CN109304140A - A kind of preparation method of phosphorus-containing wastewater adsorbent material - Google Patents
A kind of preparation method of phosphorus-containing wastewater adsorbent material Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a kind of preparation methods of phosphorus-containing wastewater adsorbent material.The method includes the steps of: natural cooling after taking excess sludge to dry, the excess sludge powder that is sieved to obtain of milling；Into bentonite plus hydrochloric acid solution, stirring are centrifuged after cooling, and washing solid deposits to neutrality are dried, and sieving is added amino starch prepolymer, mixture A is mixed to obtain with excess sludge powder；Rare earth element is configured to the aqueous solution that mass concentration is 0.2-0.4%, adds polyacrylamide, simultaneously ultrasonic disperse is stirred evenly, obtains rare-earth element modified dose, it is mixed with mixture A, steel slag is added, stirring, refuel acid, filtering drying, calcining, up to adsorbent material of the present invention after cooling.The present invention is modified processing to excess sludge, bentonite and steel slag, changes its internal structure, increases its specific surface area, improves the absorption property of adsorbent material, is conducive to the Adsorption of phosphorus in phosphorus-containing wastewater in quinacridone top grade organic pigment production.
Description
Technical field
The present invention relates to sewage treatment fields, are specifically related to a kind of preparation method of phosphorus-containing wastewater adsorbent material.
Background technique
Phosphorus is closely bound up with our life as a kind of very important element.Either in agricultural or industry, phosphorus
It is all widely used, such as fertilizer and detergent.It is synthesized newly in addition, the growth and breeding of life entity is also required to a large amount of phosphorus
Life necessary material.However, the use of phosphorus produces many problems.When the content of phosphorus is exceeded, algae meeting mass propagation is caused
Eutrophication problem influences organism in water existence, causes serious ecological to endanger, therefore recent domestic is to the emission request of phosphorus
It is increasingly stringenter.
In " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) level-one emission standard A, the index of phosphorus
For total phosphorus 0.5mg/L.Country formulates different standards according to different regions, different basins, and effluent index is improved to ground Table IV class
More than half China of regional coverage of water body.And total phosphorus index as defined in ground Table IV water body standard is also 0.3mg/L.And in recent years,
With the pay attention to day by day of the fast development of pigment industry and Environmental protection, pigment industry is creating the same of economic benefit
When, also increasingly pay attention to wastewater treatment.Wherein, quinacridone top grade organic pigment product at home and abroad has good market,
Benefit of exporting goods and earning foreign currency is fine, but product per ton by phosphate content is generated is after the hydrolysis of polyphosphoric acids closed loop in process of production
The phosphorus-containing wastewater of 10%-20%, wastewater flow rate is big, and phosphorus content is high, and color is deep, and processing cost is high, if direct emission, will cause serious
Environmental pollution, directly restrict pigment production, be always perplex enterprise development problem.Therefore, deep phosphorous removal processing is close
The inevitable requirement of wastewater treatment over year.
Currently, the method for removing phosphorus in water removal has very much, mainly there are chemical method and bioanalysis, but due to biological dephosphorization
It is more unstable compared with for chemical method, so chemical method is more commonly used in removing waste water when total phosphorus.Chemical dephosphorization method mainly has
Coagulating sedimentation, electrolysis method, crystallisation, ion-exchange, absorption method etc..Absorption method has device simple, safe operation, cost
It is cheap, the advantages that effect stability, secondary pollution is small, and adsorbent material is reusable, therefore have a good application prospect and send out
Open up space.The active charcoal of currently used adsorbent material, mineral-type material, waste agronomic crop material etc., although most of material
Can Phosphate Sorption to a certain extent, but the absorption property of most natural materials is poor, and desorption and regeneration rate is low, and environment adapts to energy
Power is poor, it is difficult to be applied directly as adsorbent material.Adsorption effect of activated carbon in water is preferable, but its is expensive, it is difficult to realize
Industrial large-scale application；Mineral material, such as zeolite, bentonite, montmorillonite, rich reserves are cheap, but natural
Mineral material adsorbance is lower.In addition, realizing refuse reclamation to economize on resources, adsorbent material is researched and developed for waste resource
Technology be current wastewater treatment trend, provide the technology for the treatment of of wastes with processes of wastes against one another a kind of for economizing on resources, protection environment has important
Meaning.
Summary of the invention
The purpose of the invention is to overcome the shortcomings of above-mentioned background technique, is needed for current industry, provide one kind
It economizes on resources, the preparation method of environmental-friendly phosphorus-containing wastewater adsorbent material.
To achieve the object of the present invention, the preparation method of phosphorus-containing wastewater adsorbent material of the present invention comprises the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain excess sludge powder；
(2) hydrochloric acid solution is added into bentonite, constant temperature stirs 1-2 h at 40-50 DEG C, is centrifuged after cooling, and washing solid is heavy
Product object dries in 90-105 DEG C to neutrality, crosses 100-200 mesh, addition amino starch prepolymer is remaining with step (1) gained
Sewage sludge powder mixing, obtains mixture A, spare；
(3) rare earth element is configured to the aqueous solution that mass concentration is 0.2-0.4%, added relative to the liquor capacity
The polyacrylamide of 1.2-1.5%, stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed, broken steel slag is added, at 60-80 DEG C after constant temperature stirring 2-4 h, be added dropwise
Oleic acid, then 1-2h is persistently stirred, filtering drying calcines 1-2 h at 490-550 DEG C, puts into pelletizer and be granulated after cooling,
Up to adsorbent material of the present invention.
Further, the granular size of excess sludge powder is 180-240 μm in the step (1).
Further, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be (8-10): (2-
4): 1:(4-6).
Further, the mass volume ratio of the bentonite and hydrochloric acid is 1:(6-8).
Further, the hydrochloric acid is the hydrochloric acid of 1-3mol/L.
Further, the mass volume ratio of mixture A and rare-earth modifier is 1:(5-10 in the step (4)).
Further, the steel slag be selected through 30-40 mesh, and 800-850 DEG C activation after broken steel slag.
Further, the mass ratio of oleic acid and steel slag is 1:4-1:10 in the step (4).
Further, the rare earth element is lanthanum, it is preferred that the rare earth element is lanthanum chloride or/and lanthanum nitrate.
Further, the amino starch prepolymer the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-
4, paraformaldehyde, 60-70 DEG C of reaction is added；Then urea is added；It is warming up to 80-85 DEG C again, poly-vinyl alcohol solution, heat preservation is added
It reacts, up to amino starch prepolymer after natural cooling.Preferably, wherein starch, paraformaldehyde, urea, polyvinyl alcohol quality
Than for (95-105): (4-6): (20-25): (7-9).
Currently, the processing cost of excess sludge has accounted for the 25%~65% of entire sewage treatment expense, and present on year by year
The trend of liter, the generation and development sludge reduction technology for how controlling excess sludge have become a top priority.Steel slag is to make steel
A kind of by-product generated in journey is mainly made of the oxide of calcium, iron, silicon, magnesium and a small amount of aluminium, manganese, phosphorus etc., and quantity is about steel
The 15%~20% of yield, but utilization rate is lower, and the Novel sewage few as a kind of low consumption, low cost, secondary pollution handles material
Material, steel slag can remove the phosphorus in waste water, however use common steel slag dephosphorization efficiency very low.
The each raw material component that the present invention prepares adsorbent material is nontoxic after processing, two after not will cause adsorption treatment
Secondary pollution, by being modified processing to excess sludge, bentonite and steel slag, changes it during preparing adsorbent material
Internal structure increases its specific surface area, can mutually promote and cooperate between each raw material component, and collaboration plays absorption and makees
With, and the amide groups for the polyacrylamide being added can also, absorption affine with many substances and form hydrogen bond, while polyacrylamide
" bridging " is formed between the particle being adsorbed, the absorption property of adsorbent material of the present invention is further improved, is conducive to the suction of phosphorus
Attached removal.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under
Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below
It is bright, it is not intended to limit the present invention.
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
In present specification and claims, range restriction can be combined and/or be exchanged, if without in addition saying
These bright ranges include all subranges contained therebetween.
Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one"
Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular
Element or component also include plural form, unless the quantity obviously only refers to singular.
Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can
To be combined with each other.
Embodiment 1
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 1mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:8, at 40-50 DEG C
Lower constant temperature stirs 1h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, is mixed with excess sludge powder obtained by step (1), obtain mixture A, it is spare；The amino starch is pre-
Polymers the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；Then
Urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to the pre-polymerization of amino starch after natural cooling
Object, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 95:4:20:7；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.2%, added relative to the liquor capacity 1.2%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:5, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 2 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:4, then 1h is persistently stirred, filtering drying calcines 1 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.5% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 0.5%.
Wherein, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be 8:2:1:4.
Embodiment 2
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 3mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:6, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, is mixed with excess sludge powder obtained by step (1), obtain mixture A, it is spare；The amino starch is pre-
Polymers the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；Then
Urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to the pre-polymerization of amino starch after natural cooling
Object, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 105:6:25:9；
(3) lanthanum nitrate is configured to the aqueous solution that mass concentration is 0.4%, added relative to the liquor capacity 1.5%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:10, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:10, then persistently stir 2h, filtering drying calcine 2 h at 490-550 DEG C, put into after cooling in pelletizer be granulated to get
Phosphorus-containing wastewater adsorbent material, with the phosphate-containing generated in adsorbent material processing quinacridone organic-pigment production process
18.7% phosphorus-containing wastewater, phosphate content is 0.5% after having handled.
Wherein, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be 10:4:1:6.
Embodiment 3
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 2mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:7, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, is mixed with excess sludge powder obtained by step (1), obtain mixture A, it is spare；The amino starch is pre-
Polymers the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；Then
Urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to the pre-polymerization of amino starch after natural cooling
Object, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 100:5:23:8；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.8% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 0.6%.
Wherein, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be 9:3:1:5.
Embodiment 4
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(3) excess sludge powder and rare-earth modifier being mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid, the quality of oleic acid and steel slag is added dropwise in broken steel slag after 800-850 DEG C of activation
Than for 1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated after cooling, i.e.,
Phosphorus-containing wastewater adsorbent material is obtained, with the phosphate-containing generated in adsorbent material processing quinacridone organic-pigment production process
18.6% phosphorus-containing wastewater, phosphate content is 10.2% after having handled.
Wherein, the excess sludge, steel slag mass ratio be 9:5.
Embodiment 5
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) hydrochloric acid solution of 2mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:7, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, obtains mixture A, it is spare；The amino starch prepolymer distills the preparation method comprises the following steps: starch is put into
In water, adjusting pH is 3-4, and paraformaldehyde, 60-70 DEG C of reaction is added；Then urea is added；It is warming up to 80-85 DEG C again, is added poly-
Glycohol solution, insulation reaction, up to amino starch prepolymer after natural cooling, wherein starch, paraformaldehyde, urea, poly- second
Enol mass ratio is 100:5:23:8；
(2) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(3) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.3% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 12.5%.
Wherein, the bentonite, amino starch prepolymer, steel slag mass ratio be 3:1:5.
Embodiment 6
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) amino starch prepolymer is mixed with excess sludge powder obtained by step (1), obtains mixture A, spare；The amino forms sediment
Powder prepolymer the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；
Then urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to amino starch after natural cooling
Prepolymer, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 100:5:23:8；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.5% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 9.3%.
Wherein, the excess sludge, amino starch prepolymer, steel slag mass ratio be 9:1:5.
Embodiment 7
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 2mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:7, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, is mixed with excess sludge powder obtained by step (1), obtain mixture A, it is spare；The amino starch is pre-
Polymers the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；Then
Urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to the pre-polymerization of amino starch after natural cooling
Object, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 100:5:23:8；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, after constant temperature stirs 4 h at 60-80 DEG C, then
2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get phosphorus-containing wastewater after cooling
Adsorbent material handles the phosphorous of the phosphate-containing 18.9% generated in quinacridone organic-pigment production process with the adsorbent material
Waste water, phosphate content is 7.1% after having handled.
Wherein, the excess sludge, bentonite, amino starch prepolymer mass ratio be 9:3:1.
Embodiment 8
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 2mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:7, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, with
The mixing of excess sludge powder obtained by step (1), obtains mixture A, spare；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.4% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 3.8%.
Wherein, the excess sludge, bentonite, steel slag mass ratio be 9:3:5.
Embodiment 9
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) hydrochloric acid solution of 2mol/L is added into bentonite, the mass volume ratio of bentonite and hydrochloric acid is 1:7, at 40-50 DEG C
Lower constant temperature stirs 2 h, is centrifuged after cooling, and washing solid deposits to neutrality are dried in 90-105 DEG C, crosses 100-200 mesh, adds
Enter amino starch prepolymer, is mixed with excess sludge powder obtained by step (1), obtain mixture A, it is spare；The amino starch is pre-
Polymers the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；Then
Urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction, up to the pre-polymerization of amino starch after natural cooling
Object, wherein starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are 100:5:23:8；
(3) it is added into mixture A and is selected through 30-40 mesh, and the broken steel slag after 800-850 DEG C of activation, at 60-80 DEG C
After constant temperature stirs 4 h, oleic acid is added dropwise, the mass ratio of oleic acid and steel slag is 1:7, then persistently stirs 2h, filtering drying, in 490-
2 h are calcined at 550 DEG C, are put into pelletizer and are granulated to get phosphorus-containing wastewater adsorbent material after cooling, are handled with the adsorbent material
The phosphorus-containing wastewater of the phosphate-containing 18.8% generated in quinacridone organic-pigment production process, phosphate content is after having handled
4.7%。
Wherein, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be 9:3:1:5.
Embodiment 10
A kind of preparation method of phosphorus-containing wastewater adsorbent material comprising the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain the excess sludge powder that granular size is 180-240 μm
End；
(2) bentonite is dried at 90-105 DEG C, crosses 100-200 mesh, and amino starch prepolymer is added, and is remained with obtained by step (1)
Remaining sewage sludge powder mixing, obtains mixture A, spare；The amino starch prepolymer the preparation method comprises the following steps: starch is put into distilled water
In, adjusting pH is 3-4, and paraformaldehyde, 60-70 DEG C of reaction is added；Then urea is added；It is warming up to 80-85 DEG C again, poly- second is added
Enolate solution, insulation reaction, up to amino starch prepolymer after natural cooling, wherein starch, paraformaldehyde, urea, polyethylene
Alcohol mass ratio is 100:5:23:8；
(3) lanthanum chloride is configured to the aqueous solution that mass concentration is 0.3%, added relative to the liquor capacity 1.3%
Polyacrylamide stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed by mass volume ratio for 1:8, addition is selected through 30-40 mesh, and in 800-
After constant temperature stirs 4 h at 60-80 DEG C, oleic acid is added dropwise in broken steel slag after 850 DEG C of activation, and the mass ratio of oleic acid and steel slag is
1:7, then 2h is persistently stirred, filtering drying calcines 2 h at 490-550 DEG C, puts into pelletizer and be granulated to get containing after cooling
Phosphorus waste water adsorbent material, with the phosphate-containing 18.2% generated in adsorbent material processing quinacridone organic-pigment production process
Phosphorus-containing wastewater, handled after phosphate content be 5.9%.
Wherein, the excess sludge, bentonite, amino starch prepolymer, steel slag mass ratio be 9:3:1:5.
As it will be easily appreciated by one skilled in the art that the above description is only an embodiment of the present invention, not to limit
The present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in this
Within the protection scope of invention.
Claims (10)
1. a kind of preparation method of phosphorus-containing wastewater adsorbent material, which is characterized in that the method includes the steps of:
(1) natural cooling after taking excess sludge to dry, sieving of milling obtain excess sludge powder；
(2) hydrochloric acid solution is added into bentonite, constant temperature stirs 1-2 h at 40-50 DEG C, is centrifuged after cooling, and washing solid is heavy
Product object dries in 90-105 DEG C to neutrality, crosses 100-200 mesh, addition amino starch prepolymer is remaining with step (1) gained
Sewage sludge powder mixing, obtains mixture A, spare；
(3) rare earth element is configured to the aqueous solution that mass concentration is 0.2-0.4%, added relative to the liquor capacity
The polyacrylamide of 1.2-1.5%, stirs evenly, and ultrasonic disperse, obtains rare-earth element modified dose；
(4) mixture A and rare-earth modifier are mixed, broken steel slag is added, at 60-80 DEG C after constant temperature stirring 2-4 h, be added dropwise
Oleic acid, then 1-2h is persistently stirred, filtering drying calcines 1-2 h at 490-550 DEG C, puts into pelletizer and be granulated after cooling,
Up to the phosphorus-containing wastewater adsorbent material.
2. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that in the step (1)
The granular size of excess sludge powder is 180-240 μm.
3. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the excess sludge,
Bentonite, amino starch prepolymer, steel slag mass ratio be (8-10): (2-4): 1:(4-6).
4. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the bentonite and salt
The mass volume ratio of acid is 1:(6-8).
5. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the hydrochloric acid is 1-
The hydrochloric acid of 3mol/L.
6. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that in the step (4)
The mass volume ratio of mixture A and rare-earth modifier is 1:(5-10).
7. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the steel slag be through
The choosing of 30-40 mesh, and the broken steel slag after 800-850 DEG C of activation.
8. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that in the step (4)
The mass ratio of oleic acid and steel slag is 1:4-1:10.
9. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the rare earth element is
Lanthanum, it is preferred that the rare earth element is lanthanum chloride or/and lanthanum nitrate.
10. the preparation method of phosphorus-containing wastewater adsorbent material according to claim 1, which is characterized in that the amino starch
Prepolymer the preparation method comprises the following steps: by starch put into distilled water in, adjustings pH be 3-4, be added paraformaldehyde, 60-70 DEG C react；So
After urea is added；It is warming up to 80-85 DEG C again, is added poly-vinyl alcohol solution, insulation reaction is pre- up to amino starch after natural cooling
Polymers；Preferably, the starch, paraformaldehyde, urea, polyvinyl alcohol mass ratio are (95-105): (4-6): (20-25): (7-
9).
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| CN112108114A (en) * | 2020-09-09 | 2020-12-22 | 中国科学院武汉岩土力学研究所 | Preparation method of permeable reactive barrier material |
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| CN114392718A (en) * | 2021-12-29 | 2022-04-26 | 杭州万向职业技术学院 | Method for preparing phosphorus-absorbing biochar by using chalk dust and plant waste |
| CN115305095A (en) * | 2022-09-13 | 2022-11-08 | 江苏润天建材(集团)有限公司 | Heavy metal contaminated soil remediation agent based on smelting slag and preparation method thereof |
| CN115305095B (en) * | 2022-09-13 | 2023-10-20 | 江苏润天建材(集团)有限公司 | Heavy metal contaminated soil restoration agent based on smelting slag and preparation method thereof |
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