide content of coexistence is 1～20wt%, and the specific surface area of this ferric oxide is 0.1m
2More than/the g, the denitrogenation material that can suppress the generation of hydrogen sulfide is good.In addition, use beyond sulphur removal and the calcium set member, also coexisted for suppressing the denitrogenation material that hydrogen sulfide produces the ferric oxide of speech significant quantity, and to use the spy to drive the treatment unit of putting down in writing in the 2002-159993 communique also be favourable.Promptly, be suitable for the nourish one's nature denitrogenation method of sulphur oxidation process denitrification bacterium by independent battalion, to be arranged in the groove by the filter material bed that granular or blocky sulfur-bearing filter material is made, simultaneously, the feedwater piping system that to send into processed water in groove is disposed at than the filter material bed groove bottom of below more, and will treating water be sent the outer drainage piping system configuration of groove in than the filter material bed groove top of top more by the filter material bed, as make processed water from the below of filter material bed mobile upward flow mode water treatment trough and constituting upward, and, the denitrogenation material preferably comprises beyond sulphur removal and the calcium set member, also coexisted for suppress hydrogen sulfide produce for the denitrogenation material of ferric oxide of significant quantity.
Embodiment
Embodiment 1:
Use nitrate nitrogen shown in Figure 1 to remove device 1, at the draining round-robin simultaneously, handled nitrate nitrogen.At first, make by water-in 5 flow into draining in the device be filled to decide liquid level (height of water outlet 6).Afterwards, operation cycle pump 4 makes upper water 9 be recycled to the below from the top by managing 3, flows out from the square outlet of bottom.Effusive draining evenly infiltration is filled into the denitrogenation material packing layer 2 on the base plate with open pore and is supplied in denitrogenation.Afterwards from the treating water through denitrogenation of water outlet 6 discharges with the corresponding amount of flow of the draining that flows into from water-in 5.
In the present embodiment, be in the rectangular parallelepiped treatment trough of 100L at capacity, filled sulphur, the lime carbonate blend compositions (tamped density 1.2) of 40kg particle diameter 5～20mm as the denitrogenation material, handled the processed water (water planting draining) 9 of the about 200mg/L of nitrate nitrogen.The denitrogenation material uses by sulphur and limestone powder with 1: 1 (weight ratio) melting mixing, and material crushed, and makes sulphur oxidation process denitrification bacterial adhesion fix and make at normal temperatures.Draining from water-in 5 with flow 6L/hr water flowing, and with the circulation of the internal circulating load of 1200L/hr.Water temperature maintains 25 ℃.
Confirm nitrate nitrogen remove treatment situation over time the time, no significant nitrogen is detained between the denitrogenation material granule, even through 300 days, nitrate nitrogen concentration remaining in the treating water also remained on below the 10mg/L, keeps good denitrification effect after denitrogenation processing begins.
Embodiment 2:
To the inner 3kg denitrogenation material of filling of treatment trough, this denitrogenation material comprises the inorganic materials of the sulphur molten mixture that contains 50 weight part sulphur and 50 weight part lime carbonate being made the particle of diameter 5～20mm scope and obtaining.With this denitrogenation material use from green onion ground, adopt soil in the denitrifier that contains cultivated for 3 weeks.
Use nitrate nitrogen shown in Figure 5 to remove device.Treatment trough is diameter 10cm, the cylinder of long 70cm, and the groove volume of preparation groove 16 is made as about 20L, and the groove volume of treatment trough is made as about 5L, and preparation groove and treatment trough are set at 30 ℃.Draining has been used and big tomb chemistry system OK-F-2 mixed with tap water and has been mixed with the artificial draining of nitrate nitrogen concentration as 200mg/L.Should artificial draining 10 ℃ of temperature at discharging condensates, with the continuous water flowing of 400mL/hr 3 days, studied the nitrate nitrogen (NO of the processing draining of discharging from the treatment trough outlet
3Value) concentration over time.Wherein, internal circulating load is made as 100L/hr or 0.When internal circulating load was 0, its concentration limit value was 3mg/L, and higher limit is 7mg/L; When internal circulating load was 100L/hr, its concentration limit value was 1mg/L, and higher limit is 3mg/L.
On the other hand, when removing device and under similarity condition, handle with the nitrate nitrogen that does not prepare groove, the draining that temperature at discharging condensate is 10 ℃ is directly packed into this temperature from treatment trough inlet, and then the lower value of the nitrate nitrogen concentration of the processing draining of discharging from outlet is 25mg/L, and higher limit is 42mg/L.This moment, internal circulating load was made as 0.
Embodiment 3:
Used nitrate nitrogen shown in Figure 5 to remove device.By big tomb chemistry system OK-F-2 and tap water are hybridly prepared into the artificial draining that nitrate nitrogen concentration is 50mg/L; at 5 ℃ of temperature at discharging condensates, drainage speed 1L/hr; continuous water flowing in 12 hours; during the nitrate nitrogen concentration of the treatment trough outlet after the research internal circulating load is made as 10L/hr or 12 hours at 0 o'clock; internal circulating load be 0 o'clock be 5mg/L, internal circulating load is 2mg/L during for 10L/hr.
Embodiment 4:
With embodiment 3 the same experimentizing.Be mixed with nitrate nitrogen concentration be the artificial draining of 50mg/L under 5 ℃ of temperature at discharging condensates, drainage speed 50mL/min, alternately repeat continuous water flowing in 3 times 1 hour and 1 hour stand-by time, studied the outlet nitrate nitrogen concentration of each groove after the 3rd draining.At this moment, the feed speed that will lead to the draining pump of constant delivery type of treatment trough is set at 400mL/hr.As a result, the nitrate nitrogen concentration of the draining of discharging from treatment trough after the 3rd draining is 3mg/L (internal circulating load 0) and 1mg/L (internal circulating load 40L/hr).
Embodiment 5:
Sulphur and Wingdale with 1: 1 (weight ratio) melting mixing, are ground it and obtain the denitrogenation material.Obtain adhering to the denitrogenation material of having fixed sulphur oxidation process denitrification bacterium at normal temperatures by common method.To adhere to the denitrogenation material of having fixed sulphur oxidation process denitrification bacterium and the denitrogenation material balanced mix of adhering to before fixing, add with saltpetre being adjusted in the substratum that nitrate nitrogen concentration is 200mg/L to, cultivate, adhere to fixing.Substratum remains under 5 ℃ the water temperature, reach time point below the 10mg/L in nitrate nitrogen concentration adds saltpetre and makes nitrate nitrogen concentration reach 200mg/L, cultivates 1 month and obtains low temperature-denitrogenation material.
In the present embodiment, be to fill 40kg low temperature-denitrogenation material in the rectangular parallelepiped treatment trough of 100L to capacity, treatment of nitric acid salt nitrogen is about the draining of 100mg/L.Draining is from the flow water flowing of water-in 5 with 6L/hr, and the internal circulating load circulation with 120L/hr or 0 keeps 5 ℃ or 30 ℃ of water temperatures, has measured the denitrogenation material at low temperature and pyritous nitrogen removal performance.
The draining that will 10 days on-tests to the and the nitrate nitrogen concentration determination for the treatment of water the results are shown in the mean value between 10 days in the table 1.
Wherein, except that substratum remains under 20 ℃ the water temperature, carry out same operation, thereby obtain 20 ℃-denitrogenation material.This denitrogenation material is carried out and above-mentioned same operation, measured the nitrogen removal performance of this denitrogenation material under low temperature and high temperature.Shown the mean value between 10 days in the table 1.If use 20 ℃-denitrogenation material, under 30 ℃, can handle to the lower concentration of the nitrate nitrogen concentration average out to 0.4mg/L for the treatment of water, denitrification percent is the result of demonstration 99.6%; But under 5 ℃ of water temperatures, then can only handle the nitrate nitrogen concentration average out to 63.9mg/L to treating water, denitrification percent is the result of demonstration 41.4%.
[table 1]
| ? | Internal circulating load L/hr | Water temperature | Draining NO 3-N concentration mg/L | Treating water NO 3-N concentration mg/L | Denitrification percent % |
| Low temperature-denitrogenation material | 120 | 5℃ 30℃ | 108.7 107.1 | 0.2 0.2 | 99.8 99.8 |
| Low temperature-denitrogenation material | 0 | 5℃ 30℃ | 108.7 107.1 | 0.4 0.4 | 99.6 99.6 |
| 20 ℃-denitrogenation material | 120 | 5℃ 30℃ | 108.7 107.1 | 35.9 0.2 | 77.0 99.8 |
| 20 ℃-denitrogenation material | 0 | 5℃ 30℃ | 108.7 107.1 | 63.9 0.4 | 41.4 99.6 |
[0103]
Embodiment 6:
Use treatment unit shown in Figure 6; in treatment trough 11 (volume 200L), fill the denitrogenation material (having adhered to autotrophy on the molten mixture of sulphur and Wingdale is the denitrogenation material of sulphur oxidation process denitrification bacterium) of 200kg; to dissolve water culture and be adjusted to the artificial draining that nitrate ion concentration is about 200mg/L, and days flow into and implement denitrogenation processing with 20 ℃ of temperature at discharging condensates, flow 700L/ with fertilizer (big tomb chemistry system OK-F1).Internal circulating load is 7000L/ days or 0.
As monitoring device 23, use nitrate ion transmitter and Personal Computer, according to the nitrate nitrogen denitrification percent of handling draining, the control bubble is removed means (running of the switch of valve 24 and valve 25 and pump 26/stop) and is constituted.
The nitrate nitrogen concentration of setting monitoring device 23 is 10mg/L (denitrification percent 95%), continues to carry out denitrogenation processing in the time of the nitrate nitrogen change in concentration of METHOD FOR CONTINUOUS DETERMINATION treating water.The nitrate nitrogen concentration for the treatment of water is 5mg/L following (denitrification percent 97.5%), but from handling slow increase about two weeks of beginning, when the 23rd day (internal circulating load 0) and the 50th day (internal circulating load 7000L/ days), the running bubble is removed means.At this moment, the draining in the treatment trough 11 is moved to storage groove 21, makes treatment trough 11 emptyings, and afterwards, the draining of storage groove 21 imports draining continuously to treatment trough 11 when returning treatment trough 11, confirm to begin once more denitrogenation processing.
Embodiment 7:
Use device shown in Figure 7, nitrate nitrogen is implemented in the draining of dissolved oxygen 4.5mg/L, nitrate nitrogen 104.1mg/L removed test.
Draining enters dissolved oxygen from water-in 5 and removes groove 61, by having filled the packing layer 62 of denitrogenation material.The denitrogenation material of this packing layer 62 is identical with the denitrogenation material of filling in the treatment trough 11.But adhering to the aerobic-type sulfur-oxidizing bacteria.The draining of removing groove 61 by dissolved oxygen enters treatment trough 11, by denitrogenation material packing layer 2, utilizes the aerobic-type sulfur-oxidizing bacteria to carry out denitrogenation.Draining by packing layer 2 is discharged from water outlet, but wherein a part can be via pump 4 and be managed 3 and circulate.
As the denitrogenation material, used 100 weight part limestone powders and 120 weight part sulphur powder have been mixed, with 650kg/cm
2The particulate matter that compression molding obtains.Filled denitrogenation material 10 weight parts that will adhere in packing layer 2 and 62 the denitrogenation material separately and mixed the material that obtains with new SC material 90 weight parts that do not adhere to sulfur-oxidizing bacteria as the Thiobacillus denitrificans of amphimicrobian type sulfur-oxidizing bacteria.
Dissolved oxygen is removed the denitrogenation material in the groove 61, carries out aerobic treatment in advance, makes sulfur-oxidizing bacteria become the aerobic-type sulfur-oxidizing bacteria, and the denitrogenation material of treatment trough 11 has directly used amphimicrobian type Liu oxidizing bacteria.
Making design temperature is 25 ℃, and with the artificial draining of 5L/ days usefulness pump delivery, internal circulating load was made as 500L/ days or 0 o'clock, final treating water, dissolved oxygen is 0.3mg/L, nitrate nitrogen 0.4mg/L (internal circulating load is 0 o'clock) or 0.2mg/L (when internal circulating load is 500L/ days), and denitrification percent is 99.6% or 99.8%.
Wherein, when the denitrogenation material of removing the denitrogenation material of groove 61 and treatment trough 11 when dissolved oxygen all directly used amphimicrobian type sulfur-oxidizing bacteria, the denitrification percent of final treating water was 94.6% (internal circulating load is 0).
In the glass encloses container of 2000mL, put into the artificial draining that 400mL nitrate ion concentration is 100mg/L, behind dilute sulphuric acid adjusting pH to 4.5, having added Nitchitsu (strain) the system sulphur lime carbonate that 400g inoculated commercially available sulfur-oxidizing bacteria (DSM807) is denitrogenation material (SC material, median size 5～20mm), reach various ferric oxide as shown in table 2 and iron sulphide, iron powder, carry out denitrification test by bulge test.Value in the table is for adding the weight % that material accounts for integral material.Denitrification test carries out under 20 ℃ of the sealing that keeps container and average water temperatures.
Determination experiment begins the nitrate ion concentration and the interior sulfureted hydrogen gas concentration of encloses container of the 5th day the artificial draining in back, and the result is as shown in table 2.
Can confirm: ferric oxide can not make nitrogen removal performance reduce, and can suppress the generation of hydrogen sulfide.On the other hand, do not add, add the situation of iron sulphide and iron powder, though nitrogen removal performance does not reduce, do not observe the inhibition effect to the generation of hydrogen sulfide, the un-added situation of phase inverse ratio also increases.
[table 2]
| ? | |
|
|
Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hydrous |
2 | ? | ? | ? | ? | ? |
| Magnetite | ? | 5 | ? | ? | ? | ? |
| Rhombohedral iron ore | ? | ? | 8 | ? | ? | ? |
| Iron sulphide | ? | ? | ? | ? | 10 | ? |
| Iron | ? | ? | ? | ? | ? | 10 |
| Nitrate ion concentration (mg/l) | 1.8 | 2.1 | 2.2 | 2.0 | 2.6 | 2.2 |
| Hydrogen sulfide generation (ppm) | ＜0.2 | 2.6 | 3.5 | 120 | 390 | 350 |
| Synthetic determination | ○ | ○ | ○ | × | × | × |
To making it integrated by the prescription of table 2 by heating-quick cooling method sulphur/lime carbonate/ferric oxide, after the denitrogenation processing material 200g of 5～10mm Φ that fragmentation obtains inoculates commercially available sulfur-oxidizing bacteria (DSM807), it is preserved in the glass encloses container (4000mL) of artificial draining that 2000mL is adjusted to concentration of nitric acid 50mg/L is housed, carry out denitrification test by bulge test.Denitrification test carries out under 20 ℃ of the sealing that keeps container and average water temperatures.
Determination test begins the nitrate ion concentration and the interior sulfureted hydrogen gas concentration of encloses container of the 5th day the draining in back, and the result is as shown in table 3.
Can confirm: the ferric oxide that coexists in same particle, can not reduce nitrogen removal performance, and can suppress the generation of hydrogen sulfide under this surface-area and coexistence ratio.On the other hand, un-added situation has produced a large amount of hydrogen sulfide.And learn,, and in the many situations of ferric oxide addition,, aspect nitric efficiency can not agree though can prevent the generation of hydrogen sulfide even if ferric oxide when specific surface area hour, then can not fully prevent the generation of hydrogen sulfide.
[table 3]
| ? | |
|
|
Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Sulphur | 58.2 | 54.0 | 57.0 | 54.0 | 59.7 | 45.0 |
| Limestone powder | 38.8 | 36.0 | 38.0 | 36.0 | 39.8 | 30.0 |
| Hydrous |
3 | ? | ? | ? | 0.5 | 25 |
| Rhombohedral iron ore | ? | 10 | ? | ? | ? | ? |
| Rhombohedral iron ore B | ? | ? | ? | 10 | ? | ? |
| Magnetite | ? | ? | 5 | ? | ? | ? |
| Nitrate ion concentration (mg/l) | 0.2 | 0.1 | 0.8 | 1.0 | 0.1 | 13.6 |
| Hydrogen sulfide generation (ppm) | 0.3 | 3.4 | 1.3 | 65 | 62 | 0.4 |
| Synthetic determination | ○ | ○ | ○ | × | × | × |
The proterties of used ferric oxide etc. is as follows.
Hydrous ferric oxide: loess, specific surface area; 40m
2/ g
Magnetite: Fe
3O
4, specific surface area; 80m
2/ g
Rhombohedral iron ore: α-Fe
2O
3, specific surface area; 5m
2/ g
Rhombohedral iron ore B: α-Fe
2O
3, specific surface area; 0.01m
2/ g
Iron sulphide: FeS, specific surface area; 8m
2/ g
Iron: Fe, specific surface area; 1m
2/ g.
Claims (14)
1. nitrate nitrogen is removed method, it is characterized in that,
In the draining treatment trough of the packing layer of denitrogenation material with sulfur-bearing and calcium set member, make the draining that contains nitrate nitrogen packing layer by the denitrogenation material, use sulfur-oxidizing bacteria to remove nitrate nitrogen in the draining, make at least a portion of the processing draining by packing layer be recycled to the middle layer of the inlet side or the packing layer of packing layer.
2. the nitrate nitrogen of claim 1 is removed method, wherein, dispose the preparation groove that is equipped with the temperature control device before the draining treatment trough, when the temperature at discharging condensate that imports the preparation groove is outside institute's fixed temperature scope, use the preparation groove between 10～50 ℃ it, be adjusted to the institute's fixed temperature scope that is suitable at the sulfur-oxidizing bacteria growing multiplication of denitrogenation material internal or periphery existence.
3. nitrate nitrogen is removed method in the draining of claim 1, wherein, after dissolved oxygen reduces processing, imports draining to the draining treatment trough.
4. the nitrate nitrogen of claim 1 is removed method, and wherein, it is fixing in cultivating sulfur-oxidizing bacteria 2 days under 1～10 ℃ the temperature on the denitrogenation material it to be adhered to.
5. the nitrate nitrogen of claim 1 is removed method, wherein, when predetermined space or denitrification percent reduction, carries out the processing of removing that the denitrogenation material surface adheres to bubble, and denitrification activity is recovered.
6. the nitrate nitrogen of claim 5 is removed method, and wherein, the processing of removing of bubble is undertaken by the combination of following method or following method:
● get rid of the treatment trough internal drainage, in case after the emptying, the method that draining is flowed into again;
● make the method for decompression in the treatment trough;
● in treatment trough, apply the method for vibration by ultrasonic wave etc.;
● increase the method for draining flow velocity;
● the circulated in countercurrent method of draining;
● be blown into the method for air to treatment trough.
7. nitrate nitrogen is removed device, it is in the draining treatment trough of the packing layer with the denitrogenation material of having filled sulfur-bearing and calcium set member, use sulfur-oxidizing bacteria to remove the device of nitrate nitrogen, it is characterized in that having and make at least a portion of the draining by the packing layer in the described draining treatment trough be recycled to the inlet side of packing layer or the recycle pump in middle layer.
8. the nitrate nitrogen of claim 7 is removed device, wherein, has the temperature regulation of outfit means before the draining treatment trough, and imports the preparation groove of the draining that contains nitrate nitrogen.
9. the nitrate nitrogen of claim 7 is removed device, and wherein, the draining treatment trough of having filled the denitrogenation material is disposed at preparation groove inside, and the mode that is dipped in the draining for preparing in the groove with at least a portion constitutes.
10. the nitrate nitrogen of claim 7 is removed device, and wherein, the draining treatment trough is equipped with the temperature regulation means.
11. the nitrate nitrogen of claim 7 is removed device, wherein, has dissolved oxygen before the draining treatment trough and reduces means.
12. the nitrate nitrogen of claim 11 is removed device, wherein, dissolved oxygen reduction means are at least a kind of means that is selected from the following means:
● with the processing of aerobic-type oxidizing bacteria,
● add reductive agent,
● heat treated, and
● with the gas aeration of oxygen-free gas.
13. the nitrate nitrogen of claim 7 is removed device, wherein, the denitrogenation material comprises the coexisting body of carbonate salt and sulphur and ferric oxide, and can suppress the material of the generation of hydrogen sulfide.
14. nitrate nitrogen denitrogenation processing material, it is to be used for using sulfur-oxidizing bacteria the nitrate nitrogen of water to be carried out the denitrogenation material of denitrogenation processing, it is characterized in that, described denitrogenation material is formed the coexisting body that comprises carbonate salt and sulphur and ferric oxide, and the iron oxide content of coexistence is that the specific surface area of 1～20wt% and described ferric oxide is 0.1m
2More than/the g, can suppress the generation of hydrogen sulfide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626293A (en) * | 2013-12-17 | 2014-03-12 | 南京大学 | Natural pyrrhotite biological filter and method for synchronously removing nitrate nitrogen and phosphorus out of water by using natural pyrrhotite biological filter |
| CN104609545A (en) * | 2013-11-05 | 2015-05-13 | 中国科学院沈阳应用生态研究所 | Method and apparatus for biochemical treatment of high concentration nitrate wastewater |
| CN105923757A (en) * | 2016-05-11 | 2016-09-07 | 深圳市瑞清环保科技有限公司 | Method for phosphorus removal and denitrification through iron elementary substance cooperating with sulfur autotrophic denitrification |
| CN108793408A (en) * | 2018-07-23 | 2018-11-13 | 萍乡市华星环保工程技术有限公司 | A kind of aerator based on A1-A2-O techniques |
| CN109607778A (en) * | 2019-01-31 | 2019-04-12 | 北京潮白环保科技股份有限公司 | The processing method of the carrier of nitrate in a kind of removal water body |
| CN115231692A (en) * | 2022-09-23 | 2022-10-25 | 中科格润(唐山)环境技术有限公司 | Synchronous nitrogen and phosphorus removal filler and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003024989A (en) * | 2001-07-19 | 2003-01-28 | Mitsubishi Heavy Ind Ltd | Denitrification apparatus |
| WO2003093180A1 (en) * | 2002-05-02 | 2003-11-13 | Korea Institute Of Science And Technology | Biological denitrification apparatus and method using fluidized-bed reactor filled with elemental sulfur |
| WO2004031084A1 (en) * | 2002-09-30 | 2004-04-15 | Nippon Steel Chemical Co., Ltd. | Method of removing nitrate nitrogen and device used for the method |
| JP2004154759A (en) * | 2002-09-10 | 2004-06-03 | Nippon Steel Chem Co Ltd | Nitrate nitrogen denitrifying treatment material |
| CN101050031A (en) * | 2007-05-11 | 2007-10-10 | 哈尔滨工业大学 | Method and reactor for removing organic matter, sulfide, and nitrate in wastewater synchronistically |
| CN201024125Y (en) * | 2007-02-07 | 2008-02-20 | 北京市环境保护科学研究院 | Nitrosation-anaerobic ammonium oxidation coupled synergistic biological denitrification device |
-
2010
- 2010-06-28 CN CN2010102182260A patent/CN102295352A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003024989A (en) * | 2001-07-19 | 2003-01-28 | Mitsubishi Heavy Ind Ltd | Denitrification apparatus |
| WO2003093180A1 (en) * | 2002-05-02 | 2003-11-13 | Korea Institute Of Science And Technology | Biological denitrification apparatus and method using fluidized-bed reactor filled with elemental sulfur |
| JP2004154759A (en) * | 2002-09-10 | 2004-06-03 | Nippon Steel Chem Co Ltd | Nitrate nitrogen denitrifying treatment material |
| WO2004031084A1 (en) * | 2002-09-30 | 2004-04-15 | Nippon Steel Chemical Co., Ltd. | Method of removing nitrate nitrogen and device used for the method |
| CN201024125Y (en) * | 2007-02-07 | 2008-02-20 | 北京市环境保护科学研究院 | Nitrosation-anaerobic ammonium oxidation coupled synergistic biological denitrification device |
| CN101050031A (en) * | 2007-05-11 | 2007-10-10 | 哈尔滨工业大学 | Method and reactor for removing organic matter, sulfide, and nitrate in wastewater synchronistically |
Non-Patent Citations (1)
| Title |
|---|
| 王占生 等: "硫/石灰石滤柱去除地下水中硝酸盐的研究", 《环境工程》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104609545A (en) * | 2013-11-05 | 2015-05-13 | 中国科学院沈阳应用生态研究所 | Method and apparatus for biochemical treatment of high concentration nitrate wastewater |
| CN103626293A (en) * | 2013-12-17 | 2014-03-12 | 南京大学 | Natural pyrrhotite biological filter and method for synchronously removing nitrate nitrogen and phosphorus out of water by using natural pyrrhotite biological filter |
| CN105923757A (en) * | 2016-05-11 | 2016-09-07 | 深圳市瑞清环保科技有限公司 | Method for phosphorus removal and denitrification through iron elementary substance cooperating with sulfur autotrophic denitrification |
| CN108793408A (en) * | 2018-07-23 | 2018-11-13 | 萍乡市华星环保工程技术有限公司 | A kind of aerator based on A1-A2-O techniques |
| CN108793408B (en) * | 2018-07-23 | 2021-10-08 | 萍乡市华星环保工程技术有限公司 | Aeration device based on A1-A2-O process |
| CN109607778A (en) * | 2019-01-31 | 2019-04-12 | 北京潮白环保科技股份有限公司 | The processing method of the carrier of nitrate in a kind of removal water body |
| CN115231692A (en) * | 2022-09-23 | 2022-10-25 | 中科格润(唐山)环境技术有限公司 | Synchronous nitrogen and phosphorus removal filler and preparation method thereof |
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