CN106892481A - Magnetic coupling algicide and its application method - Google Patents
Magnetic coupling algicide and its application method Download PDFInfo
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- CN106892481A CN106892481A CN201710101905.1A CN201710101905A CN106892481A CN 106892481 A CN106892481 A CN 106892481A CN 201710101905 A CN201710101905 A CN 201710101905A CN 106892481 A CN106892481 A CN 106892481A
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention relates to a kind of magnetic coupling algicide and its application method, adsorbent is dispersed in Shui Zhongjiang and is placed in water-bath tank, by FeCl3·6H2O and FeCl2·4H2O is with mol ratio 2:1 amount puts into water-bath tank, quick stirring, and temperature control adds ammoniacal liquor at 60 DEG C 90 DEG C after 15 30min of stirring, continues to react 2 4h, and the unassembled magnetic Nano material of washing removal and adsorbent are obtained composite magnetic adsorbent；Composite magnetic adsorbent and photochemical catalyst precursor liquid are added in hydrothermal reaction kettle again, in 160 DEG C 220 DEG C, 10 24h of reaction, reaction completion is cooled to room temperature, scrubbed, Magneto separate, drying, by adsorbent and photocatalyst on magnetic Nano material.The pollutants such as the nitrogen phosphorus in the efficient adsorption-flocculation algae of magnetic coupling algicide energy of the invention and water, the toxin of algae release of being degraded by photocatalysis improves algae treatment effeciency.
Description
Technical field
The present invention relates to a kind of magnetic coupling algicide and its application method, belong to technical field of water pollution treatment.
Background technology
With urbanization and the development of process of industrialization, the mankind by a large amount of sanitary sewages and industrial wastewater be drained into river and
Lake, causes water body self-purification ability weak, causes body eutrophication, have impact on water safety and living environment.Wherein algae is quick-fried
Hair can exhaust water oxygen causes fish dead, and the toxin of some algae release can poison biology, such as the micro-capsule in blue-green algae
Algae meeting release microcapsule Algae toxins, are highly toxic, have harm to aquatile and the mankind.Therefore how fast and effectively to process
Algae, be administer water pollution in the urgent need to.
The algae administered in water at present, frequently with artificial removing, wastes time and energy, and treatment effeciency is low.Also some processing methods
It is, to agent of being spread pesticides in water body, to make algae dead or precipitation.Can be bubbled through the water column by carrier of float stone as disclosed in CN102249369A
Cyanobacterial scavenger, float stone outside parcel TiO2Pillared montmorillonite photochemical catalyst, medicament is on the water surface by absorption and photocatalysis
Coordinative role degraded blue-green algae, with removing blue-green algae efficiency high, instant effect, the advantage of non-secondary pollution, but collecting needs by beating
Drag for, operation inconvenience.Disclosed in CN103030203A composite type inorganic polymer stabilization algicide preparation and algae-removing method, be
Graft acrylic acid forms floccule body on magnetic, then compound with attapulgite and activated carbon, finally mixed with aluminium chloride ferrum and shitosan
Synthesis algicide, algae is adsorbed using suction-operated, then reclaims algicide with magnet, but only there is the technical scheme absorption to make
With, and the algae toxin that can not degrade.
The content of the invention
It is an object of the invention to provide a kind of magnetic coupling algicide and its application method, can efficient adsorption-flocculation algae
And the pollutant such as the nitrogen phosphorus in water, can also be degraded the toxin that algae discharges by photocatalysis, by the effect of external magnetic field
Algae is removed into water body, the treatment effeciency of algae is improved.
The present invention is that the technical scheme for reaching above-mentioned purpose is：A kind of magnetic coupling algicide, it is characterised in that：Including solid
The magnetic Nano material of phase, the adsorbent for adsorbing algae porous material and the photocatalysis for degrade algae and algae toxin
Agent, described magnetic Nano material is ferriferrous oxide nano-particle, and described adsorbent is montmorillonite, attapulgite, mesoporous
One or more mixing in carbon, during described photochemical catalyst is nano level titanium dioxide, bismuth tungstate or bismuth ferrite
One of them；First adsorbent is dispersed in water-bath tank is subsequently placed in water, be passed through nitrogen protection, then by FeCl3·
6H2O and FeCl2·4H2O is with mol ratio 2:1 amount is put into water-bath tank, by the throwing of adsorbent and magnetic Nano material
Material mass ratio control is 1:0.4-1.4, quick stirring, bath temperature is controlled at 60 DEG C -90 DEG C, and matter is added after stirring 15-30min
Amount fraction is 30% ammoniacal liquor, by the pH value control of solution in 11-13, continues to react 2-4h, the unassembled magnetic of washing removal
Nano material and adsorbent, are obtained the composite magnetic adsorbent that magnetic Nano material is loaded with adsorbent；Will be obtained compound
During magnetic adsorbent is added to hydrothermal reaction kettle together with photochemical catalyst precursor liquid, by composite magnetic adsorbent and photochemical catalyst
The mass ratio that feeds intake is controlled 1:1-3, described photochemical catalyst precursor liquid is titanium dioxide precursor liquid or bismuth tungstate precursor liquid or iron
Sour bismuth precursor liquid, with hydro-thermal method in 160 DEG C -220 DEG C, reaction 10-24h, photochemical catalyst is loaded with composite magnetic adsorbent,
Room temperature is cooled to after the completion of reaction, scrubbed, Magneto separate is dried, by adsorbent and photocatalyst in 60-80 DEG C of baking oven
On magnetic Nano material, magnetic coupling algicide is obtained.
Wherein：Described titanium dioxide precursor liquid, bismuth tungstate precursor liquid and bismuth ferrite precursor liquid are obtained by sol-gal process.
Described titania precursor liquid includes TiCl4Raw material, by mass fraction ratio, by 1：1 TiCl4 is added to the water and is made
Vitreosol, adds the concentrated sulfuric acid, and the pH value of vitreosol is controlled in 1-3, and titanium dioxide precursor liquid is obtained.
Described bismuth tungstate precursor liquid includes Bi (NO3)3·5H2O and Na2WO4·2H2O, and Bi (NO3)3·5H2O with
Na2WO4·2H2The mol ratio of O is 2:1, by Bi (NO3)3·5H2O and Na2WO4·2H2O is dissolved in ethylene glycol solvent respectively, then
Will both mixing and stirrings, prepared bismuth tungstate precursor liquid.
Described bismuth ferrite precursor liquid includes Bi (NO3)3·5H2O and Fe (NO3)3·9H2O, and Bi (NO3)3·5H2O with
Fe(NO3)3·9H2The mol ratio of O is 1:1, by Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is dissolved in second two plus ether solvents respectively
In, then will both mixing and stirrings, add glacial acetic acid to continue to stir bismuth ferrite precursor liquid is obtained, wherein, glacial acetic acid and second two
The volume ratio of methyl ether is 1:2-6.
The application method of magnetic coupling algicide of the invention, it is characterised in that：By magnetic coupling algicide according to 0.8-
The dosage of 1.5g/L is added in the eutrophic water containing algae, is stirred 1-10 minutes, stands 5-10 minutes, then will with magnet
Algae floccule body removes the water surface.
Present invention employs the magnetic Nano material carrier of solid phase, and the adsorbent of algae porous material can be adsorbed and energy is used
On magnetic Nano material, the illiteracy present invention employs porous material takes off the photocatalyst of degraded algae and algae toxin
Stone, attapulgite or mesoporous carbon make that adsorbent is nontoxic, specific surface area is big and stable chemical nature excellent as adsorbent
Point, makes adsorbent have good absorption property, the blue-green algae in energy adsorbed water body.The nano level titanium dioxide of present invention use,
Bismuth tungstate or bismuth ferrite make photochemical catalyst have the spies such as photocatalysis efficiency is high, non-toxic, chemical stability is good as photochemical catalyst
Point, degrade algae and algae toxin, it is low to the blue alga clearing efficiency in water body to compensate for adsorbent, and the cyanophycean toxin that can not degrade
Defect, while by photocatalyst on magnetic Nano material, also solving because nano-photocatalyst particle diameter is small, after reaction
The problem being easily lost in.The present invention is first by adsorbent and FeCl3·6H2O and FeCl2·4H2O is reacted, and magnetic is obtained and receives
Rice material load has the composite magnetic adsorbent of adsorbent, then obtained composite magnetic adsorbent and photochemical catalyst precursor liquid are entered
Row reaction, the photochemical catalyst in load on composite magnetic adsorbent.The magnetic that the present invention is made by the mass ratio that specifically feeds intake
Composite algicide has preferable chemical stability, makes the dirts such as the nitrogen phosphorus that algicide can efficiently in adsorption-flocculation algae and water
Dye thing, and the transparency in water can be improved, purify water, the toxin of solution algae release can be declined in photocatalysis again, degraded
Water pollutant and algae toxin, in the presence of externally-applied magnetic field, energy fast enriching algae solves asking for the difficult salvaging of algae
Topic, can realize that quick, safety, non-secondary pollution are administered to the algae in water.
Specific embodiment
A kind of magnetic coupling algicide of the invention, including solid phase magnetic Nano material, for adsorbing the porous material of algae
The adsorbent of material and the photochemical catalyst for degrade algae and algae toxin, magnetic Nano material of the invention are ferroso-ferric oxide
Nano-particle, by ferriferrous oxide nano-particle as carrier supported sorbents and photochemical catalyst.
Adsorbent of the invention is one or more mixing, photochemical catalyst in montmorillonite, attapulgite, mesoporous carbon
One of in for nano level titanium dioxide, bismuth tungstate or bismuth ferrite.
First adsorbent is dispersed in water-bath tank is subsequently placed in water, deionized water or distilled water etc. can be used,
Nitrogen protection is passed through, then by FeCl3·6H2O and FeCl2·4H2O is with mol ratio 2:1 amount is put into water-bath tank, will
Adsorbent is controlled 1 with the mass ratio that feeds intake of magnetic Nano material:0.4-1.4, quick stirring, bath temperature control 60 DEG C-
90 DEG C, the ammoniacal liquor that mass fraction is 30% is added after stirring 15-30min, by the pH value control of solution in 11-13, continue to react
2-4h, washing removal unassembled magnetic Nano material and adsorbent, obtains the compound magnetic of magnetic Nano material supported sorbents
Property adsorbent.
Obtained composite magnetic adsorbent is added in hydrothermal reaction kettle together with photochemical catalyst precursor liquid, by compound magnetic
Property adsorbent and photochemical catalyst the mass ratio that feeds intake control 1:1-3, photochemical catalyst precursor liquid of the invention is for before titanium dioxide
Drive liquid or bismuth tungstate precursor liquid or bismuth ferrite precursor liquid, titanium dioxide precursor liquid of the invention, bismuth tungstate precursor liquid and bismuth ferrite
Precursor liquid is obtained by sol-gal process, with hydro-thermal method in 160 DEG C -220 DEG C, reaction 10-24h, is born on composite magnetic adsorbent
Photocatalyst-bearing, is cooled to room temperature after the completion of reaction, scrubbed, Magneto separate is dried, by adsorbent in 60-80 DEG C of baking oven
With photocatalyst on magnetic Nano material, magnetic coupling algicide is obtained.
Magnetic coupling algicide of the invention, in substep building-up process, by feeding intake for adsorbent and magnetic Nano material
Mass ratio is controlled 1:0.4-1.4, and the mass ratio that feeds intake of composite magnetic adsorbent and photochemical catalyst is controlled 1:1-3, passes through
Specific ingredient proportion, can make algicide of the invention have preferable chemical stability, can efficiently removing blue algae, blue-green algae of degrading
Toxin, it is easy to be recycled under additional magnetic fields.
Titania precursor liquid of the invention includes TiCl4Raw material, by mass fraction ratio, by 1：1 TiCl4It is added to the water system
Into vitreosol, the concentrated sulfuric acid can be added using deionized water or distilled water etc., by the pH value control of vitreosol in 1-3, system
Obtain titanium dioxide precursor liquid.
Bismuth tungstate precursor liquid of the present invention includes Bi (NO3)3·5H2O and Na2WO4·2H2O, and Bi (NO3)3·5H2O with
Na2WO4·2H2The mol ratio of O is 2:1, by Bi (NO3)3·5H2O and Na2WO4·2H2O is dissolved in ethylene glycol solvent respectively, then
Will both mixing and stirrings, prepared bismuth tungstate precursor liquid.
Bismuth ferrite precursor liquid of the invention includes Bi (NO3)3·5H2O and Fe (NO3)3·9H2O, and Bi (NO3)3·5H2O
With Fe (NO3)3·9H2The mol ratio of O is 1:1, by Bi (NO3)3·5H2O and Fe (NO3)3·9H2O is dissolved in second two respectively plus ether is molten
In agent, then will both mixing and stirrings, add glacial acetic acid to continue to stir bismuth ferrite precursor liquid is obtained, wherein, glacial acetic acid and second
The volume ratio of dimethyl ether is 1:2-6.
It is pure that the above-mentioned each raw material of the present invention is chemistry.
Magnetic coupling algicide of the invention when in use, by magnetic coupling algicide according to 0.8-1.5g/L dosage
It is added in the eutrophic water containing algae, stirs 1-10 minutes, stand 5-10 minutes, then is removed algae floccule body with magnet
The water surface.
The content of the invention of the invention is elaborated with reference to instantiation, but following instance is not intended to limit the present invention
Scope.
Embodiment 1
(1), 4.34g montmorillonites are dispersed in water-bath tank is subsequently placed in the deionized water of 50ml, be passed through nitrogen
Protection, by 50ml 0.6mol/LFeCl3·6H2O and 50ml 0.3mol/LFeCl2·4H2O is put into water-bath tank, soon
Speed stirring, 85 DEG C -90 DEG C of bath temperature adds the ammoniacal liquor that mass fraction is 30% after stirring 30min, the pH value of solution is controlled
11, continue to react 4h, washing removal unassembled magnetic Nano material and adsorbent obtain magnetic Nano material and be loaded with inhaling
Attached dose of composite magnetic adsorbent.Montmorillonite and the mass ratio that feeds intake of the ferriferrous oxide nano-particle for being formed are 1 during this:
0.8。
(2), by the TiCl of 11.87g4It is added in the deionized water of 11.87ml, stirring forms vitreosol, adds dense
Sulfuric acid, the pH value of vitreosol is controlled 1.5, and titanium dioxide precursor liquid is obtained.
(3), take during the above-mentioned composite magnetic adsorbents of 2g are added to hydrothermal reaction kettle together with photochemical catalyst precursor liquid, use
Hydro-thermal method is cooled to room temperature in 160 DEG C, reaction 24h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction,
Scrubbed, Magneto separate, dries in 60 DEG C of baking ovens, and magnetic coupling algicide is obtained.Ferriferrous oxide nano-particle during this
It is 1 that the composite magnetic adsorbent of montmorillonite is loaded with the mass ratio that feeds intake of the titanium dioxide nano photocatalysis agent for being formed:2.5.
The magnetic coupling algicide of 1g of the present invention is added in eutrophic waters of the 1L containing algae, under 15W uviol lamps,
Stirring 10 minutes, stands 10 minutes, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》Inspection
Chlorophyll a, algae density and the turbidity surveyed in eutrophic water, experimental result such as table 1 below.
Table 1
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.39 | 93.6 |
| Algae density (individual/L) | 94.3 | ||
| Turbidity (%) | 27 | 4.05 | 85 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 93.6%, the clearance of algae density is up to 94.3%, turbidity 85% for rate.As can be seen here, the magnetic coupling algicide effect is significant.
Embodiment 2
(1) the attapulgite of 3.475g is dispersed in and water-bath tank is subsequently placed in the deionized water of 50ml, be passed through
Nitrogen is protected, by 50ml 0.6mol/LFeCl3·6H2O and 50ml 0.3mol/LFeCl2·4H2O puts into water-bath tank
In, quick stirring, 75 DEG C -85 DEG C of bath temperature adds the ammoniacal liquor that mass fraction is 30%, by the PH of solution after stirring 25min
Value control continues to react 3.5h 12, and washing removal unassembled magnetic Nano material and adsorbent obtain magnetic Nano material
It is loaded with the composite magnetic adsorbent of adsorbent.Attapulgite feeds intake with the ferriferrous oxide nano-particle for being formed during this
Mass ratio is 1:1.
(2), by 8mmolBi (NO3)3·5H2O and 4mmolNa2WO4·2H2O is added separately in the ethylene glycol solvent of 60ml
Vitreosol is prepared into, then two vitreosols are mixed, bismuth tungstate precursor liquid is obtained.
(3), the above-mentioned composite magnetic adsorbents of 1.35g are added in hydrothermal reaction kettle together with bismuth tungstate precursor liquid, water is used
Hot method is cooled to room temperature, passes through in 175 DEG C, reaction 22h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction
Washing, Magneto separate, dry in 70 DEG C of baking ovens, and magnetic coupling algicide is obtained.During this, ferriferrous oxide nano-particle is born
It is 1 that the composite magnetic adsorbent of attapulgite is loaded with the mass ratio that feeds intake of the bismuth tungstate photocatalyst for being formed:2.
The magnetic coupling algicide of 0.8g of the present invention is added in eutrophic waters of the 1L containing algae, under sunshine,
Stirring 1 minute, stands 5 minutes, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》Detection
Chlorophyll a, algae density and turbidity in eutrophic water, experimental result such as table 2 below.
Table 2
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.57 | 90.8 |
| Algae density (individual/L) | 91.0 | ||
| Turbidity (%) | 27 | 6.10 | 77.4 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 90.8%, the clearance of algae density is up to 91.0%, turbidity 77.4% for rate.As can be seen here, the magnetic coupling algicide effect shows
Write.
Embodiment 3
(1), the mesoporous carbon of 4.63g is dispersed in water-bath tank is subsequently placed in the deionized water of 80ml, be passed through nitrogen
Gas shielded, by 80ml 0.6mol/LFeCl3·6H2O and 80ml 0.3mol/LFeCl2·4H2O is put into water-bath tank,
Quick stirring, 65 DEG C -75 DEG C of bath temperature adds the ammoniacal liquor that mass fraction is 30%, by the pH value control of solution after stirring 20min
System continues to react 3h 13, and washing removal unassembled magnetic Nano material and adsorbent obtain magnetic Nano material and be loaded with
The composite magnetic adsorbent of adsorbent.Mesoporous carbon is with the mass ratio that feeds intake of the ferriferrous oxide nano-particle for being formed during this
1:1.2。
(2), by 8mmolBi (NO3)3·5H2O and 8mmol Fe (NO3)3·9H2O is added separately to the second two plus ether of 60ml
Vitreosol is prepared into solvent, then two vitreosols are mixed, add the glacial acetic acid of 10ml to continue to stir prepared ferrous acid
Bismuth precursor liquid.
(3), the above-mentioned composite magnetic adsorbents of 5g are added in hydrothermal reaction kettle together with bismuth ferrite precursor liquid, hydro-thermal is used
Method is cooled to room temperature, through washing in 200 DEG C, reaction 18h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction
Wash, Magneto separate, dried in 70 DEG C of baking ovens, magnetic coupling algicide is obtained, ferriferrous oxide nano-particle load during this
The composite magnetic adsorbent of mesoporous carbon is 1 with the mass ratio that feeds intake of the bismuth ferrite photocatalyst for being formed:1.
The magnetic coupling algicide of 1.5g of the present invention is added in eutrophic waters of the 1L containing algae, is stirred under sunshine
8 minutes, 8 minutes are stood, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》The rich battalion of detection
Chlorophyll a, algae density and turbidity in fosterization water, experimental result such as table 3 below.
Table 3
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.34 | 94.5 |
| Algae density (individual/L) | 95.4 | ||
| Turbidity (%) | 27 | 3.45 | 87.2 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 94.5%, the clearance of algae density is up to 95.4%, turbidity 87.2% for rate.As can be seen here, the magnetic coupling algicide effect shows
Write.
Embodiment 4
(1), the montmorillonite of the attapulgite of 1.6g and 1.6g is dispersed in the deionized water of 80ml and is subsequently placed in water
Bath retort, is passed through nitrogen protection, by 60ml 0.6mol/LFeCl3·6H2O and 60ml 0.3mol/LFeCl2·4H2O puts into
To in water-bath tank, quick stirring, 60 DEG C -70 DEG C of bath temperature adds the ammonia that mass fraction is 30% after stirring 15min
Water, by the pH value control of solution 12.5, continues to react 2.5h, and washing removes unassembled magnetic Nano material and adsorbent,
Obtain the composite magnetic adsorbent that magnetic Nano material is loaded with adsorbent.Adsorbent total amount and four oxidations for being formed during this
The mass ratio that feeds intake of three Fe nanometer particles is 1:1.3.
(2), by 8mmolBi (NO3)3·5H2O and 4mmolNa2WO4·2H2O is added separately in the ethylene glycol solvent of 60ml
Vitreosol is prepared into, then two vitreosols are mixed, bismuth tungstate precursor liquid is obtained.
(3), the above-mentioned composite magnetic adsorbents of 2.473g are added in hydrothermal reaction kettle together with bismuth tungstate precursor liquid, are used
Hydro-thermal method is cooled to room temperature in 220 DEG C, reaction 10h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction,
Scrubbed, Magneto separate, dries in 70 DEG C of baking ovens, and magnetic coupling algicide, ferriferrous oxide nano-particle during this is obtained
It is 1 that attapulgite and the composite magnetic adsorbent of montmorillonite are loaded with the mass ratio that feeds intake of the bismuth tungstate photocatalyst for being formed:
1.5。
The magnetic coupling algicide of 0.9g of the present invention is added in eutrophic waters of the 1L containing algae, is stirred under sunshine
10 minutes, 5 minutes are stood, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》Detection is rich
Chlorophyll a, algae density and turbidity in nutrient laden water, experimental result such as table 4 below.
Table 4
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.63 | 89.8 |
| Algae density (individual/L) | 91.3 | ||
| Turbidity (%) | 27 | 5.8 | 78.5 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 89.8/%, the clearance of algae density is up to 91.3%, turbidity 78.5% for rate.As can be seen here, the magnetic coupling algicide effect shows
Write.
Embodiment 5
By the montmorillonite of 0.9928g, 0.9928g attapulgites and 0.9928g mesoporous carbons be dispersed in 70ml go from
Water-bath tank is subsequently placed in sub- water, nitrogen protection is passed through, by 60ml 0.6mol/LFeCl3·6H2O and 60ml0.3mol/
LFeCl2·4H2O is put into water-bath tank, quick stirring, and 75 DEG C -85 DEG C of bath temperature adds quality after stirring 25min
Fraction is 30% ammoniacal liquor, by the pH value control of solution 12, continues to react 3.5h, the unassembled magnetic Nano material of washing removal
Material and adsorbent, obtain the composite magnetic adsorbent that magnetic Nano material is loaded with adsorbent.During this adsorbent total amount with
The mass ratio that feeds intake of the ferriferrous oxide nano-particle of formation is 1:1.4.
(2), by 10mmolBi (NO3)3·5H2O and 10mmol Fe (NO3)3·9H2The second two that O is added separately to 60ml adds
Vitreosol is prepared into ether solvents, then two vitreosols are mixed, add the glacial acetic acid of 20ml to continue to stir prepared iron
Sour bismuth precursor liquid.
(3), the above-mentioned composite magnetic adsorbents of 1.042g are added in hydrothermal reaction kettle together with bismuth tungstate precursor liquid, are used
Hydro-thermal method is cooled to room temperature in 175 DEG C, reaction 22h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction,
Scrubbed, Magneto separate, dries in 70 DEG C of baking ovens, and magnetic coupling algicide, ferriferrous oxide nano-particle during this is obtained
It is loaded with the composite magnetic adsorbent of montmorillonite, attapulgite and mesoporous carbon and the quality that feeds intake of the bismuth tungstate photocatalyst for being formed
Than being 1:3.
The magnetic coupling algicide of 1.2g of the present invention is added in eutrophic waters of the 1L containing algae, is stirred under solar irradiation
Mix 5 minutes, stand 10 minutes, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》Detection
Chlorophyll a, algae density and turbidity in eutrophic water, experimental result such as table 5 below.
Table 5
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.56 | 91 |
| Algae density (individual/L) | 92.6 | ||
| Turbidity (%) | 27 | 5.1 | 81.1 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 91%, the clearance of algae density is up to 92.6%, turbidity 81.1% for rate.As can be seen here, the magnetic coupling algicide effect is significant.
Embodiment 6
(1), the mesoporous carbon of the attapulgite of 2.6g and 2.6g is dispersed in the deionized water of 800ml and is subsequently placed in
Water-bath tank, is passed through nitrogen protection, by 30ml 0.6mol/LFeCl3·6H2O and 30ml 0.3mol/L FeCl2·4H2O
Put into water-bath tank, quickly stir, 60 DEG C -70 DEG C of bath temperature, it is 30% to add mass fraction after stirring 15min
Ammoniacal liquor, by the pH value control of solution 12.5, continues to react 2.5h, the unassembled magnetic Nano material of washing removal and absorption
Agent, obtains the composite magnetic adsorbent that magnetic Nano material is loaded with adsorbent.Adsorbent total amount and four for being formed during this
The mass ratio that feeds intake of Fe 3 O nano-particle is 1:0.4.
(2), by 8mmolBi (NO3)3·5H2O and 4mmolNa2WO4·2H2O is added separately in the ethylene glycol solvent of 60ml
Vitreosol is prepared into, then two vitreosols are mixed, bismuth tungstate precursor liquid is obtained.
(3), the above-mentioned composite magnetic adsorbents of 2.066g are added in hydrothermal reaction kettle together with bismuth tungstate precursor liquid, are used
Hydro-thermal method is cooled to room temperature in 220 DEG C, reaction 10h, the photochemical catalyst in load on composite magnetic adsorbent after the completion of reaction,
Scrubbed, Magneto separate, dries in 70 DEG C of baking ovens, and magnetic coupling algicide, ferriferrous oxide nano-particle during this is obtained
It is 1 that attapulgite and the composite magnetic adsorbent of mesoporous carbon are loaded with the mass ratio that feeds intake of the bismuth tungstate photocatalyst for being formed:
1.8.The magnetic coupling algicide of 1g of the present invention is added in eutrophic waters of the 1L containing algae, 10 points are stirred under sunshine
Clock, stands 5 minutes, then algae floccule body is removed into the water surface with magnet.Press《Water and effluent monitoring analysis method》Detection eutrophy
Chlorophyll a, algae density and turbidity in change water, experimental result such as table 6 below.
Table 6
| Index | Raw water | Water sample after agent-feeding treatment | Clearance (%) |
| Chlorophyll a (mg/L) | 6.2 | 0.52 | 91 |
| Algae density (individual/L) | 92.1 | ||
| Turbidity (%) | 27 | 6.3 | 76.7 |
Water sample after being processed through magnetic coupling algicide of the invention, visually sees that water body is substantially limpid, the removal of chlorophyll a
Up to 91%, the clearance of algae density is up to 92.1%, turbidity 76.7% for rate.As can be seen here, the magnetic coupling algicide effect is significant.
Claims (6)
1. a kind of magnetic coupling algicide, it is characterised in that：Magnetic Nano material including solid phase, for adsorbing the porous material of algae
The adsorbent of material and the photochemical catalyst for degrade algae and algae toxin, described magnetic Nano material are received for ferroso-ferric oxide
Rice corpuscles, described adsorbent is one or more mixing in montmorillonite, attapulgite, mesoporous carbon, and described light is urged
Agent be nano level titanium dioxide, bismuth tungstate or bismuth ferrite in one of；First adsorbent is dispersed in water so
After be placed in water-bath tank, be passed through nitrogen protection, then by FeCl3·6H2O and FeCl2·4H2O is with mol ratio 2:1 amount input
To in water-bath tank, the mass ratio that feeds intake of adsorbent and magnetic Nano material is controlled 1:0.4-1.4, quick stirring, water
Bath temperature is controlled at 60 DEG C -90 DEG C, and the ammoniacal liquor that mass fraction is 30% is added after stirring 15-30min, and the pH value of solution is controlled
In 11-13, continue to react 2-4h, washing removal unassembled magnetic Nano material and adsorbent are obtained magnetic Nano material
It is loaded with the composite magnetic adsorbent of adsorbent；Obtained composite magnetic adsorbent is added to together with photochemical catalyst precursor liquid
In hydrothermal reaction kettle, the mass ratio that feeds intake of composite magnetic adsorbent and photochemical catalyst is controlled 1:1-3, described photochemical catalyst
Precursor liquid is titanium dioxide precursor liquid or bismuth tungstate precursor liquid or bismuth ferrite precursor liquid, with hydro-thermal method in 160 DEG C -220 DEG C, reaction
10-24h, is loaded with photochemical catalyst on composite magnetic adsorbent, is cooled to room temperature after the completion of reaction, scrubbed, Magneto separate,
Dried in 60-80 DEG C of baking oven, by adsorbent and photocatalyst on magnetic Nano material, obtain magnetic coupling algicide.
2. magnetic coupling algicide according to claim 1, it is characterised in that：Described titanium dioxide precursor liquid, bismuth tungstate
Precursor liquid and bismuth ferrite precursor liquid are obtained by sol-gal process.
3. magnetic coupling algicide according to claim 1 or claim 2, it is characterised in that：Described titania precursor liquid includes
TiCl4Raw material, by mass fraction ratio, by 1：1 TiCl4 is added to the water and is made vitreosol, adds the concentrated sulfuric acid, will be transparent molten
The pH value of glue is controlled in 1-3, and titanium dioxide precursor liquid is obtained.
4. magnetic coupling algicide according to claim 1 or claim 2, it is characterised in that：Described bismuth tungstate precursor liquid includes Bi
(NO3)3·5H2O and Na2WO4·2H2O, and Bi (NO3)3·5H2O and Na2WO4·2H2The mol ratio of O is 2:1, by Bi
(NO3)3·5H2O and Na2WO4·2H2O is dissolved in ethylene glycol solvent respectively, then will both mixing and stirrings, prepared bismuth tungstate
Precursor liquid.
5. magnetic coupling algicide according to claim 1 and 2, it is characterised in that：Described bismuth ferrite precursor liquid includes
Bi(NO3)3·5H2O and Fe (NO3)3·9H2O, and Bi (NO3)3·5H2O and Fe (NO3)3·9H2The mol ratio of O is 1:1, by Bi
(NO3)3·5H2O and Fe (NO3)3·9H2O is dissolved in second two plus ether solvents respectively, then will both mixing and stirrings, addition ice
Acetic acid continues to stir prepared bismuth ferrite precursor liquid, wherein, glacial acetic acid is 1 with the volume ratio of second dimethyl ether:2-6.
6. the application method of magnetic coupling algicide according to claim 1, it is characterised in that：Magnetic coupling algicide is pressed
Dosage according to 0.8-1.5g/L is added in the eutrophic water containing algae, is stirred 1-10 minutes, stands 5-10 minutes, then use
Algae floccule body is removed the water surface by magnet.
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| CN107473345A (en) * | 2017-07-31 | 2017-12-15 | 常州诺澜复合材料有限公司 | A kind of preparation method of composite algicide |
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Application publication date: 20170627 |