CN109626582A - The method for removing lead in water removal using the modified microalgae of high phosphorus culture - Google Patents
The method for removing lead in water removal using the modified microalgae of high phosphorus culture Download PDFInfo
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- CN109626582A CN109626582A CN201811593329.8A CN201811593329A CN109626582A CN 109626582 A CN109626582 A CN 109626582A CN 201811593329 A CN201811593329 A CN 201811593329A CN 109626582 A CN109626582 A CN 109626582A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a kind of methods for removing lead in water removal using the modified microalgae of high phosphorus culture, this method cultivates microalgae first with phosphorus-containing wastewater, to obtain the waste water up to standard after modified microalgae and dephosphorization, then modified microalgae is added in lead waste water and carries out adsorption treatment, be separated by solid-liquid separation after adsorption equilibrium and obtain de- lead waste water up to standard.This method is using microalgae as adsorbent, and compared with, with relatively simple technique, completing and effectively remove to phosphorus in different sewage and lead ion under low energy consumption, and removal efficiency is high, selectivity is strong, has good promotion and application value.
Description
Technical field
The present invention relates to microorganism and water-treatment technology fields, and in particular to a kind of micro- using high phosphorus sewage culture modification
Algae, and the method for removing Pb In Exhausted Water ion using it.
Background technique
Lead is one of pollutant common in water.Caused by lead contamination in water body is mainly the production and life of the mankind,
Including being manufactured from the industry such as food (such as lime-preserved egg, puffed rice, lead matter scolding tin tinned food), cosmetics, automobile, ceramics
The improper discarding of the waste water and Medicines that are discharged in journey.Lead in atmosphere can largely pass through wet deposition or dry deposition
Into in ground or water body, and the lead in soil can be by precipitation shower inflow surface water or the water that permeates the ground.In fresh water
Lead content 0.06-120 μ g/L, intermediate value are 3 μ g/L, and the leaded intermediate value of seawater is that (He Xiaobo temperature disappears to liquid chlorine to 0.03 μ g/L
Lead, zinc, the influence of cadmium content and its mechanism study in malicious tap water).Pb content difference in the swimming of Xiang River areas in Changsha section upper, middle and lower
For 0.3584,0.4515, (lead, cadmium, chromium content are to light in Peng Xianglian, Liu Zongmin, Liu Yun Xiang River areas in Changsha section water by 0.5097mg/L
The influence of water fish).
Lead has biggish harm to organism.The content of lead, also can be to the mind of the mankind even under micro-concentrations in water
It is damaged through, cardiovascular and reproductive system.This group food is eaten for a long time just into food in excessive lead (chromium class is seemingly) easily dissolution
It will cause lead to deposit in blood, lead to the damage of brain centres nerve and kidney and other organs.
At present in water the removal methods of lead mainly include flocculation, precipitating, reduction, it is cementing, evaporation, reverse osmosis, ultrafiltration and from
Son exchange etc., however the generally existing operating cost of these Conventional processing methods is higher, is also easy to produce toxic sludge, tracer dilution solution
The problems such as removal efficiency of middle lead is poor, and can only often handle the waste water that lead content is 1-100mg/L, these problems and deficiency
Significantly limit its large-scale promotion application.
Biological adsorption is considered as a huge sum of money that is a kind of preferable while having cost-effectiveness and environmental-friendly two aspects advantage
Belong to water pollution control substitute technology.The technology can almost completely remove all kinds of metal ions in water, at low concentrations effect
Also very well, it is often more important that secondary pollution problems are not present.Up to the present, researcher has developed many and has been used for
The biomaterial that removing heavy metals are removed from water, as Lu Yanqin et al. disclose it is a kind of for handling the microbial flocculation of lead zinc waste water
Agent (CN108658245A), Hu Yiqing disclose a kind of microorganism for quickly administering lead zinc pollution water body and corresponding administering method
(CN106222113A), Xie Fuhong et al. discloses a kind of method using microbial cells processing lead waste water
(CN104386832A), Chen Xiao et al. discloses de- to waste water progress dephosphorization using the granule sludge in brewery's anaerobic reactor
(Chen Xiao anaerobic grain sludge is ground in the application that waste water dephosphorization denitrogenation and lead ion are adsorbed for the application study of nitrogen and lead ion absorption
Study carefully [D] Guangxi University, 2009.).But these method higher operating costss, process flow is complicated, generally requires using specific
Culture medium purifies bacterial strain, is cultivated, and is then seeded into lead waste water.In addition, these methods can only often handle one kind
Waste water (i.e. lead waste water), it is then at one's wit's end for phosphorus-containing wastewater.
By long-term a large amount of investigations and experiment discovery, algae bio, which has many advantages, to be made for the present inventor team
It is used for the processing of heavy metal containing sewage for biological adsorption agent, and achieves preferable effect.On the one hand, algae bio is widely distributed,
Type is more, and raw material are readily available；On the other hand, usually there is polar functional group abundant in algae bio surface, make it
Removal efficiency and adsorption capacity with higher, and the sludge generated after adsorbing minimizes.In view of high phosphorus pollution is held in water
It easily causes the phosphate in earth's surface wawter bloom and waste water that can precipitate lead (need higher concentration and lead cannot be completely removed), invents
People team further attempts to be modified it culture using high phosphate waste water using microalgae as intermediary, by changing its superficiality
Matter and functional group further improve the removal ability to Pb in water (II), while realizing the efficient process of phosphorus-containing wastewater again,
It achieves many things at one stroke.
Summary of the invention
It is an object of the invention to solve the above problem existing for existing lead waste water biological adsorption processing technique, develop
A method of utilizing algae while Removal of Phosphorus in Wastewater and leaded sewage.This method provides not only the new biology of one kind except lead
Material, and two distinct types of waste water high-efficiency, quickly processing are realized, with method is simple, removal efficiency is high, safety collar
The advantages that guarantor.To achieve the above object, the technical solution adopted in the present invention is as follows:
A method of lead in water removal is removed using the modified microalgae of high phosphorus culture, comprising the following steps: is first inoculated with microalgae
It is cultivated into phosphorus-containing wastewater, the microalgae and dephosphorization waste water of isolated modification；Then modified microalgae is mixed with lead waste water
It closes, separation.
Further, the microalgae be selected from least one of aquatic monoplast green alga, cyanobacteria, specifically include chlorella,
Scenedesmus, Chlorococcum, Microcystis aeruginosa etc..
Further, the phosphorus-containing wastewater source is sanitary sewage, industrial wastewater, animal husbandry waste water, agricultural effluent, waste water
The existence form of middle phosphorus is organic phosphorus compound or inorganic phosphonium ion (such as phosphate radical).
Further, the concentration (in terms of P) of phosphorus is no more than 130mg/L, lead in the lead waste water in the phosphorus-containing wastewater
Ion concentration is 10-300mg/L.Waste strength is excessively high dilute after handled again.
Further, mass ratio when microalgae is mixed with phosphorus-containing wastewater during dephosphorization is 1:10-1000, and incubation time is
5-20 days, cultivation temperature was 20-40 DEG C, and culture environment is to have illumination-no light alternately.
Further, microalgae is centrifugated after cultivating in phosphorus-containing wastewater to stationary phase, after being washed with deionized again
Centrifuge separation, be centrifuged repeatedly separation-washing it is multiple after, obtain modified microalgae, it is then dry, pulverize.
Further, the drying be specially nature dry in the shade, 60 DEG C drying, -50 DEG C freeze-drying one of.
Mass ratio when modified microalgae is mixed with lead waste water when further, except lead is 1:10-1000.
Further, after microalgae is mixed with lead waste water when removing lead, pH value of solution is adjusted to 3-6, is vibrated at 20-40 DEG C
Absorption, adsorption time 0.5-6h.
The pH of mixed solution is 6 when further, except lead, and mass ratio when modified microalgae is mixed with lead waste water is
1:5, except lead adsorption time is 6h.
The present invention is first handled phosphorus-containing wastewater with microalgae, total phosphorus concentration therein can be reduced to 0.2mg/L with
Under, reach surface water environment quality Group III effluent standard；Then isolated modification microalgae powder is mixed with lead waste water
Conjunction carries out oscillation absorption, in the case where microalgae itself absorption removes the double action of lead and calcium phosphate precipitation except lead, completes the efficient of lead
Enriching and recovering.
Compared with prior art, the invention has the following advantages: (1) can be successive using single creature matter adsorbent material
Removal of Phosphorus in Wastewater and lead waste water, and it is higher to the selectivity of phosphorus and lead in waste water, adsorption capacity is strong, the rate of adsorption is fast；
(2) raw material microalgae is from a wealth of sources, cheap and easy to get, and processing cost is lower, more economical environmental protection；(3) entire process has
Certain universality is conducive to realize engineer application, extend in the modification adsorption applications of other fronds；(4) using frond to phosphorus
Absorption achieve the purpose that it is modified, to improve frond to the adsorption capacity of lead.
Detailed description of the invention
Fig. 1 is that the dry biomass after culture is modified to microalgae using different phosphorus concentration waste water in the embodiment of the present invention 1
Quality changes over time curve graph；
Fig. 2 is that different phosphorus concentrations are modified algae powder to the adsorbance of same concentration lead waste water with pH in the embodiment of the present invention 1
Change curve；
Fig. 3 be under conditions of pH is 6 in the embodiment of the present invention 1 the different modified algae powder of phosphorus concentrations to same concentration lead waste water
Adsorbance change over time curve graph；
Fig. 4 is that difference phosphorus concentration is modified algae powder to the adsorption capacity of lead with lead in solution when pH is 6 in the embodiment of the present invention 1
The change curve fitted figure of levels.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further described.
Embodiment 1
Microalgae used in various embodiments of the present invention is specially chlorella (Chlorellasp., QB-102), from Jiangxi Province
Qibaoshan Iron lead-zinc ore tailings are discarded isolated using conventional method in ground.The chlorella has small in size, growth and breeding speed
The advantages that fast, has certain tolerance to various environment.Phosphorus-containing wastewater is by K used in various embodiments of the present invention2HPO4It is pressed with water
It is formulated according to the concentration in terms of P.Lead waste water used in various embodiments of the present invention is by nitric acid dithizone and dilute nitric acid solution
Mixed preparing forms under certain proportion.
Embodiment 1
(1) the phosphorus-containing wastewater culture experiment of different phosphorus contents
Above-mentioned chlorella (Chlorellasp., QB-102) is seeded in respectively according to the mass ratio of 1:100-150
K2HPO4Concentration is 0.00,20.0,40.0,120,280, in the solution of 580mg/L (the corresponding concentration in terms of P is 0.00,4.48,
8.96, in the phosphorus-containing wastewater of 26.9,62.7 and 130mg/L), at 25 DEG C, 3600LX intensity of illumination, Light To Dark Ratio 14h:10h
Lower culture.Culture is centrifugated after 20 days, and the 3-5 phosphorus sufficiently to remove frond surface is washed with deionized, and then will
It, which is dispersed in water, is centrifugated again and washs, and finally isolated frond is placed at -50 DEG C and is lyophilized, is pulverized i.e.
For modified microalgae powder, it is denoted as B-0, B-20, B-40, B-120, B-280, B-580 respectively.Sampling and measuring solution during culture
In concentration of algae (sampling interval 48h measures frond absorbance in 680nm with ammonium molybdate ultraviolet spectrophotometry), as a result such as Fig. 1
It is shown.
As seen from Figure 1, frond by logarithmic phase reaches stationary phase after cultivating 20 days, and frond concentration is all in solution at this time
Reach maximum value, wherein B-280 frond increment highest, B-0 and B-20 frond concentration has almost no change.This illustrates higher phosphorous
Content facilitates frond growth.
(2) under difference pH lead waste water adsorption experiment
The modified microalgae powder of 10mg (B-0, B-20, B-40, B-120, B-280, B-580) sample (every seeds algae is taken respectively
3 groups of parallel samples are arranged in powder), it is added in 100mL conical flask together with 50mL lead waste water, adjusts pH value of solution to reality
Value is tested, absorption 360min is shaken with 180rpm revolving speed at 25 DEG C, is then centrifugated, takes 0.23 μm of filter mistake of supernatant
Filter tries Pb (II) content in filtrate with Atomic Absorption Spectrometry, as a result as shown in Figure 2.As seen from Figure 2, pH value can
To significantly affect microalgae to the absorption property of metal lead ion；When pH is 6, all fronds are maximum to the adsorbance of lead.
(3) different adsorption time lead waste water adsorption experiments
Taking the modified microalgae powder of 50mg respectively, (B-0, B-20, B-40, B-120, B-280, B-580, every seeds algae powder are arranged 3 groups
Parallel sample), it is added in 500mL conical flask together with 250mL lead waste water, with the concussion of 180rpm revolving speed at 25 DEG C
Absorption, samples 3-5mL in 1,5,10,30,60,120,360min, after 0.23 μm of membrane filtration, uses atomic absorption spectrum
Method measures the lead concentration in solution, as a result as shown in Figure 3.From the figure 3, it may be seen that the ability of microalgae absorption Pb (II) increases with the time
It improves rapidly, all microalgaes complete 85% or more biological adsorption, and B-280 pairs contacting with lead waste water in 30 minutes
The biological adsorption ability of Pb (II) is highest in other fronds.
(4) the lead waste water adsorption experiment of different lead contents
Taking modified microalgae powder (B-0, B-20, B-40, B-120, the B-280, B-580) sample of 10mg respectively, (every seeds algae powder is set
Set 3 groups of parallel samples), be respectively 10 with 50mL concentration under conditions of pH=6,40,80,100,120,160,200,250,
The lead waste water of 300mg/L is added to together in 100mL conical flask, shakes absorption 360min at 25 DEG C with 180rpm revolving speed,
Then it is centrifugated, appropriate supernatant is taken to be filtered with 0.23 μm of filter, using the Pb in Atomic Absorption Spectrometry examination filtrate
(II) content is fitted absorption result, obtains Fig. 4.
As shown in Figure 4, B-280 is the stable biological adsorption product for having high-affinity to Pb (II).By fitting result
It is calculated, the maximal absorptive capacity of Pb (II) is followed successively by B-280 (635mg/g) > B-580 (444mg/g) > B-120 (405mg/g)
>B-40(300mg/g)>B-20(138mg/ g)>B-0(110mg/g).This also illustrates, chlorella selected by the present invention
(Chlorellasp., QB-102) is strong to the adsorption capacity of Pb (II), and the reaction time is short, is a kind of removal Pb (II) well
Biological adsorption agent.
Embodiment 2
(5) the absorption research of practical lead waste water
The waste water containing lead contamination is fetched from certain factory, it will according to the mass ratio of 1:10-1000 with 0.45 μm of membrane filtration
In modified chlorella (Chlorellasp., QB-102) is inoculated into that treated water body, 25 DEG C, 150 revolving speeds it is per minute
Lower carry out adsorption experiment, adsorbs the lead concentration after 0.5-5h in sampling and measuring solution, and the results are shown in Table 1 after adsorption equilibrium.
As shown in Table 1, contained heavy metal ion type is more in the batch industrial wastewater, and Pb and Fe is not examined after absorption
Out, this illustrate QB-102 by waste water lead and iron ion adsorb it is complete；The heavy metal ion such as Co, Cu, Mn, Sb, Ti, V, Zn
Content be decreased obviously, this explanation in the presence of contents of many kinds of heavy metal ion, QB-102 to the lead in lead waste water still
So there is good adsorption effect, and absorption well can be played to other metal ions and made while complete Adsorption of Lead
With.
Each element changes of contents before and after the modified algae powder absorption lead-containing industrial wastewater of 1. B-280 of table
Note: ND is not detected.
Claims (10)
1. a kind of method for removing lead in water removal using the modified microalgae of high phosphorus culture, which comprises the following steps: first will
Microalgae is inoculated into phosphorus-containing wastewater and cultivates, the microalgae and dephosphorization waste water of isolated modification；Then by modified microalgae with contain
The mixing of lead waste water, separation.
2. the method as described in claim 1, it is characterised in that: the microalgae in aquatic monoplast green alga, cyanobacteria extremely
Few one kind, including chlorella, scenedesmus, Chlorococcum, Microcystis aeruginosa.
3. the method as described in claim 1, it is characterised in that: the phosphorus-containing wastewater source is sanitary sewage, industrial wastewater, poultry
Animal husbandry waste water, agricultural effluent, the existence form of Phosphorus From Wastewater are organic phosphorus compound or inorganic phosphonium ion.
4. the method as described in claim 1, it is characterised in that: the concentration of phosphorus is no more than 130mg/L, institute in the phosphorus-containing wastewater
Stating plumbum ion concentration in lead waste water is 10-300mg/L.
5. the method as described in claim 1, it is characterised in that: mass ratio when microalgae is mixed with phosphorus-containing wastewater during dephosphorization
For 1:10-1000, incubation time is 5-20 days, and cultivation temperature is 20-40 DEG C, culture environment be have illumination-no light replace into
Row.
6. the method as described in claim 1, it is characterised in that: centrifugation point after microalgae was cultivated in phosphorus-containing wastewater to stationary phase
From, be centrifugated again after being washed with deionized, be centrifuged repeatedly separation-washing it is multiple after, obtain modified microalgae, then do
It is dry, pulverize.
7. method as claimed in claim 6, it is characterised in that: the drying be specially nature dry in the shade, 60 DEG C drying, -50 DEG C
One of freeze-drying.
8. the method as described in claim 1, it is characterised in that: matter when modified microalgae is mixed with lead waste water when except lead
Amount is than being 1:10-1000.
9. the method as described in claim 1, it is characterised in that: after microalgae is mixed with lead waste water when removing lead, adjust pH value of solution
To 3-6, oscillation absorption, adsorption time 0.5-6h are carried out at 20-40 DEG C.
10. the method as described in claim 1, it is characterised in that: when except lead the pH of mixed solution be 6, modified microalgae with
Mass ratio when lead waste water mixes is 1:5, except lead adsorption time is 6h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621423A (en) * | 2020-05-27 | 2020-09-04 | 武汉理工大学 | High-phosphorus-loading living microalgae and preparation method and application thereof |
| CN112547784A (en) * | 2020-11-10 | 2021-03-26 | 武汉理工大学 | Method for repairing heavy metal contaminated soil by high-phosphorus-loading microalgae passivator |
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| CN103304031A (en) * | 2012-03-09 | 2013-09-18 | 中国海洋石油总公司 | System and method for treating coal gasification wastewater by using microalgae |
| CN108546649A (en) * | 2018-05-16 | 2018-09-18 | 中国科学院水生生物研究所 | Chlorella W2 and the application of the heavy metal in high content of beary metal water body can be removed |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103304031A (en) * | 2012-03-09 | 2013-09-18 | 中国海洋石油总公司 | System and method for treating coal gasification wastewater by using microalgae |
| CN108546649A (en) * | 2018-05-16 | 2018-09-18 | 中国科学院水生生物研究所 | Chlorella W2 and the application of the heavy metal in high content of beary metal water body can be removed |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621423A (en) * | 2020-05-27 | 2020-09-04 | 武汉理工大学 | High-phosphorus-loading living microalgae and preparation method and application thereof |
| CN112547784A (en) * | 2020-11-10 | 2021-03-26 | 武汉理工大学 | Method for repairing heavy metal contaminated soil by high-phosphorus-loading microalgae passivator |
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Application publication date: 20190416 |