CN106890625A - 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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- CN106890625A CN106890625A CN201710177741.0A CN201710177741A CN106890625A CN 106890625 A CN106890625 A CN 106890625A CN 201710177741 A CN201710177741 A CN 201710177741A CN 106890625 A CN106890625 A CN 106890625A
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- shell whiting
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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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- 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
- B01J20/28—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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to the nanometer additive of nitrogen phosphorus lead in efficiently removal aquiculture waste water, and using the aquiculture waste water processing method of 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.The present invention can realize quickly going to denitrogenate the treatment effect of phosphorus lead for aquiculture waste water, and to environment green non-pollution.
Description
Technical field
The present invention relates to the nanometer additive of nitrogen, phosphorus and lead in a kind of efficient removal aquiculture waste water, and use should
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 useless 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 that nano material has, the strange physics for making it show not available for many macro objects is 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 clearance of nitrogen, phosphorus and lead is relatively low, the shortcomings of process 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 the nano level modified shell that obtains for the treatment of
Powder, modified loofah sponge, sodium aluminate and titanium dioxide through processing the nano level modified diatomite for obtaining, obtain through treatment.But
It is that the preparation process of the technical scheme is more complicated, and needs to be used in the lump with reference to its purifier when water is processed, 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 to predetermined size, can remove Heavy Metals in Waters ion.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
The preparation method of the plain sorbing material of dimension》Chinese invention patent application, pre-processed respectively by with scallop shell and egg shell,
Crush afterwards, powder pulverized powder is mixed calcining in being put into Muffle furnace and obtains activity calcium oxide high, 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 treatment
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 for overcoming prior art to exist, proposes that one kind efficiently goes water removal
The nanometer additive of nitrogen phosphorus lead in aquaculture waste, can realize quickly going 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, make the additive capacity at least 2g/ of nanometer additive
L；By decentralized processing, it is dispersed in water nanometer additive, it is at least 0.5 hour to preset process time；Reached between when treated
During to default process time, treatment terminates；
Wherein, when process time reaches 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 process time is 0.5~1 hour.
Preferably, the decentralized processing includes stirring water body using Mixing Machine, 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 and the nanometer of defined particle size of defined particle size
Zeroth order iron powder, than composition inorganic agent, can be obviously improved the removal speed of nitrogen phosphorus lead in aquiculture waste water by the weight of above-mentioned restriction
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 treatment of 0.5 hour
Reason, very efficiently, beneficial to extensive treatment 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 nitrogen phosphorus lead clearance existed during water process is relatively low, and process time it is long the shortcomings of, also overcome exclusive use nanometer
Treatment effeciency relatively low shortcoming during oyster shell whiting, can realize quickly going to denitrogenate the treatment effect of phosphorus lead for aquiculture waste water, 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 different nanometer oyster shell whiting additions in different time to the removal efficiency curve map of 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.
It is total in different time is to water body with the different ratio of nano zero-valence iron powder that Fig. 6 to Fig. 8 is respectively nanometer oyster shell whiting
The influence curve figure of nitrogen, ammoniacal nitrogen and Nitrate Nitrogen Residue amount.
Fig. 9 is nanometer oyster shell whiting with the different ratio of nano zero-valence iron powder in different time to the removal effect of total phosphorus in water
Rate curve map.
Figure 10 Pb that are nanometer oyster shell whiting with the different ratio of nano zero valence iron in different time is to water body2+The shadow of residual quantity
Ring curve map.
Specific 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 be given
The example for going out.
Embodiment 1 prepares the aquiculture waste water of simulation
According to the measured data of accumulation, common contaminant species and corresponding concentration the level such as 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
Using the nanometer oyster shell whiting of 100~300nm of particle diameter, can be by country of Institutes Of Technology Of Nanjing special type superfine powder engineering skill
Art research center provides.
To the gained waste water of 300ml embodiments 1 is separately added into 5 conical flasks of 500ml, a nanometer shell is then weighed 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.Successively in shake 0, sampled after 0.05,0.5,5,50,500h, determine 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.
To the gained waste water of 300ml embodiments 1 is separately added into 6 conical flasks of 500ml, wherein 1 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
(concentration 0.5g/L is reached in bottle)；During this 6 conical flasks are placed into shaking table, 25 DEG C of shaking table temperature, rotating speed 150rpm/ are set
min.Successively in shake 0, sampled after 0.05,0.5,5,50,500h, determine total nitrogen, ammoniacal nitrogen, nitrate nitrogen, total phosphorus and heavy metal
The content of lead.
The experimental result of comparative example and embodiment 2 is comprehensively described below：
(1) determination of most suitable nanometer oyster shell whiting addition scope
1st, influence of the different nanometer oyster shell whiting additions to different shape nitrogen removal 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, up to 91.1%, the clearance of nitrate nitrogen is up to 96.8%, the clearance of ammoniacal nitrogen for the clearance of total nitrogen in 5h
Up to 92.9%.
2nd, the influence that different nanometer oyster shell whiting additions are removed 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 is raised.In addition
During for 2~4g/L, 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 (residual quantity 0.02mg/L is less than water quality standard for fishery) up to 80%, 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 substantially, especially when addition is 2g/L, imitate by removal
It is really 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 is removed to Water
In embodiment 2, nanometer oyster shell whiting and the nano zero-valence iron powder weight ratio of each treatment are 2:Isosorbide-5-Nitrae:1,6:1 and 8:1.
From Fig. 6 to Fig. 8, with the extension of process 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.Nanometer oyster shell whiting is 8 with the adding proportion of nano zero-valence iron powder:1~4:1 (2~4g/
0.5g/L nano zero-valences iron powder is added in L nanometers of oyster shell whiting) when, the clearance of total nitrogen, nitrate nitrogen and ammoniacal nitrogen is higher.Namibe
Shell powder is 4 with the adding proportion of nano zero-valence iron powder:Effect is the most notable when 1, in 0.5h the clearance of total nitrogen up to 92.1%,
Up to 95.3%, the clearance of ammoniacal nitrogen is up to 96.8% for the clearance of nitrate nitrogen.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 is removed to total phosphorus in water
As shown in figure 9, with the extension of process time, the clearance of total phosphorus in water is raised.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 nanometers of oyster shell whiting), total phosphorus
Removal efficiency it is high.Nanometer oyster shell whiting is 4 with the adding proportion of nano zero-valence iron powder: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 process 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 nanometers of oyster shell whiting), Pb2+
Removal efficiency it is high.Nanometer oyster shell whiting is 4 with the adding proportion of nano zero-valence iron powder: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 understands：
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, it is impossible 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 processes aquiculture waste water using nanometer additive
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 the processing pond for having measured volume in advance and having marked 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, by nanometer additive input waste water, water body is then stirred using Mixing Machine, make nanometer
Inorganic agent is dispersed in water.Note：Also water circulation can be made using pumping equipment herein, or water body flow is made using aerator
Decentralized approach.
After treatment 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 after before processing.
This shows, more than 90% is reached through each pollutants removal rate in the waste water after treatment, subsequently can be by after treatment
Discharge of wastewater.
In addition to the implementation, the present invention can also have other embodiment.All use equivalents or equivalent transformation shape
Into technical scheme, all fall within the protection domain of application claims.
Claims (7)
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 composition, the particle diameter of the nanometer oyster shell whiting is at most 300nm, the grain of the nano zero-valence iron powder
Footpath is at most 30nm.
2. the nanometer additive addressed according to claim 1, it is characterized in that, the particle diameter of the nanometer oyster shell whiting for 100~
300nm, the particle diameter of the nano zero-valence iron powder is 10~30nm.
3. the nanometer additive addressed 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.
4. the aquiculture waste water processing method of nanometer additive is addressed using claim 1 or 2 or 3, it is characterized in that, including with
Lower step：
By the nanometer additive goals of investment aquiculture waste water, make the additive capacity at least 2g/L of nanometer additive；It is logical
Decentralized processing is crossed, nanometer additive is dispersed in water, it is at least 0.5 hour to preset process time；Reach default process time
Afterwards, treatment terminates；
Wherein, it is total nitrogen in target aquiculture waste water, ammoniacal nitrogen, nitrate nitrogen, total when process time reaches 0.5 hour
Phosphorus and Pb2+Removal efficiency respectively reach more than 90%.
5. the aquiculture waste water processing method addressed according to claim 4, it is characterized in that, the additive of the nanometer additive
It is 2~4g/L to measure.
6. the aquiculture waste water processing method addressed according to claim 4, it is characterized in that, the process time is 0.5~1 small
When.
7. the aquiculture waste water processing method addressed according to claim 4, it is characterized in that, the decentralized processing 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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| CN110314655A (en) * | 2019-06-03 | 2019-10-11 | 武汉工程大学 | A kind of bagasse load zeroth order iron adsorbent and its preparation method and application |
| CN114368859A (en) * | 2022-01-12 | 2022-04-19 | 四川轻化工大学 | Breeding wastewater treatment device |
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| CN114368859A (en) * | 2022-01-12 | 2022-04-19 | 四川轻化工大学 | Breeding wastewater treatment device |
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| CN106890625B (en) | 2018-03-20 |
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