CN107473387A - A kind of artificial swamp dephosphorization matrix fill and preparation method thereof - Google Patents
A kind of artificial swamp dephosphorization matrix fill and preparation method thereof Download PDFInfo
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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
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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
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Abstract
The invention discloses a kind of artificial swamp dephosphorization matrix fill and preparation method thereof, first by wollastonite, flyash and shale crush, sieving, washing, dry, mixed by proportioning, obtain mixed powder, then γ aminopropyl trimethoxysilanes are grafted to mixed powder surface, obtain γ aminopropyl trimethoxysilane functionalization composites, again by methacrylate monomer polymerisation to γ aminopropyl trimethoxysilane functionalization composite material surfaces, obtain PMA functionalization composite, PMA functionalization composite and diethylenetriamine are reacted, obtain the composite of amido grafting, pass through cross-linking reaction, it is granulated, produce.Gained filler of the invention has the advantages that nontoxic, intensity is high, constitution is light, absorption property is strong and stability is good, and production cost is low, contaminant removal capacity is strong, phosphor-removing effect is good.
Description
Technical field
The invention belongs to environment functional material technical field, and in particular to a kind of artificial swamp dephosphorization matrix fill and its system
Preparation Method.
Background technology
In recent years, with the development of the society, the raising of human living standard, the discharge capacity of pollutant is increasing, causes
There is Eutrophication Status in the surface water body such as part river course and lake, and phosphorus is the restriction factor of lake eutrophication, is that water body is repaiied
Top-priority factor during multiple, once a large amount of phosphorus enter water body, often cause the swift and violent growth of phytoplankton, and then influence
To drinking water safety.
The method of dephosphorization mainly has chemical precipitation method, microbial method, physisorphtion etc..Chemical precipitation method mainly includes stone
The grey precipitation method, molysite deposition method, the aluminium salt precipitation method.But these three phosphorus removing methods for low-concentration phosphorus-containing wastewater removal effect not
Good, reason is that the solubility product of calcium phosphate is larger, can not be produced a desired effect with lime treatment low phosphorus；Low phosphorus in water
Colloidal sol can be formed with iron, aluminium ion, solubility is big, is not easy to be separated from the water, and to reach phosphor-removing effect, need to increase pharmaceutical quantities, lead
Cause iron, aluminum metal ion residues amount high, be also easy to produce secondary pollution.Therefore, molysite and aluminium salt can not be directly used in low concentration and contain
The processing of phosphorus waste water.In addition, chemical precipitation method can produce substantial amounts of chemical sludge, if mishandling, secondary pollution is easily caused, is limited
Make its application；Microbial method dephosphorization is both economical, removal effect is good, but due to microorganism growth to environment temperature, pH value,
The requirements such as nutrient, dissolved oxygen are strict, and stability is poor, and stronger to the concentration dependent of organic matter, and water outlet phosphorus concentration exists
Discharge standard is not reached under the conditions of a lot；Physisorphtion, to the efficient absorption of phosphorus, has reached the mesh of dephosphorization using functional material
, conventional adsorbent mainly has zeolite molecular sieve, laterite, flyash, physisorphtion with its capacity is big, power consumption less, pollution
It is small, remove it is fast and recyclable the advantages that, be widely used in terms of dephosphorization.
At present, advanced treating is carried out to low-concentration phosphorus-containing wastewater frequently with artificial swamp, artificial swamp is a kind of new
Ecological sewage treatment technology, compared with traditional sewage water treatment method, there is maintenance management conveniently, high treating effect, running cost
The advantages that high is worth with the low and aesthetics of environment, is widely used in town domestic sewage and industrial and agricultural production field of waste water treatment.People
The removal of work wetland phosphor in sewage be mainly with filling adsorption, microorganism absorption degradation and sludge settling based on, energy of adsorption
The quality of power, depending on whether medium filler has higher specific surface area and good hydraulic conductivity, therefore, selection has
Removal of the Wetland Substrate filler of effect to phosphorus in water body is most important.
General artificial Wetland Substrate mainly includes gravel, sand, rubble etc., and the phosphor-removing effect of such matrix is poor, and other are more
Pore structure matrix such as calcite, hydrotalcite, gangue etc., Application No. CN201510178728.8 patent user solve masonry
For dephosphorization filler, Application No. CN201611004494.6 patent uses hydrotalcite as dephosphorization filler, Application No.
CN201610036142.2 patent makes dephosphorization haydite using gangue, preferable to the Adsorption effect of phosphorus, but cost
Higher, popularization and application are difficult.Therefore, new efficient dephosphorization Wetland Substrate filler is developed, the phosphorus removed to depth in sewage has
There is important practical significance.
The content of the invention
, should object of the present invention is to provide a kind of artificial swamp dephosphorization matrix fill based on the deficiencies in the prior art
Filler has the advantages that nontoxic, intensity is high, constitution is light, absorption property is strong and stability is good.
Present invention also offers the preparation method of the artificial swamp dephosphorization matrix fill.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of artificial swamp dephosphorization matrix fill, comprises the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, sieving, washing, dry, obtain wollastonite in powder, flyash
Powder and shale powder, and by wollastonite in powder, fine coal ashes and shale powder according to parts by weight (40~60): (20~30): (10~
30) mix, obtain mixed powder；
(2) mixed powder obtained by step (1) is scattered in toluene, in a nitrogen atmosphere, is warming up to 110~120 DEG C, adds
Enter γ-aminopropyltrimethoxysilane, and stir 10~12 hours, then separation of solid and liquid, takes solid to be washed with ethanolic extraction, very
Sky is dried, grinding, obtains γ-aminopropyltrimethoxysilane functionalization composite；Wherein, mixed powder and γ-aminopropyl
The mass ratio of trimethoxy silane is (1~2): (0.6~1.1)；
(3) γ-aminopropyltrimethoxysilane functionalization composite obtained by step (2) and methyl acrylate are scattered in
In water, in a nitrogen atmosphere, 55~65 DEG C are warming up to, add ammonium persulfate, stirred 10~12 hours, then separation of solid and liquid, takes
Solid is washed with ethanolic extraction, is dried in vacuo, and obtains PMA functionalization composite；Wherein, γ-aminopropyl front three
The mass ratio of TMOS functionalization composite, methyl acrylate and ammonium sulfate is (0.5~1): (10~15): (0.1~
0.3)；
(4) PMA functionalization composite obtained by step (3) is scattered in acetone, in a nitrogen atmosphere,
It is 7~8 to adjust pH value of solution, then adds diethylenetriamine, is stirred in 90~98 DEG C 6~8 hours, then separation of solid and liquid, takes solid
Body washing, vacuum drying, obtain the composite of amido grafting；Wherein, PMA functionalization composite and diethyl
The mass ratio of alkene triamine is 1：14~20；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, stirring crosslinking 4~6
Hour, through being granulated, produce；Wherein, the addition for the composite that amido is grafted is 0.5~1g/ in the aqueous solution of polyvinyl alcohol
L。
Preferably, the screen-aperture to be sieved described in step (1) is 80~120 mesh, and washing is using steaming described in step (1)
Distilled water concussion washing, drying described in step (1) are dried 1.5~3 hours in 80~100 DEG C.
Preferably, it is true in 60~90 DEG C to be dried in vacuo described in vacuum drying described in step (2) and step (3)
Sky is dried 10~12 hours.
Preferably, washing described in step (4) is adopted to be washed with distilled water to and is dried in vacuo in neutrality, step described in (4)
Temperature be 50~70 DEG C, duration 12~24 hours.
Preferably, described in step (5) in the aqueous solution of polyvinyl alcohol the mass percent of polyvinyl alcohol for 0.8~
1.2%.
Preferably, be granulated described in step (5) is the microballoon that 3~4 millimeters of diameter is made in comminutor.
The artificial swamp dephosphorization matrix fill being prepared using the above method.
Wollastonite, flyash, shale, γ-aminopropyltrimethoxysilane, methyl acrylate and divinyl of the present invention
Triamine is ordinary commercial products.
The preparation method of artificial swamp dephosphorization matrix fill of the present invention, it is by wollastonite (Wo), flyash first
(FA) and shale (Sh) is crushed, sieved, washing, drying, being mixed by proportioning, mixed powder is obtained, then by γ-aminopropyl three
Methoxy silane (APTMS) is grafted to mixed powder surface, obtains γ-aminopropyltrimethoxysilane functionalization composite
(WFS-APTMS), then by methacrylate monomer (Ma) polymerisation to WFS-APTMS surfaces, PMA is obtained
Functionalization composite (WFS-APTMS-PMa), WFS-APTMS-PMa and diethylenetriamine (DETA) are reacted, obtain amido
The composite (WFS-APTMS-PMa-DETA) of grafting, after cross-linking reaction, is granulated into the functionalized microsphere of high intensity.It is whole
The reaction mechanism of individual preparation process is as follows：
Beneficial effects of the present invention：Using the inorganic material commonly used in life, prepare suitable for artificial swamp, biological filter
The filler of the ecological water processing establishment such as pond, the filler have that nontoxic, intensity is high, constitution is light, absorption property is strong and stability is good
The advantages that, the filler is both microorganism carrier, can carry out efficient absorption to the phosphorus in waste water again.Production cost of the present invention
Low, contaminant removal capacity is strong, phosphor-removing effect is higher by more than 10% than other common dephosphorization fillers, bar existing for Organic substance in water
Under part, be advantageous to increase its Adsorption to phosphorus.
Embodiment
In order that the technical purpose of the present invention, technical scheme and beneficial effect are clearer, with reference to specific embodiment
Technical scheme is further illustrated, but the embodiment is intended to explain the present invention, and it is not intended that right
The limitation of the present invention, in the examples where no specific technique or condition is specified, according to the technology described by document in the art or
Condition is carried out according to product description.
Embodiment 1
A kind of preparation method of artificial swamp dephosphorization matrix fill, comprises the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, cross 100 mesh sieves, then shaken in an oscillator with distilled water
Washing 1.5 hours is swung, then is dried 2 hours in 90 DEG C in thermostatic drying chamber, obtains wollastonite in powder, fine coal ashes and shale powder；
And by wollastonite in powder, fine coal ashes and shale powder according to parts by weight 40：30：30 mix, and obtain mixed powder；
(2) mixed powder obtained by 7.5g steps (1) is added in flask, and adds 125mL toluene, ultrasonic disperse 18 divides
Clock, it is subsequently placed in oil bath pan, in a nitrogen atmosphere, is warming up to 115 DEG C, adds 4mL γ-aminopropyltrimethoxysilanes, and
Constant temperature stirs 11 hours, then filters, takes filter residue first to be wrapped up with filter paper, then is put into after being packaged with gauze in extraction device, makes
By the use of absolute ethyl alcohol as detergent, and bead is put into prevent bumping, be heated to seething with excitement and extract washing 11 hours, then take out
By the filter residue of extracting washing, it is placed in vacuum drying chamber, is dried in vacuo 11 hours in 80 DEG C, pulverizes, obtain γ-ammonia
Propyl trimethoxy silicane functionalization composite；
(3) by γ-aminopropyltrimethoxysilane functionalization composite obtained by 0.75g steps (2) and 12.5g propylene
Sour methyl esters is added in three-necked flask, is added 125mL distilled water, ultrasonic disperse 18 minutes, is subsequently placed in water-bath, in nitrogen
Under atmosphere, 60 DEG C are warming up to, adds 0.2g ammonium persulfates, is stirred 11 hours, is then filtered, take filter residue first to be wrapped up with filter paper, then
It is put into after being packaged with gauze in extraction device, using absolute ethyl alcohol as detergent, and is put into bead to prevent bumping, heating
To seething with excitement and extracting washing 11 hours, the filter residue by extracting washing is then taken out, is placed in vacuum drying chamber, it is true in 80 DEG C
Sky is dried 11 hours, obtains PMA functionalization composite；
(4) PMA functionalization composite obtained by 1g steps (3) is added in three-necked flask, added
22.5mL acetone, ultrasonic disperse 18 minutes, in a nitrogen atmosphere, add 0.01g NaOH and be sufficiently stirred 3 minutes, it is molten to adjust
Liquid pH is 7~8, then adds 17.5mL diethylenetriamines, is stirred 7 hours under 95 DEG C of water bath conditions, then filter, take filter residue
Neutrality is washed with distilled water to, is subsequently placed in vacuum drying chamber, is dried in vacuo 18 hours in 60 DEG C, obtains answering for amido grafting
Condensation material；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, and stirring crosslinking 5 is small
When, the microballoon of 3~4 millimeters of diameter is then made in comminutor, produces dephosphorization matrix fill；Wherein, the polyvinyl alcohol
The mass percent of polyvinyl alcohol is 1% in the aqueous solution, the addition for the composite that amido is grafted in the aqueous solution of polyvinyl alcohol
Measure as 0.75g/L.
Dephosphorization matrix fill obtained above is entered into the processing of luggage post, the cross-sectional diameter of pillar is 0.2m, packed height
1m, control water velocity 5mL/min；Adsorption, the initial phosphorus of phosphorus-containing wastewater are carried out to phosphorus-containing wastewater using manufactured filled column
Concentration is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, after filled column is handled, water outlet is phosphorus-containing wastewater containing phosphorus concentration
0.18mg/L, water outlet reach the class standard of surface water environment quality III, clearance 87.1%.
Embodiment 2
A kind of preparation method of artificial swamp dephosphorization matrix fill, comprises the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, cross 80 mesh sieves, then shaken in an oscillator with distilled water
Washing 1 hour is swung, then is dried 2 hours in 80 DEG C in thermostatic drying chamber, obtains wollastonite in powder, fine coal ashes and shale powder；And
By wollastonite in powder, fine coal ashes and shale powder according to parts by weight 50：30：20 mix, and obtain mixed powder；
(2) mixed powder obtained by 5g steps (1) is added in flask, and adds 100mL toluene, ultrasonic disperse 15 minutes,
It is subsequently placed in oil bath pan, in a nitrogen atmosphere, is warming up to 110 DEG C, adds 3mL γ-aminopropyltrimethoxysilanes, and constant temperature
Stirring 10 hours, then filters, takes filter residue first to be wrapped up with filter paper, then is put into after being packaged with gauze in extraction device, uses nothing
Water-ethanol is put into bead to prevent bumping as detergent, is heated to seething with excitement and extracts washing 10 hours, then take out by
The filter residue of washing is extracted, is placed in vacuum drying chamber, is dried in vacuo 12 hours in 60 DEG C, is pulverized, obtain γ-aminopropyl
Trimethoxy silane functionalization composite；
(3) by γ-aminopropyltrimethoxysilane functionalization composite obtained by 0.5g steps (2) and 10g acrylic acid
Methyl esters is added in three-necked flask, is added 100mL distilled water, ultrasonic disperse 15 minutes, is subsequently placed in water-bath, in nitrogen gas
Under atmosphere, 55 DEG C are warming up to, adds 0.1g ammonium persulfates, is stirred 10 hours, is then filtered, take filter residue first to be wrapped up with filter paper, then use
Gauze is put into extraction device after packaging, and using absolute ethyl alcohol as detergent, and is put into bead to prevent bumping, is heated to
Seethe with excitement and extract washing 10 hours, then take out the filter residue by extracting washing, be placed in vacuum drying chamber, in 60 DEG C of vacuum
Dry 12 hours, obtain PMA functionalization composite；
(4) PMA functionalization composite obtained by 1g steps (3) is added in three-necked flask, adds 20mL
Acetone, ultrasonic disperse 15 minutes, in a nitrogen atmosphere, regulation pH value of solution are 7~8,15mL diethylenetriamines are then added, in 90
Stirred 6 hours under DEG C water bath condition, then filter, take filter residue to be washed with distilled water to neutrality, be subsequently placed in vacuum drying chamber,
It is dried in vacuo 24 hours in 50 DEG C, obtains the composite of amido grafting；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, and stirring crosslinking 4 is small
When, the microballoon of 3~4 millimeters of diameter is then made in comminutor, produces dephosphorization matrix fill；Wherein, the polyvinyl alcohol
The mass percent of polyvinyl alcohol is 0.8% in the aqueous solution, and the composite that amido is grafted in the aqueous solution of polyvinyl alcohol adds
It is 0.5g/L to enter amount.
Dephosphorization matrix fill obtained above is entered into the processing of luggage post, the cross-sectional diameter of pillar is 0.2m, packed height
1m, control water velocity 5mL/min；Adsorption, the initial phosphorus of phosphorus-containing wastewater are carried out to phosphorus-containing wastewater using manufactured filled column
Concentration is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, after filled column is handled, water outlet is phosphorus-containing wastewater containing phosphorus concentration
0.15mg/L, water outlet reach the class standard of surface water environment quality III, clearance 89.3%.
Embodiment 3
A kind of preparation method of artificial swamp dephosphorization matrix fill, comprises the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, cross 120 mesh sieves, then shaken in an oscillator with distilled water
Washing 2 hours is swung, then is dried 2 hours in 100 DEG C in thermostatic drying chamber, obtains wollastonite in powder, fine coal ashes and shale powder；And
By wollastonite in powder, fine coal ashes and shale powder according to parts by weight 60：30：10 mix, and obtain mixed powder；
(2) mixed powder obtained by 10g steps (1) is added in flask, and adds 150mL toluene, ultrasonic disperse 20 minutes,
It is subsequently placed in oil bath pan, in a nitrogen atmosphere, is warming up to 120 DEG C, adds 5mL γ-aminopropyltrimethoxysilanes, and constant temperature
Stirring 12 hours, then filters, takes filter residue first to be wrapped up with filter paper, then is put into after being packaged with gauze in extraction device, uses nothing
Water-ethanol is put into bead to prevent bumping as detergent, is heated to seething with excitement and extracts washing 12 hours, then take out by
The filter residue of washing is extracted, is placed in vacuum drying chamber, is dried in vacuo 10 hours in 90 DEG C, is pulverized, obtain γ-aminopropyl
Trimethoxy silane functionalization composite；
(3) by γ-aminopropyltrimethoxysilane functionalization composite obtained by 1g steps (2) and 15g acrylic acid first
Ester is added in three-necked flask, is added 150mL distilled water, ultrasonic disperse 20 minutes, is subsequently placed in water-bath, in nitrogen atmosphere
Under, 65 DEG C are warming up to, adds 0.3g ammonium persulfates, is stirred 12 hours, is then filtered, take filter residue first to be wrapped up with filter paper, then use yarn
Cloth is put into extraction device after packaging, and using absolute ethyl alcohol as detergent, and is put into bead to prevent bumping, is heated to boiling
Rise and extract washing 12 hours, then take out the filter residue by extracting washing, be placed in vacuum drying chamber, done in 90 DEG C of vacuum
Dry 10 hours, obtain PMA functionalization composite；
(4) PMA functionalization composite obtained by 1g steps (3) is added in three-necked flask, adds 25mL
Acetone, ultrasonic disperse 20 minutes, in a nitrogen atmosphere, regulation pH value of solution are 7~8,20mL diethylenetriamines are then added, in 98
Stirred 8 hours under DEG C water bath condition, then filter, take filter residue to be washed with distilled water to neutrality, be subsequently placed in vacuum drying chamber,
It is dried in vacuo 12 hours in 70 DEG C, obtains the composite of amido grafting；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, and stirring crosslinking 6 is small
When, the microballoon of 3~4 millimeters of diameter is then made in comminutor, produces dephosphorization matrix fill；Wherein, the polyvinyl alcohol
The mass percent of polyvinyl alcohol is 1.2% in the aqueous solution, and the composite that amido is grafted in the aqueous solution of polyvinyl alcohol adds
It is 1g/L to enter amount.
Dephosphorization matrix fill obtained above is entered into the processing of luggage post, the cross-sectional diameter of pillar is 0.2m, packed height
1m, control water velocity 5mL/min；Adsorption, the initial phosphorus of phosphorus-containing wastewater are carried out to phosphorus-containing wastewater using manufactured filled column
Concentration is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, after filled column is handled, water outlet is phosphorus-containing wastewater containing phosphorus concentration
0.13mg/L, water outlet reach the class standard of surface water environment quality III, clearance 90.7%.
Embodiment 4
A kind of preparation method of artificial swamp dephosphorization matrix fill, comprises the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, cross 100 mesh sieves, then shaken in an oscillator with distilled water
Washing 1.5 hours is swung, then is dried 2 hours in 90 DEG C in thermostatic drying chamber, obtains wollastonite in powder, fine coal ashes and shale powder；
And by wollastonite in powder, fine coal ashes and shale powder according to parts by weight 60：20：10 mix, and obtain mixed powder；
(2) mixed powder obtained by 7.5g steps (1) is added in flask, and adds 125mL toluene, ultrasonic disperse 18 divides
Clock, it is subsequently placed in oil bath pan, in a nitrogen atmosphere, is warming up to 115 DEG C, adds 4mL γ-aminopropyltrimethoxysilanes, and
Constant temperature stirs 11 hours, then filters, takes filter residue first to be wrapped up with filter paper, then is put into after being packaged with gauze in extraction device, makes
By the use of absolute ethyl alcohol as detergent, and bead is put into prevent bumping, be heated to seething with excitement and extract washing 11 hours, then take out
By the filter residue of extracting washing, it is placed in vacuum drying chamber, is dried in vacuo 11 hours in 80 DEG C, pulverizes, obtain γ-ammonia
Propyl trimethoxy silicane functionalization composite；
(3) by γ-aminopropyltrimethoxysilane functionalization composite obtained by 0.75g steps (2) and 12.5g propylene
Sour methyl esters is added in three-necked flask, is added 125mL distilled water, ultrasonic disperse 18 minutes, is subsequently placed in water-bath, in nitrogen
Under atmosphere, 60 DEG C are warming up to, adds 0.2g ammonium persulfates, is stirred 11 hours, is then filtered, take filter residue first to be wrapped up with filter paper, then
It is put into after being packaged with gauze in extraction device, using absolute ethyl alcohol as detergent, and is put into bead to prevent bumping, heating
To seething with excitement and extracting washing 11 hours, the filter residue by extracting washing is then taken out, is placed in vacuum drying chamber, it is true in 80 DEG C
Sky is dried 11 hours, obtains PMA functionalization composite；
(4) PMA functionalization composite obtained by 1g steps (3) is added in three-necked flask, added
22.5mL acetone, ultrasonic disperse 18 minutes, in a nitrogen atmosphere, add 0.01g NaOH and be sufficiently stirred 3 minutes, it is molten to adjust
Liquid pH is 7~8, then adds 17.5mL diethylenetriamines, is stirred 7 hours under 95 DEG C of water bath conditions, then filter, take filter residue
Neutrality is washed with distilled water to, is subsequently placed in vacuum drying chamber, is dried in vacuo 18 hours in 60 DEG C, obtains answering for amido grafting
Condensation material；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, and stirring crosslinking 5 is small
When, the microballoon of 3~4 millimeters of diameter is then made in comminutor, produces dephosphorization matrix fill；Wherein, the polyvinyl alcohol
The mass percent of polyvinyl alcohol is 1% in the aqueous solution, the addition for the composite that amido is grafted in the aqueous solution of polyvinyl alcohol
Measure as 0.75g/L.
Dephosphorization matrix fill obtained above is entered into the processing of luggage post, the cross-sectional diameter of pillar is 1m, packed height 1m,
Control water velocity 5mL/min；Adsorption, the initial phosphorus concentration of phosphorus-containing wastewater are carried out to phosphorus-containing wastewater using manufactured filled column
For 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, for phosphorus-containing wastewater after filled column is handled, water outlet is 0.25mg/ containing phosphorus concentration
L, water outlet reach the class standard of surface water environment quality IV, removal efficiency 82.1%.
Embodiment 5
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.5m, packed height 1m, control water velocity 5mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, phosphorus-containing wastewater is handled through filled column
Afterwards, water outlet is 0.23mg/L containing phosphorus concentration, and water outlet reaches the class standard of surface water environment quality IV, removal efficiency 83.6%.
Embodiment 6
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.2m, packed height 1m, control water velocity 15mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, phosphorus-containing wastewater is handled through filled column
Afterwards, water outlet is 0.3mg/L containing phosphorus concentration, and water outlet reaches the class standard of surface water environment quality IV, removal efficiency 78.6%.
Embodiment 7
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.2m, packed height 1m, control water velocity 25mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 4.0；Under conditions of 25 DEG C, phosphorus-containing wastewater is handled through filled column
Afterwards, water outlet is 0.32mg/L containing phosphorus concentration, and water outlet reaches the class standard of surface water environment quality IV, removal efficiency 77.1%.
Embodiment 8
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.2m, packed height 1m, control water velocity 5mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 7.0；Under conditions of 25 DEG C, phosphorus-containing wastewater is handled through filled column
Afterwards, water outlet is 0.26mg/L containing phosphorus concentration, and water outlet reaches the class standard of surface water environment quality IV, removal efficiency 81.4%.
Embodiment 9
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.2m, packed height 1m, control water velocity 5mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 10.0；Under conditions of 25 DEG C, phosphorus-containing wastewater is handled through filled column
Afterwards, water outlet is 0.33mg/L containing phosphorus concentration, and water outlet reaches the class standard of surface water environment quality IV, removal efficiency 76.4%.
Embodiment 10
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.5m, packed height 1m, control water velocity 5mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 4.0, COD 50.2mg/L；It is phosphorous useless under conditions of 25 DEG C
For water after filled column is handled, water outlet is 0.21mg/L containing phosphorus concentration, and water outlet COD is 32.3mg/L, and water outlet reaches surface water environment
The class standard of quality IV, phosphorus ligands efficiency are 85%.
Embodiment 11
Dephosphorization matrix fill is prepared in method according to embodiment 3, and is entered the processing of luggage post, the cross section of pillar
A diameter of 0.2m, packed height 1m, control water velocity 5mL/min；Phosphorus-containing wastewater is adsorbed using manufactured filled column
Remove, the initial phosphorus concentration of phosphorus-containing wastewater is 1.4mg/L, pH 4.0, COD 60.1mg/L；It is phosphorous useless under conditions of 25 DEG C
For water after filled column is handled, water outlet is 0.22mg/L containing phosphorus concentration, and water outlet COD is 30.2mg/L, and water outlet reaches surface water environment
The class standard of quality IV, phosphorus ligands efficiency are 84.3%.
Embodiment 12
Dephosphorization matrix fill is prepared in method according to embodiment 3, and it is used into artificial swamp, artificial swamp
Type is horizontal drowned flow type wetland, and area is 10m × 3m × 1m, and wetland plant matches its of reed, calamus, cattail and giantreed
In two kinds, line-spacing and spacing in the rows are 30cm, and wetland is arranged at flourishing age gardens Group Plc ecology fine work garden base, people
The water inlet of work wet land system is the sanitary sewage after biological treatment in the fine work garden, and phosphorus concentration is that 1.53mg/L, COD are in water inlet
65.5mg/L；Sanitary sewage passes through the processing of artificial wet land system, and the concentration of phosphorus is 0.2mg/L in water outlet, and water outlet is better than earth's surface
The class standard of quality of water environment III, tp removal rate 86.9%, water outlet COD are 38.2mg/L.
As fully visible, dephosphorization matrix fill phosphor-removing effect produced by the present invention is good, and condition existing for Organic substance in water
Under, be advantageous to increase its Adsorption to phosphorus.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although by referring to the present invention it is preferred
Invention has been described for embodiment, it should be appreciated by those of ordinary skill in the art that can in form and carefully
Various changes are made to it on section, the spirit and scope of the present invention limited without departing from appended claims.
Claims (7)
1. a kind of preparation method of artificial swamp dephosphorization matrix fill, it is characterised in that comprise the following steps：
(1) by wollastonite, flyash and shale respectively through crushing, sieving, washing, dry, obtain wollastonite in powder, fine coal ashes and
Shale powder, and by wollastonite in powder, fine coal ashes and shale powder according to parts by weight (40~60): (20~30): (10~30) are mixed
It is even, obtain mixed powder；
(2) mixed powder obtained by step (1) is scattered in toluene, in a nitrogen atmosphere, is warming up to 110~120 DEG C, adds
γ-aminopropyltrimethoxysilane, and stir 10~12 hours, then separation of solid and liquid, takes solid to be washed with ethanolic extraction, vacuum
Dry, grinding, obtain γ-aminopropyltrimethoxysilane functionalization composite；Wherein, mixed powder and γ-aminopropyl three
The mass ratio of methoxy silane is (1~2): (0.6~1.1)；
(3) γ-aminopropyltrimethoxysilane functionalization composite obtained by step (2) and methyl acrylate are scattered in water
In, in a nitrogen atmosphere, 55~65 DEG C are warming up to, add ammonium persulfate, stirred 10~12 hours, then separation of solid and liquid, takes solid
Body is washed with ethanolic extraction, is dried in vacuo, and obtains PMA functionalization composite；Wherein, γ-aminopropyl trimethoxy
The mass ratio of base silane functionalization composite, methyl acrylate and ammonium sulfate is (0.5~1): (10~15): (0.1~
0.3)；
(4) PMA functionalization composite obtained by step (3) is scattered in acetone, in a nitrogen atmosphere, regulation
PH value of solution is 7~8, then adds diethylenetriamine, is stirred 6~8 hours in 90~98 DEG C, then separation of solid and liquid, takes solid to wash
Wash, be dried in vacuo, obtain the composite of amido grafting；Wherein, PMA functionalization composite and divinyl three
The mass ratio of amine is 1：14~20；
(5) composite by amido grafting obtained by step (4) is added in the aqueous solution of polyvinyl alcohol, and stirring crosslinking 4~6 is small
When, through being granulated, produce；Wherein, the addition for the composite that amido is grafted is 0.5~1g/L in the aqueous solution of polyvinyl alcohol.
2. the preparation method of artificial swamp dephosphorization matrix fill according to claim 1, it is characterised in that：In step (1)
The screen-aperture of the sieving is 80~120 mesh, and washing described in step (1) is washed using distilled water concussion, institute in step (1)
Stating drying is dried 1.5~3 hours in 80~100 DEG C.
3. the preparation method of artificial swamp dephosphorization matrix fill according to claim 1, it is characterised in that：In step (2)
Be dried in vacuo described in the vacuum drying and step (3) is dried in vacuo 10~12 hours in 60~90 DEG C.
4. the preparation method of artificial swamp dephosphorization matrix fill according to claim 1, it is characterised in that：In step (4)
It is described washing adopt is washed with distilled water in neutrality, vacuum drying temperature described in step (4) be 50~70 DEG C, duration 12~
24 hours.
5. the preparation method of artificial swamp dephosphorization matrix fill according to claim 1, it is characterised in that：In step (5)
The mass percent of polyvinyl alcohol is 0.8~1.2% in the aqueous solution of the polyvinyl alcohol.
6. the preparation method of artificial swamp dephosphorization matrix fill according to claim 1, it is characterised in that：In step (5)
The granulation is the microballoon that 3~4 millimeters of diameter is made in comminutor.
7. the artificial swamp dephosphorization matrix fill being prepared using any described method of claim 1 to 6.
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