CN106890625B - Efficiently remove the nanometer additive and aquiculture waste water processing method of nitrogen phosphorus lead in aquiculture waste water - Google Patents
Efficiently remove the nanometer additive and aquiculture waste water processing method of nitrogen phosphorus lead in aquiculture waste water Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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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Abstract
The present invention relates to the efficient nanometer additive for removing nitrogen phosphorus lead in aquiculture waste water, and the aquiculture waste water processing method using the inorganic agent.The inorganic agent is by nanometer oyster shell whiting and nano zero-valence iron powder by weight 4~8:1 composition, the particle diameter of nanometer oyster shell whiting is at most 300nm, and the particle diameter of nano zero-valence iron powder is at most 30nm.Of the invention can be realized for aquiculture waste water quickly goes to denitrogenate the treatment effect of phosphorus lead, and to environment green non-pollution.
Description
Technical field
The present invention relates to a kind of nanometer additive for efficiently removing nitrogen, phosphorus and lead in aquiculture waste water, and use and be somebody's turn to do
The aquiculture waste water processing method of inorganic agent, belongs to aquiculture waste water processing technology field.
Background technology
China's freshwater aquiculture area the first in the world, the row of a large amount of aquiculture waste waters (nitrogen, phosphorus and lead containing high concentration)
Put and cause tremendous influence to surrounding enviroment, cause water environment to deteriorate, frequent occurrence, the ecological balance and bio-diversity also meet with
To destruction.The decline of Cultivated water water quality also brings huge loss to China's fishery economic, therefore strengthens giving up to aquaculture
The research of water process has great importance to China.
Nowadays, with the development of nanometer technology, nano material is widely applied to the every field such as human being's production, life.
Sizable specific surface area possessed by nano material, the strange physics for making it show not available for many macro objects are special
Property, such as quantum size effect, macro quanta tunnel effect, bulk effect and skin effect.
At present, when traditional material (such as activated carbon, attapulgite) is applied to wastewater treatment as adsorbent, exist
The shortcomings of clearance of nitrogen, phosphorus and lead is relatively low, and processing time is long.Shell is existing as a kind of nontoxic material
Oyster shell whiting is used for purifying water body by research report.
Application number CN201510507598.8, application publication number CN105174321A, title《Nanoscale heavy metal water purification agent
And preparation method, purifier》Chinese invention patent application, its water purification agent contains through handling obtained nano level modified shell
Powder, modified loofah sponge, sodium aluminate and titanium dioxide through handling obtained nano level modified diatomite, being obtained through processing.But
It is that the preparation process of the technical scheme is more complicated, and needs to use in the lump with reference to its purifier when handling water, not
It is adapted to efficient process aquiculture waste water.
Application number CN200910070793.3, application publication number CN101690882A, title《One kind removes heavy metal in water removal
Natural adsorbent of ion and its preparation method and application》Chinese invention patent application, using clean shell, drying, it is broken,
Ball mill grinding obtains powder of natural shell adsorbent, can remove Heavy Metals in Waters ion to predetermined size.But the adsorbent
Processing speed is relatively low, is not suitable for efficient process aquiculture waste water.
Application number CN201510877258.4, application publication number CN105413645A, title《A kind of calcium base modified epoxy is fine
Tie up the preparation method of plain sorbing material》Chinese invention patent application, pre-processed respectively by using scallop shell and egg shell,
Crush afterwards, the mixing of powder pulverized powder is put into calcining in Muffle furnace obtains the high calcium oxide of activity, and itself and cellulose are mixed
Close, and add epoxychloropropane activating agent, obtain calcium oxide modified epoxy cellulose sorbing material.But the technical scheme
Preparation process it is more complicated, it is necessary to raw material it is more；Only determine the removal effect of chromium, copper, manganese, zinc, and undetermined nitrogen,
Phosphorus, lead.
Application number CN201510938652.4, application publication number CN105561912A, title《A kind of modified oyster shell whiting processing
The method of effluent containing heavy metal ions》Chinese invention patent application, modified oyster shell whiting is prepared with oyster shell whiting and modified carbon nano-tube,
The heavy metal ion in waste water can be removed.However, the technical scheme needs to use modified carbon nano-tube, and preparation process is more multiple
It is miscellaneous；Only determine the removal effect of cyanogen, chromium, copper, zinc, nickel, and undetermined nitrogen, phosphorus, lead.
The content of the invention
The technical problems to be solved by the invention are：The problem of overcoming prior art to exist, propose that one kind efficiently goes to remove water
The nanometer additive of nitrogen phosphorus lead in aquaculture waste, it can realize and quickly go to denitrogenate the water treatment efficiency of phosphorus lead, and to environment green
It is pollution-free.In addition, it is also proposed that using the aquiculture waste water processing method of the inorganic agent.
The technical scheme that the present invention solves its technical problem is as follows：
The nanometer additive of nitrogen phosphorus lead in aquiculture waste water is efficiently removed, it is characterized in that, by nanometer oyster shell whiting and nanometer
Zeroth order iron powder is by weight 4~8:1 composition, the particle diameter of the nanometer oyster shell whiting is at most 300nm, the nano zero-valence iron powder
Particle diameter is at most 30nm.
Preferably, the particle diameter of the nanometer oyster shell whiting is 100~300nm, the particle diameter of the nano zero-valence iron powder for 10~
30nm。
Preferably, the weight ratio of the nanometer oyster shell whiting and nano zero-valence iron powder is 4:1.
Using the aquiculture waste water processing method of foregoing nanometer additive, it is characterized in that, comprise the following steps：
By the nanometer additive goals of investment aquiculture waste water, the additive capacity of nanometer additive is set to be at least 2g/
L；By decentralized processing, it is dispersed in water nanometer additive, it is at least 0.5 hour to preset processing time；Reached between when treated
During to default processing time, processing terminates；
Wherein, at the time of reaching in processing time 0.5 hour, total nitrogen, ammoniacal nitrogen, nitre state in target aquiculture waste water
Nitrogen, total phosphorus and Pb2+Removal efficiency respectively reach more than 90%.
Preferably, the additive capacity of the nanometer additive is 2~4g/L.
Preferably, the processing time is 0.5~1 hour.
Preferably, the decentralized processing is included using Mixing Machine stirring water body, or makes water circulation using pumping equipment,
Or water body flow is made using aerator.
Inventor has found through in depth repeatedly practising research, by the nanometer oyster shell whiting of defined particle size and the nanometer of defined particle size
For zeroth order iron powder by the weight of above-mentioned restriction than composition inorganic agent, the removal that can be obviously improved nitrogen phosphorus lead in aquiculture waste water is fast
Rate；It is aided with the additive capacity of restriction in the specific implementation, the place to aquiculture waste water can be completed after the processing of 0.5 hour
Reason, very efficiently, beneficial to extensive processing aquiculture waste water.
Compared with prior art, the present invention not only overcomes traditional material (such as activated carbon, attapulgite) and is applied to give up
The shortcomings of existing nitrogen phosphorus lead clearance is relatively low during water process, and processing time is long, also overcomes exclusive use nanometer
The shortcomings that treatment effeciency is relatively low during oyster shell whiting, aquiculture waste water realization can be directed to and quickly go to denitrogenate the treatment effect of phosphorus lead, and
To environment green non-pollution.
Brief description of the drawings
Fig. 1 to Fig. 3 is respectively different nanometer oyster shell whiting additions total nitrogen, ammoniacal nitrogen and nitre state in different time is to water body
The influence curve figure of nitrogen residual quantity.
Fig. 4 is removal efficiency curve map of the different nanometer oyster shell whiting additions in different time to total phosphorus in water.
Fig. 5 is different nanometer oyster shell whiting additions Pb in different time is to water body2+The influence curve figure of residual quantity.
Fig. 6 to Fig. 8 be respectively nanometer oyster shell whiting with the different ratio of nano zero-valence iron powder in different time is to water body it is total
The influence curve figure of nitrogen, ammoniacal nitrogen and Nitrate Nitrogen Residue amount.
Fig. 9 is that the different ratio of nanometer oyster shell whiting and nano zero-valence iron powder is imitated in removal of the different time to total phosphorus in water
Rate curve map.
Figure 10 Pb in different time is to water body for the different ratio of nanometer oyster shell whiting and nano zero valence iron2+The shadow of residual quantity
Ring curve map.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and in conjunction with the embodiments.But the invention is not restricted to given
The example gone out.
Embodiment 1 prepares the aquiculture waste water of simulation
According to the measured data of accumulation, common contaminant species and corresponding concentration are horizontal such as the institute of table 1 in aquiculture waste water
Show.
Table 1：Common contaminant and corresponding concentration level in aquiculture waste water
The aquiculture waste water of simulation, and water body pH 6.8 ± 0.1,25 DEG C ± 0.5 DEG C of temperature are prepared by table 1.Comparative example
Individually with the gained waste water of nanometer oyster shell whiting Processing Example 1
, can be by the extraordinary superfine powder engineering skill of country of Institutes Of Technology Of Nanjing using 100~300nm of particle diameter nanometer oyster shell whiting
Art research center provides.
The gained waste water of 300ml embodiments 1 is separately added into 5 500ml conical flask, then weighs a nanometer shell successively
Powder is added thereto, and the addition of nanometer oyster shell whiting is reached 0,1,2,3,4g/L successively, is put into shaking table, sets shaking table temperature 25
DEG C, rotating speed 150rpm/min.Sampled successively after shaking 0,0.05,0.5,5,50,500h, measure total nitrogen, ammoniacal nitrogen, nitre state
The content of nitrogen, total phosphorus and heavy metal lead.
Embodiment 2 is with the nanometer oyster shell whiting of different ratio and the gained waste water of nano zero-valence iron powder Processing Example 1
Using with comparative example identical nanometer oyster shell whiting；Using commercially available nano zero-valence iron powder, 10~30nm of particle diameter can be by upper
Extra large Aladdin biochemical technology limited company provides.
The gained waste water of 300ml embodiments 1 is separately added into 6 500ml conical flask, wherein 1 is used as blank
(Control), 1 plus nano zeroth order iron powder (reaching concentration 0.5g/L).In other 4, a nanometer oyster shell whiting is weighed successively
It is added thereto, the addition of nanometer oyster shell whiting is reached 1,2,3,4g/L successively, then nano zero-valence iron powder is put into this 4 tapers
(reach concentration 0.5g/L) in bottle；This 6 conical flasks are placed into shaking table, 25 DEG C of shaking table temperature, rotating speed 150rpm/ are set
min.Sampled successively after shaking 0,0.05,0.5,5,50,500h, measure total nitrogen, ammoniacal nitrogen, nitrate nitrogen, total phosphorus and heavy metal
The content of lead.
The experimental result of comparative example and embodiment 2 synthesis is described below：
(1) determination of most suitable nanometer oyster shell whiting addition scope
1st, the influence that different nanometer oyster shell whiting additions remove to different shape nitrogen in water body
As shown in Figure 1 to Figure 3, with nanometer oyster shell whiting (main component 96%CaCO3) addition increase, it is total in water body
The residual quantity of nitrogen, nitrate nitrogen and ammoniacal nitrogen declines, and slippage is the most notable in 5h.
When addition is 2~4g/L, the clearance of total nitrogen, nitrate nitrogen and ammoniacal nitrogen is higher.When addition is 2g/L,
Removal efficiency highest, the clearance of total nitrogen is up to 91.1% in 5h, and the clearance of nitrate nitrogen is up to 96.8%, the clearance of ammoniacal nitrogen
Up to 92.9%.
2nd, the influence that different nanometer oyster shell whiting additions remove to total phosphorus in water
As shown in figure 4, with the increase of nanometer oyster shell whiting addition, the clearance of total phosphorus in water raises.In addition
For 2~4g/L when, the removal efficiency of total phosphorus is higher.When addition is 2g/L, removal efficiency highest, the removal of total phosphorus in 5h
Rate is up to 90.1%.
3rd, different nanometer oyster shell whiting additions Pb in different time is to water body2+The influence of residual quantity
As shown in figure 5, with the increase of nanometer oyster shell whiting addition, Pb in water body2+Residual quantity decline.It is in addition
During 2~4g/L, to Pb in water body2+Removal effect it is preferable.When addition is 2g/L, removal efficiency highest, in 0.5h
Clearance is up to 80% (residual quantity 0.02mg/L is less than water quality standard for fishery), and clearance in 5h is up to 95%.
Summary result understands that nanometer oyster shell whiting has to the total nitrogen in water body, nitrate nitrogen, ammoniacal nitrogen, total phosphorus and lead
Preferable removal effect；When addition is 2~4g/L, removal effect is obvious, especially when addition is 2g/L, removes effect
Fruit is best.
(2) nanometer oyster shell whiting and nano zero-valence iron powder are most adapted to ratio
1st, the influence that the different ratio of nanometer oyster shell whiting and nano zero-valence iron powder removes to Water
In embodiment 2, the nanometer oyster shell whiting and the nano zero-valence iron powder weight ratio that respectively handle are 2:Isosorbide-5-Nitrae:1,6:1 and 8:1.
From Fig. 6 to Fig. 8, with the extension of processing time, in water body under the residual quantity of total nitrogen, ammoniacal nitrogen and nitrate nitrogen
Drop, slippage is the most notable in 0.5h.The adding proportion of nanometer oyster shell whiting and nano zero-valence iron powder is 8:1~4:1 (2~4g/
0.5g/L nano zero-valences iron powder is added in L nanometer oyster shell whitings) when, the clearance of total nitrogen, nitrate nitrogen and ammoniacal nitrogen is higher.Namibe
The adding proportion of shell powder and nano zero-valence iron powder is 4:Effect is the most notable when 1, in 0.5h the clearance of total nitrogen up to 92.1%,
The clearance of nitrate nitrogen is up to 95.3%, and the clearance of ammoniacal nitrogen is up to 96.8%.The addition of nanometer oyster shell whiting and nano zero-valence iron powder
Ratio is 4:When 1, the removal rate (0.5h) for reaching more than 90% adds nanometer oyster shell whiting (5h) (comparative example) higher than independent.
2nd, the influence that the different ratio of nanometer oyster shell whiting and nano zero-valence iron powder removes to total phosphorus in water
As shown in figure 9, with the extension of processing time, the clearance of total phosphorus in water raises.Nanometer oyster shell whiting and nanometer
The adding proportion of Zero-valent Iron is 8:1~4:When 1 (0.5g/L nano zero-valences iron powder is added in 2~4g/L nanometer oyster shell whitings), total phosphorus
Removal efficiency it is high.The adding proportion of nanometer oyster shell whiting and nano zero-valence iron powder is 4:Effect is the most notable when 1, total in 0.5h
The clearance of phosphorus is higher to the clearance of total phosphorus than individually addition nanometer oyster shell whiting up to 92.9%, and quickly.
3rd, the different ratio of nanometer oyster shell whiting and nano zero-valence iron powder is to Pb in water body2+The influence of removal
As shown in Figure 10, with the extension of processing time, Pb in water body2+Residual quantity decline.Nanometer oyster shell whiting and nanometer
The adding proportion of zeroth order iron powder is 8:1~4:When 1 (0.5g/L nano zero-valences iron powder is added in 2~4g/L nanometer oyster shell whitings), Pb2+
Removal efficiency it is high.The adding proportion of nanometer oyster shell whiting and nano zero-valence iron powder is 4:Effect is the most notable when 1, in 0.5h
Pb2+Clearance up to 93.1%, the clearance than individually addition nanometer oyster shell whiting is high, and quickly.
In summary experimental result is understood：
Although nanometer oyster shell whiting has certain removal to the total nitrogen in water body, nitrate nitrogen, ammoniacal nitrogen, total phosphorus and lead in itself
Effect, but treatment effeciency is not high enough, is unable to reach the requirement of efficient process aquiculture waste water.By comparison, by Namibe
Shell powder is with nano zero-valence iron powder by weight 4~8:After 1 composition inorganic agent, the removal rate of nitrogen phosphorus lead can be obviously improved, it is non-
Often meet the requirement of efficient process aquiculture waste water.
Embodiment 3 is using nanometer additive processing aquiculture waste water
Using nanometer oyster shell whiting and nano zero-valence iron powder same as Example 2, by weight 4:1 composition nanometered disposal
Agent.
Aquiculture waste water is put into and has measured volume in advance and has marked in the processing pond of graduation mark, and reaches its water surface
Graduation mark.Determine Determination of Total Nitrogen in Waste Water, ammoniacal nitrogen, nitrate nitrogen, total phosphorus and Pb2+Concentration.
By additive capacity 3g/L, nanometer additive is put into waste water, water body is then stirred using Mixing Machine, makes nanometer
Inorganic agent is dispersed in water.Note：It can also use pumping equipment to make water circulation herein, or water body flow is made using aerator
Decentralized approach.
After processing 0.5 hour, stop stirring, determine now Determination of Total Nitrogen in Waste Water, ammoniacal nitrogen, nitrate nitrogen, total phosphorus and Pb2+It is dense
Degree.
Each pollutant concentration is as shown in the table before and after the processing.
This shows that each pollutants removal rate reaches more than 90% in the waste water after processing, subsequently can be by after processing
Discharge of wastewater.
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
Into technical scheme, all fall within the protection domains of application claims.
Claims (6)
1. the nanometer additive of nitrogen phosphorus lead in aquiculture waste water is efficiently removed, it is characterized in that, by nanometer oyster shell whiting and nanometer zero
Valency iron powder is by weight 4~8:1 mixes, and the particle diameter of the nanometer oyster shell whiting is 100~300nm, the nano zero valence iron
The particle diameter of powder is 10~30nm.
2. nanometer additive according to claim 1, it is characterized in that, the weight of the nanometer oyster shell whiting and nano zero-valence iron powder
Amount is than being 4:1.
3. using the aquiculture waste water processing method of the nanometer additive of claim 1 or 2, it is characterized in that, including it is following
Step：
By the nanometer additive goals of investment aquiculture waste water, the additive capacity of nanometer additive is set to be at least 2g/L；It is logical
Decentralized processing is crossed, is dispersed in water nanometer additive, it is at least 0.5 hour to preset processing time；Reach default processing time
Afterwards, processing terminates；
Wherein, it is total nitrogen in target aquiculture waste water, ammoniacal nitrogen, nitrate nitrogen, total at the time of reaching in processing time 0.5 hour
Phosphorus and Pb2+Removal efficiency respectively reach more than 90%.
4. aquiculture waste water processing method according to claim 3, it is characterized in that, the additive of the nanometer additive
Measure as 2~4g/L.
5. aquiculture waste water processing method according to claim 3, it is characterized in that, the processing time is 0.5~1 small
When.
6. aquiculture waste water processing method according to claim 3, it is characterized in that, the decentralized processing, which includes using, to be stirred
Mechanical agitation water body is mixed, or water circulation is made using pumping equipment, or water body flow is made using aerator.
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| CN101690882A (en) * | 2009-10-14 | 2010-04-07 | 南开大学 | Natural adsorbent for removing heavy metal ions in water and preparation method and application thereof |
| CN104549126A (en) * | 2015-01-28 | 2015-04-29 | 福建农林大学 | Nano iron/oyster shell composite material, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7128841B2 (en) * | 2004-03-11 | 2006-10-31 | Lehigh University | Dispersed zero-valent iron colloids |
| CN106111048A (en) * | 2016-07-12 | 2016-11-16 | 成都理工大学 | One is used for removing phosphatic eggshell loaded nano-iron material and preparation method thereof in water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101690882A (en) * | 2009-10-14 | 2010-04-07 | 南开大学 | Natural adsorbent for removing heavy metal ions in water and preparation method and application thereof |
| KR20150118259A (en) * | 2014-04-11 | 2015-10-22 | 한국지질자원연구원 | Water treating composition including zero valent iron and nano-sized magnetite and Method for nitrate nitrogen treatment in ground using the same |
| CN104549126A (en) * | 2015-01-28 | 2015-04-29 | 福建农林大学 | Nano iron/oyster shell composite material, and preparation method and application thereof |
| CN105174321A (en) * | 2015-08-10 | 2015-12-23 | 浙江品洁环保科技有限公司 | Nanometer heavy-metal water purifying agent, preparation method and water purification unit |
| CN105561912A (en) * | 2015-12-16 | 2016-05-11 | 浙江省海洋水产研究所 | Method for treating heavy metal ion wastewater with modified shell powder |
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