CN109721163A - The method for handling the waste water containing nitrate ion - Google Patents
The method for handling the waste water containing nitrate ion Download PDFInfo
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Abstract
The present invention relates to field of waste water treatment, disclose the method for waste water of the processing containing nitrate ion.The described method includes: the waste water containing nitrate ion is introduced cultivating system and provides nitrogen source for microalgae during microdisk electrode, after culture, draws at least partly micro algae culturing liquid and be separated by solid-liquid separation.The present invention absorbs the nitrate ion in waste water using microalgae, realize the purpose of microalgae processing waste water containing nitrate ion, treatment effeciency and stability are higher, and obtain microalgae biomass with high yield while handling waste water, with good economic efficiency and ecological, social benefit.
Description
Technical field
The present invention relates to field of waste water treatment, and in particular to a method of waste water of the processing containing nitrate ion.
Background technique
The fast development of human society is greatly improved the demand to water resource.And the acceleration of process of industrialization is changing
Serious water pollution is brought while philanthropists' quality of life.Many kinds of, the wherein nitrogenous effluent of water pollutant, especially
Waste water containing nitrate ion all brings serious threat to human health, ecological environment.All over the world, in drinking water
The exceeded situation of nitrate happens occasionally.And nitrogen content excessively high phenomena such as leading to eutrophication, water body aging in environment water
Bring serious ecocatastrophe, and the recovery of water environment be even more it is extremely difficult with it is very long.Therefore, waste water containing nitrate ion
Processing be always water treatment field hot spot and difficult point and emphasis.
The method handled at present waste water containing nitrate ion mainly has biological denitrification method, neutralisation and chemistry also
Former method etc. is several.The widest method of application is biological denitrification method, and this method is made using the denitrification of denitrifying bacteria
With, by nitrate-nitrogen reduction be nitrogen, discharge into atmosphere.But since the denitrifying bacteria speed of growth is slow, denitrification efficiency is low, right
The limitation for the factors such as pH tolerance range is narrow, this method can not handle the waste water containing nitrate ion of high concentration, need with a large amount of
Water be diluted, take up a large area, lead to cost for wastewater treatment height.Neutralisation using alkaline matter to the nitric acid in waste water into
Row neutralizes, then is handled by modes such as concentrates.This method is practical only to convert nitrate for nitric acid, and there is no really
Pollutant is purged.Chemical reduction method utilize nitrate ion oxidisability, using chemical reducing agent by nitrate nitrogen also
It originally was nitrogen or ammonia.This method needs to add a large amount of medicaments, may bring new pollution, and the ammoniacal nitrogen for restoring generation is also
Serious pollutant needs to be further processed, is easy to produce secondary pollution.It can be efficient as can be seen that also lacking at present
Rate handles the technology of the waste water of the nitrate ion containing higher concentration.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that treatment effeciency of the existing technology is not high, processing is provided containing nitric acid
The method of the waste water of radical ion.
The present inventor has been surprisingly found that under study for action, largely removes nitre although existing in the waste water containing nitrate ion
Ion (such as hydrogen ion, sodium ion, potassium ion) other than acid group, still, as microalgae nitrogen source culture microalgae not
The growth that microalgae can be influenced as conventional understanding, on the contrary, microalgae biomass can be obtained while efficient denitrification.Cause
This, to achieve the goals above, the present invention provides a kind of methods for handling the waste water containing nitrate ion, this method comprises:
During microdisk electrode, the waste water containing nitrate ion is introduced into cultivating system and provides nitrogen source for microalgae, after culture, is drawn
At least partly micro algae culturing liquid is separated by solid-liquid separation out.
The present invention absorbs the nitrate ion in waste water using microalgae, realizes microalgae processing (conversion) containing nitrate ion
The purpose of waste water, treatment effeciency and stability are higher, and obtain microalgae biomass with high yield while handling waste water,
With good economic efficiency and ecological, social benefit.
Particularly, in the preferred embodiment, by further film process step, in the present invention after microalgae denitrogenation
Water can be with direct emission (meeting GB31570-2015 petroleum refining industry pollutant emission standard) or reuse, and environmentally protective ground is real
The processing of waste water is showed.
Detailed description of the invention
Fig. 1 is the process flow chart according to one embodiment of the present invention；
Fig. 2 is the growth curve of chlorella in embodiment 1；
Fig. 3 is NO in the algae solution of embodiment 13 -Concentration curve；
Fig. 4 is the growth curve of chlorella in embodiment 2；
Fig. 5 is NO in the algae solution of embodiment 23 -Concentration curve.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The method of waste water of the processing containing nitrate ion provided by the invention includes: that will contain nitre during microdisk electrode
The waste water of acid ion introduces cultivating system and provides nitrogen source for microalgae, after culture, extraction at least partly micro algae culturing liquid into
Row is separated by solid-liquid separation.
In the present invention, the culture medium that waste water prepares microalgae can be used, it can also be during the cultivation process in a manner of adding
Introduce waste water.The waste water (nitrate ion especially therein) is utilized as nitrogen source by microalgae, therefore, may be used also in culture medium
To contain other nutriments, as long as using waste water that the purpose of the present invention can be realized as nitrogen source, for other nutriments
Can be this field conventional selection, for example, be referred to BG-11 culture medium, SE culture medium, Pr culture medium, f/2 culture medium,
At least one of Zarrouk culture medium (preferably BG-11 culture medium) is that microalgae selects other nutrients such as carbon source and inorganic salts
Matter.Normally, carbon source used in the present invention can be the utilizable monosaccharide of microalgaes such as glucose.
It is well known by those skilled in the art that in order to handle a greater amount of waste water and obtain further amounts of microalgae biomass,
Waste water (and other nutriments-are especially carbon source) can be added into cultivating system.Therefore, one kind according to the present invention is excellent
Embodiment is selected, waste water is introduced to the mode of cultivating system are as follows: prepares the culture medium of microalgae using waste water, and microalgae is seeded to
It is cultivated in culture medium, monitors the nitrate ion content in cultivating system during the cultivation process, thus in due course toward culture body
System adds waste water, and when in the waste water that contain nitrate ion nitrate ion in the form of nitric acid in the presence of, the waste water added makes
The pH value for obtaining cultivating system maintains within the scope of 7.5-9.5；Alternatively, when contain in the waste water of nitrate ion nitrate ion with nitre
In the presence of the form of hydrochlorate (such as sodium nitrate and/or potassium nitrate), the amount for the waste water added makes nitrate ion in cultivating system
Content within the scope of 10-30mmol/L, and by adding sour (inorganic acid such as phosphoric acid or organic acid such as acetic acid, propionic acid and lemon
Acid etc.) control cultivating system pH value.The additional amount of carbon source usually makes the content of carbon source in cultivating system in 5-10g/L range
It is interior.According to the preferred embodiment, the treating capacity of waste water and the yield of microalgae biomass can be improved simultaneously.
In the present invention, it can be judged to cultivate terminal according to the microalgae content size in cultivating system, and microalgae content can
To pass through the OD of micro algae culturing liquid680Value characterizes, and for chlorella, works as OD680When value reaches 55-70, culture knot
Beam, and carry out subsequent operation.After culture, the nitrate ion content in gained micro algae culturing liquid is in 3mmol/L or less.This
Field technical staff is it is to be understood that the culture of microalgae can be semi continuous, therefore cultivate terminal and refer to each culture week
The terminal of phase.
In order to realize being carried out continuously for wastewater treatment, in the preferred embodiment of the present invention, at least partly microalgae
Culture solution accounts for the 80-90 volume % of micro algae culturing liquid total volume, and the method also includes by fresh waste water and other nutrition
Substance mixed with the remaining micro algae culturing liquid (10-20 volume %) that do not draw carry out a new round wastewater treatment (or microalgae training
Support), it so recycles, to realize the semi-continuous process of waste water.During wastewater treatment (or microdisk electrode) of a new round, still
Waste water (and other nutriments, especially carbon source) can be added to improve the wastewater treatment capacity of the wheel and microalgae biology simultaneously
Matter yield (as previously described).By the preferred embodiment, the semi-continuous process of waste water is not only may be implemented in the present invention, may be used also
To realize the Semi-continuous cultivation of microalgae, to have the advantages that green high-efficient.
It, can be to training in order to obtain higher water treatment effect and microalgae biomass yield during microdisk electrode
Antibiotic is added in the system of supporting to control the growth of miscellaneous bacteria.The antibiotic can be antibiotic commonly used in the art, example
It such as, can be mould selected from benzyl penicillin, ampicillin, carbenicillin, streptomysin, gentamicin, kanamycins, neomycin, chlorine
At least one of element, erythromycin, tetracycline, terramycin, nalidixic acid and rifampin.
The incubation of microalgae is the process of optical-biological reaction, in this process, the nitrate ion conduct in waste water
Nitrogen source is converted by microalgae, to realize the removing of nitrate ion.The culture can be in conventional optical-biological reaction condition
Lower progress does not require temperature, illumination, pH, dissolved oxygen amount etc. particularly, can be adjusted according to the type of used microalgae
It is whole.Normally, it is 15-40 DEG C, intensity of illumination 1000-200000lux that the condition of culture, which may include: temperature, and pH value is
7.5-9.5, ventilatory capacity 0.5-1.5vvm.Wherein, " vvm " refers to the volume of minute ventilation volume (standard state) and cultivating system
Ratio.
In the present invention, before being cultivated, can to the algae of the microalgae carry out seed culture, seed culture be for
More pure and strong microalgae is obtained, that is, flushed, be inoculated with the enough algaes of quantity.It can be conventional using this field
Method carry out seed culture, details are not described herein.
In the present invention, in order to make, the liquid phase after culture is suitable for discharge or reuse, the mode of the separation of solid and liquid can be
Filter, such as the modes such as ultrafiltration, centrifugation and/or nanofiltration, preferably are as follows: near small part micro algae culturing liquid carries out ultrafiltration, obtains level-one
Algae solution and by-pass filtration liquid is concentrated；Primary concentration algae solution is centrifuged, secondary concentration algae solution and centrifugal clear liquid are obtained；It will centrifugation
Clear liquid and by-pass filtration liquid carry out nanofiltration, obtain secondary filtration liquid.Wherein, the secondary concentration algae solution obtained mainly contains microalgae biology
Matter further can be obtained microalgae biomass product through simple drying steps.Obtained secondary filtration liquid can be with direct emission
Or reuse, to realize being effectively treated for waste water.
In preferred embodiment as above, algae solution is concentrated in the first biggish hyperfiltration membrane assembly of selective retention molecular weight,
Obtain primary concentration algae solution and by-pass filtration liquid.Concentration algae solution is separately handled with filtered fluid, is on the one hand advantageously reduced
The load of subsequent algae solution centrifugation, drying process, reduces energy consumption, on the other hand advantageously reduces the load of subsequent nano-filtration process,
A possibility that reducing film blocking and fouling membrane.The molecular cut off of the ultrafiltration membrane that the ultrafiltration uses usually≤100kDa, it is excellent
Choosing≤50kDa, most preferably 30kDa.The inlet pressure of the ultrafiltration is preferably 0.12-0.2MPa, and outlet pressure is preferably
0.05-0.08MPa.In the present invention, the inlet pressure of film filtering refers to the fluid pressure before micro algae culturing liquid is contacted with film, exports
Pressure refers to that filtered fluid passes through the fluid pressure after filter membrane.
In preferred embodiment as above, centrifugal concentrating is carried out to primary concentration algae solution, further decreases concentration algae solution
On the one hand volume advantageously reduces the requirement to subsequent drying process ability, on the other hand advantageously reduces the loss of culture solution,
Keep the stabilization of microdisk electrode system.The secondary concentration algae solution that centrifugal concentrating obtains can carry out high temperature drying, can also carry out
Spray drying.The condition of the centrifugation makes the amount of centrifugal clear liquid account for the 60-70 volume % of primary concentration algae solution.
In preferred embodiment as above, the process that centrifugal clear liquid carries out nanofiltration with by-pass filtration liquid can carry out simultaneously,
It can also separate and carry out, it is contemplated that the simplicity of operation mixes by-pass filtration liquid with centrifugal clear liquid, reuses nanofiltration membrane progress
Filtration treatment obtains secondary filtration liquid.Secondary filtration hydroful foot discharge standard can be discharged, and microdisk electrode can also be recycled to
Unit can directly carry out microdisk electrode after further addition waste water and other nutriments.The nanofiltration membrane that the nanofiltration uses
Molecular cut off usually≤1000Da, preferably≤500Da, most preferably 300Da.The inlet pressure of the nanofiltration is preferably
0.6-1MPa, outlet pressure are preferably 0.3-0.5MPa.Concentrate after nanofiltration can be fed directly to drying steps and (do as spraying
It is dry), or enter drying steps after mixing with secondary concentration algae solution.
In the present invention, the waste water can be the waste water containing nitrate ion of various industrial discharges, still, of the invention
Method is particularly conducive to the nitric acid scavenger of the processing higher waste water of nitrate ion content, especially preparing process of caprolactam
The waste water that section generates.In the case of it is therefore preferable that, total nitrogen content >=200mg/L of the waste water in terms of N.Total nitrogen content (TN)
Measurement flow injection-hydrochloride naphthodiamide spectrophotometry of the measuring method referring to HJ 668-2013 water quality total nitrogen.The waste water
In other ingredients type and content are as follows: NO3 -,15-40g/L；SO4 2-,34-38mg/L；PO4 3-,90-170mg/L；Na+,0.5-
8g/L；K+,13-15mg/L；Ca2+,33-37mg/L；Toluene, (minimum can be 0.005mg/L or 0.01mg/ to 0-0.1mg/L
L)；Caprolactam, 0-1mg/L (minimum can be 0.1mg/L).
It was found by the inventors of the present invention that wastewater treatment process of the invention is particularly suitable for the treatment process phase with ammonia nitrogen waste water
Coupling, therefore, a kind of specific embodiment according to the present invention, the wastewater source are passed through in ammonia nitrogen waste water namely ammonia nitrogen waste water
The waste water containing nitrate ion obtained after the nitration reaction processing of autotrophic bacterium.The ammonia nitrogen waste water can be for various sources (such as
Chemical fertilizer, coking, petrochemical industry, pharmacy, food, refuse landfill) ammonia nitrogen waste water, in particular, NH4 +The higher ammonia nitrogen of concentration it is useless
Water, such as caprolactam production wastewater, under preferable case, in the ammonia nitrogen waste water COD be 4000-5000mg/L, ammonia nitrogen 150-
200mg/L (ammonia-nitrogen content (NH4 +- N) measuring method be Berthelot spectrophotometry (HJ 535-2009)).
Nitration reaction refers under aerobic state, and nitrococcus is carbon source by NH using inorganic carbon4 +It is converted to nitrite
(NO2 -), then nitrite-oxidizing is nitrate (NO by nitrifier3 -) process.Nitrococcus and nitrifier are for water
The microorganism being conventionally present in the activated sludge of matter purification.Normally, the sludge loading of the activated sludge used is 0.15-
0.5kg COD/ (kg sludge d).
The condition of nitration reaction includes: that dissolved oxygen is 2-4mg/L, and temperature is 10-40 DEG C, hydraulic detention time 8-16h.
" dissolved oxygen " refers to the amount (mg) of the oxygen contained in system (L) under conditions of biological denitrificaion；" hydraulic detention time " refers to
In mean residence time of the waste water to be processed in reactor, that is, waste water and reactor when the average response of microbial action
Between, therefore, if the dischargeable capacity of reactor is V (m3), water velocity is Q (m3/ h), then: hydraulic detention time (HRT)=V/
Q, i.e. hydraulic detention time are equal to the ratio between reactor dischargeable capacity and water velocity；" COD " i.e. COD is indicated in water
How many index of reducing substances, COD value is bigger, illustrates that water body is more serious by the pollution of organic matter, involved in the present invention
All COD values measuring method be dichromate titration (GB11914-89).
In the present invention, as previously mentioned, used microalgae can for it is various can using the nitrate ion in waste water as
The microalgae of nitrogen source, such as cyanobacteria or green alga, under preferable case, the microalgae is chlorella (such as chlorella vulgaris (Chlorella
Vulgaris), chlorella ellipsoidea (C.ellipsoidea) or chlorella pyrenoidosa (C.pyrenoidosa)), single needle algae (such as wears
Family name's single needle algae (Monoraphidium dybowskii)), scenedesmus (such as scenedesmus obliquus (Scenedesmusobliqnus), tapering
Scenedesmus (S.acuminatus), Scenedesmus arcuatus (S.arcuatus), by first scenedesmus (S.armatus) or Scenedesmus quadricauda
(S.quadricauda)) or spirulina (such as blunt top spirulina (Spirulina platensis)), more preferably chlorella.
In particularly preferred embodiment of the invention, the microalgae is from Inst. of Hydrobiology, Chinese Academy of Sciences
The chlorella vulgaris that the number in (Chinese Academy of Sciences's fresh water algae library) is FACHB-32.
According to the preferred embodiment of the present invention, as shown in Figure 1, which comprises
Microdisk electrode: seed culture and optical-biological reaction carried out to microalgae, during optical-biological reaction, into cultivating system
The waste water containing nitrate ion is introduced to provide nitrogen source for microalgae, monitors the nitrate ion in cultivating system and other nutrition
The content of substance (especially carbon source), and waste water (nitrogen source) and other nutriments are supplemented further to promote according to monitoring result
The growth of microalgae；
Microalgae filtering: ultrafiltration is carried out at least partly micro algae culturing liquid (or algae solution) that optical-biological reaction obtains, obtains one
Grade concentration algae solution and by-pass filtration liquid；Primary concentration algae solution is centrifuged, secondary concentration algae solution and centrifugal clear liquid are obtained；It will be from
Heart clear liquid and by-pass filtration liquid carry out nanofiltration, obtain secondary filtration liquid；Secondary filtration liquid can be obtained with direct emission or reuse
Secondary concentration algae solution can be obtained microalgae biomass product through drying.
The present invention will be described in detail by way of examples below.
In following embodiment, chlorella C2 is purchased from Inst. of Hydrobiology, Chinese Academy of Sciences, number FACHB-32；
The composition of the waste water containing nitric acid are as follows: NO3 -,38.7g/L；SO4 2-,34mg/L；PO4 3-,165mg/L；Na+,553mg/L；K+,13.1mg/L；Ca2+,36.8mg/L；Toluene, 0.01mg/L；Caprolactam, 1mg/L, from preparing process of caprolactam
Nitric acid cleans workshop section；
Composition containing nitrate wastewater: NO3 -,17.3g/L；SO4 2-,38mg/L；PO4 3-,95mg/L；Na+,7.5g/L；K+,
13.6mg/L；Ca2+,33.4mg/L；Toluene, 0.005mg/L；Caprolactam, 0.1mg/L derive from preparing process of caprolactam
Nitric acid clean workshop section；
The mode that secondary concentration algae solution is dried are as follows: spray drying is implemented by YC-015 experiment type spray drier,
Condition are as follows: 200 DEG C of inlet air temperature, 80 DEG C of leaving air temp, sample introduction speed is 80mL/h；
The absorbance (OD value) of algae solution measures: using spectrophotometric determination, is compared with distilled water, is then inhaled in maximum
Receive the light absorption value that algae solution is measured at spike long (680nm), the index as microalgae concentration；
NO3 -The measuring method of concentration be water quality nitrate nitrogen measurement gas-phase molecular absorption spectrometry method (HJ/T 198-
2005)
NO3 -Clearance rate=(NO in waste water3 -NO in algae solution after concentration-culture3 -Concentration) NO in/waste water3 -Concentration ×
100%.
Embodiment 1
Sterile chlorella algae C2 is inoculated into the BG-11 culture medium of the glucose containing 5g/L, algae solution OD after inoculation680Control
System is 1 or so, in 28 DEG C, illumination: then ventilation culture 72h under conditions of dark=12h:12h accesses 7L bioreactor
Middle carry out sterile culture.In bioreactor containing 4L with waste water containing nitric acid for inorganic nitrogen-sourced BG-11 culture medium, and add
Ampicillin is to 50mg/L.BG-11 culture medium composition is shown in Table 1.28 DEG C of cultivation temperature, filtrated air ventilatory capacity about 0.9vvm,
Speed of agitator about 280rpm, intensity of illumination 6000lux, illumination: dark=12h:12h.In incubation to cell density (with
Absorbance OD at 680nm680For index), cultivating system concentration of glucose, nitrate ion concentration be monitored, and according to prison
It surveys result and adds nutrition, add glucose and make concentration of glucose control between 5-10g/L, add waste water containing nitric acid, control
PH is between 7.5-9.0 for microdisk electrode system.
After microdisk electrode 72h, the algae solution of 80 volume % is taken out from bioreactor, into microalgae filter element.It is super
Membrane filtration device portal pressure 0.12MPa, outlet pressure 0.06MPa, membrane module molecular cut off 30kDa.Collect level-one mistake
Filtrate, algae solution recycle between fluid cylinder-filter membrane component.The stopping when by-pass filtration liquid product reaches take out algae solution volume 80%
Filtering takes out dense algae solution to get primary concentration algae solution is arrived.
Primary concentration algae solution is sent into centrifuge and carries out centrifugal concentrating, revolving speed 4500r/min is centrifuged 20min, is centrifuged
Clear liquid and secondary concentration algae solution.Secondary concentration algae solution is dried to arrive microalgae biomass product.
By-pass filtration liquid is merged with centrifugal clear liquid, into nanofiltration membrane device, collects secondary filtration liquid.Nanofiltration membrane mistake
Filter device portal pressure 0.8MPa, outlet pressure 0.4MPa, membrane module molecular cut off 300Da.Secondary filtration hydroful discharges enough
Standard (GB31570-2015 petroleum refining industry pollutant emission standard, total nitrogen < 40mg/L).
Secondary filtration liquid returns in 7L bioreactor (remaining a small amount of algae solution, 20 volume % in sampling post-reactor),
Continue to cultivate after adding glucose, waste water containing nitric acid, other nutriments.After cultivating 72h, taken again from bioreactor
The algae solution of 80 volume % out, repeats the above steps.
Chlorella growth curve is as shown in Fig. 2, NO in algae solution3 -Concentration curve is as shown in Figure 3.It is useless that microalgae handles entrance
Water NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 2.8mmol/L, NO3 -Clearance rate > 90.7%.It is computed, at above-mentioned waste water
In reason system, about 13kg microalgae biomass product can averagely be obtained by handling waste water containing nitric acid per ton.
Table 1
Embodiment 2
Sterile chlorella algae C2 is inoculated into the BG-11 culture medium of the glucose containing 5g/L, algae solution OD after inoculation680Control
System is 1 or so, in 28 DEG C, illumination: then ventilation culture 72h under conditions of dark=12h:12h accesses 7L bioreactor
Middle carry out sterile culture.Containing 4L, for inorganic nitrogen-sourced BG-11 culture medium, and to add containing nitrate wastewater in bioreactor
Plus ampicillin is to 50mg/L.BG-11 culture medium composition is shown in Table 1.28 DEG C of cultivation temperature, filtrated air ventilatory capacity is about
0.8vvm, speed of agitator about 260rpm, intensity of illumination 6000lux, illumination: dark=12h:12h.It is close to cell in incubation
Degree is (with the absorbance OD at 680nm680For index), cultivating system concentration of glucose, nitrate ion concentration be monitored, and
Nutrition is added according to monitoring result, glucose is added and makes concentration of glucose control between 5-10g/L；It adds useless containing nitrate
Water makes nitrate ion concentration reach 0.01mol/L to 0.03mol/L；Add 10 weight % phosphoric acid control microdisk electrode system
PH is between 7.5-9.0.
After microdisk electrode 72h, the algae solution of 90 volume % is taken out from bioreactor, into microalgae filter element.It is super
Membrane filtration device portal pressure 0.12MPa, outlet pressure 0.06MPa, membrane module molecular cut off 30kDa.Collect level-one mistake
Filtrate, algae solution recycle between fluid cylinder-filter membrane component.The stopping when by-pass filtration liquid product reaches take out algae solution volume 80%
Filtering takes out dense algae solution to get primary concentration algae solution is arrived.
Primary concentration algae solution is sent into centrifuge and carries out centrifugal concentrating, when centrifugal clear liquid volume reaches primary concentration algae solution body
Stop centrifugation when long-pending 65%, obtains centrifugal clear liquid and secondary concentration algae solution.Secondary concentration algae solution is dried to arrive microalgae
Biomass product.
By-pass filtration liquid is merged with centrifugal clear liquid, into nanofiltration membrane device, collects secondary filtration liquid.Nanofiltration membrane mistake
Filter device portal pressure 0.8MPa, outlet pressure 0.4MPa, membrane module molecular cut off 300Da.Secondary filtration hydroful discharges enough
Standard.
Secondary filtration liquid returns in 7L bioreactor (remaining a small amount of algae solution, 10 volume % in sampling post-reactor),
Add glucose, containing continuing to cultivate after nitrate wastewater, other nutriments.After cultivating 72h, from bioreactor again
The algae solution for taking out 90 volume %, repeats the above steps.
Chlorella growth curve is as shown in figure 4, NO in algae solution3 -Concentration curve is as shown in Figure 5.It is useless that microalgae handles entrance
Water NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 2.6mmol/L, NO3 -Clearance rate > 91.3%.It is computed, at above-mentioned waste water
In reason system, about 12kg microalgae biomass product can averagely be obtained by handling waste water containing nitric acid per ton.
Embodiment 3
Wastewater treatment is carried out according to the method for embodiment 1, unlike, using another chlorella Chl (purchased from Chinese section
Aquatile research institute, institute, number FACHB-37) chlorella in alternative embodiment 1.
Microalgae handles inlet wastewater NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 13.6mmol/L, NO3 -Clearance rate >
54.7%.It is computed, in above-mentioned wastewater treatment system, about 7.2kg microalgae biology can averagely be obtained by handling waste water containing nitric acid per ton
Matter product.
Embodiment 4
Wastewater treatment is carried out according to the method for embodiment 1, unlike, (the aquatic life of the Chinese Academy of Sciences is purchased from using scenedesmus
Object research institute, number FACHB-416) chlorella in alternative embodiment 1.
Microalgae handles inlet wastewater NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 27.8mmol/L, NO3 -Clearance rate >
7.3%.It is computed, in above-mentioned wastewater treatment system, about 0.9kg microalgae biomass can averagely be obtained by handling waste water containing nitric acid per ton
Product.
Embodiment 5
Wastewater treatment is carried out according to the method for embodiment 1, unlike, the amount for the algae solution taken out from bioreactor
For 75 volume %.
Microalgae handles inlet wastewater NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 5.3mmol/L, NO3 -Clearance rate >
82%.It is computed, in above-mentioned wastewater treatment system, about 10.8kg microalgae biomass can averagely be obtained by handling waste water containing nitric acid per ton
Product.
Embodiment 6
Wastewater treatment is carried out according to the method for embodiment 1, unlike, the amount for the algae solution taken out from bioreactor
For 95 volume %.
Microalgae handles inlet wastewater NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 8.1mmol/L, NO3 -Clearance rate >
73%.It is computed, in above-mentioned wastewater treatment system, about 9.6kg microalgae biomass can averagely be obtained by handling waste water containing nitric acid per ton
Product.
Embodiment 7
Wastewater treatment is carried out in the way of embodiment 1, unlike, the inlet pressure 0.2MPa of ultrafiltration, outlet pressure
0.1MPa。
Microalgae handles inlet wastewater NO3 -Concentration >=30mmol/L is discharged NO3 -Concentration < 10.4mmol/L, NO3 -Clearance rate >
65.3%.It is computed, in above-mentioned wastewater treatment system, about 8.6kg microalgae biology can averagely be obtained by handling waste water containing nitric acid per ton
Matter product.
By result above as can be seen that can be obtained while handling waste water containing nitrate ion using the method for the present invention
Obtain the microalgae biomass of high yield.Moreover, the present invention still is able to obtain higher after circulation 300h (carrying out 4 circulations)
Treatment effeciency and microalgae biomass yield, illustrate that method stability of the invention is strong.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for handling the waste water containing nitrate ion, which is characterized in that this method comprises: in microdisk electrode process
In, the waste water containing nitrate ion is introduced into cultivating system and provides nitrogen source for microalgae, after culture, draws at least partly microalgae
Culture solution is separated by solid-liquid separation.
2. according to the method described in claim 1, wherein, waste water to be introduced to the mode of cultivating system are as follows: prepare using waste water micro-
The culture medium of algae, and microalgae is seeded in culture medium and is cultivated, the nitrate anion in cultivating system is monitored during the cultivation process
Ion concentration, to add waste water toward cultivating system in due course, and when in the waste water that contain nitrate ion nitrate ion with nitric acid
Form in the presence of, the waste water added maintains the pH value of cultivating system within the scope of 7.5-9.5；
Alternatively, when contain in the presence of nitrate ion is in the form of nitrate in the waste water of nitrate ion, the amount for the waste water added
So that the content of nitrate ion controls cultivating system within the scope of 10-30mmol/L, and by adding acid in cultivating system
PH value.
3. according to the method described in claim 1, wherein, at least partly micro algae culturing liquid 80- that accounts for micro algae culturing liquid total volume
90 volume %, and the method also includes mixing fresh waste water and other nutriments with the remaining micro algae culturing liquid that do not draw
The wastewater treatment for carrying out a new round is closed, is so recycled.
4. method described in any one of -3 according to claim 1, wherein the mode of the separation of solid and liquid are as follows: will at least portion
Divide micro algae culturing liquid to carry out ultrafiltration, obtains primary concentration algae solution and by-pass filtration liquid；Primary concentration algae solution is centrifuged, is obtained
Secondary concentration algae solution and centrifugal clear liquid；Centrifugal clear liquid and by-pass filtration liquid are subjected to nanofiltration, obtain secondary filtration liquid.
5. according to the method described in claim 4, wherein, the molecular cut off≤100kDa for the ultrafiltration membrane that the ultrafiltration uses,
The inlet pressure of the ultrafiltration is preferably 0.12-0.2MPa, and outlet pressure is preferably 0.05-0.08MPa.
6. according to the method described in claim 4, wherein, the condition of the centrifugation makes the amount of centrifugal clear liquid account for primary concentration algae
The 60-70 volume % of liquid.
7. according to method described in claim 4,5 or 6, wherein the molecular cut off for the nanofiltration membrane that the nanofiltration uses≤
1000Da, the inlet pressure of the nanofiltration are preferably 0.6-1MPa, and outlet pressure is preferably 0.3-0.5MPa.
8. according to the method described in claim 1, wherein, the waste water total nitrogen content >=200mg/L in terms of N, NO3 -Content
For 15-40g/L, SO4 2-Content be 34-38mg/L, PO4 3-Content be 90-170mg/L, Na+Content be 0.5-8g/L, K+
Content be 13-15mg/L, Ca2+Content be 33-37mg/L, the content of toluene is 0-0.1mg/L, and the content of caprolactam is
0-1mg/L。
9. according to the method described in claim 1, wherein, the microalgae is chlorella, single needle algae, scenedesmus or spirulina.
10. according to claim 1 or method described in 9, wherein the microalgae is chlorella.
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