CN108658194A - A kind of preparation method and applications except phosphorus composite material - Google Patents
A kind of preparation method and applications except phosphorus composite material Download PDFInfo
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- CN108658194A CN108658194A CN201810604848.3A CN201810604848A CN108658194A CN 108658194 A CN108658194 A CN 108658194A CN 201810604848 A CN201810604848 A CN 201810604848A CN 108658194 A CN108658194 A CN 108658194A
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
It is using magnesium salts waste liquid and to clear up dolime as raw material, or using magnesium salts waste liquid, resolution dolime and calcium sulfate as raw material, mixed-forming forms the invention discloses a kind of preparation method and applications except phosphorus composite material.Resulting materials of the present invention can be used as the phosphorus that filter medium is gone for depth in water removal.
Description
Technical field
The present invention relates to a kind of preparation method and applications except phosphorus composite material, belong to the contamination control of surface water body phosphorus
Method.
Background technology
Body eutrophication is increasingly severe, needs the purified treatment for reinforcing nitrogen and phosphorus pollutants in water.Urban life at present
Sewage disposal generally uses oxic activated sludge process, and sanitary sewage is difficult to stably reach by two stage treatment in many cases
Country-level emission standard A needs to increase advanced treating facility to ensure standard water discharge.Even and if sanitary sewage disposal reaches row
Water quality standard, but for the water body of eutrophication, needs to carry out tightened up denitrogenation dephosphorizing to waste water just to can guarantee water body
Ecological environment.Sewage treatment plants secondary treatment yielding water needs further denitrogenation dephosphorizing that could meet waste water money in many cases
Source application requirement.
In addition, the concentration of nitrogen and phosphorus of urban ground initial rainwater is also far beyond surface water body quality standard and city river
Stream, the pool, library body eutrophication pollutant one of source.How eutrophication problem, the economical and effective of urban water-body are solved
Rainwater treatment, river water processing be current China's urban construction and management in urgent technical need.
Lime precipitation, molysite deposition method or the aluminium salt precipitation method are generally used in the processing of Coal Gas Washing Cycling Water phosphorus.However work as water
When middle phosphorus concentration is very low, calcium, iron, aluminium ion and phosphate radical form colloidal sol, it is difficult to which phosphate is sunk with usually used sedimentation basin
Shallow lake is separated from the water out.In order to improve precipitation phosphor-removing effect, it is necessary to add far more than the precipitating reagent of dosage needed for precipitation phosphorus, lead
Cause calcium, iron, aluminum metal ion dosage big.
Absorption method dephosphorization is the hot spot of extensive concern, and common dephosphorization adsorbent has zeolite, calcite, bentonite, bumps
Mineral materials and the solid waste such as stick stone clay, vermiculite, red mud, flyash, these clay minerals and material have phosphorus certain
Suction-operated, but adsorption capacity is low, regeneration is relatively difficult.In order to improve the adsorption capacity of dephosphorization adsorbent, many scholars into
Row including makees the metal ions such as carrier loaded La, Ce, Fe except the preparation research of phosphorus composite material with debirs, with quartz sand,
The mineral such as montmorillonite, attapulgite, zeolite are carrier loaded La, Al, Fe and prepare modified adsorbent, these compound adsorbents have
Higher dephosphorization suction-operated.From the point of view of domestic and international result of study, above-mentioned composite material is with the reason of preferable suction-operated
Adsorbent surface active component Fe3+、Al3+、La3+、Ce3+Hydroxide has stronger chemical bonding effect with phosphate radical.With dilute
The sorbing material dephosphorization efficiency that earth elements are modified is high, but expensive, and the foreground of popularization and application is little.Cheap efficient dephosphorization
Adsorbent still has to be developed.
It is above-mentioned to add the chemical agent precipitation method and absorption method is unsuitable at city initial rainwater, sludge with high silver
It is applied in reason.Artificial swamp and latent filter system are the technical methods for the processing eutrophic water for having development potentiality, but difficult point exists
Very low to phosphorus fixation efficiency in materials such as common sandstones, filler seepage flow is easy to block.In order to solve both of these problems with honest and clean
It is crucial that valence material construction, which can prevent the efficient dephosphorization material blocked,.
Invention content
The present invention is to provide a kind of preparation except phosphorus composite material to avoid above-mentioned existing deficiencies in the technology
Method and its application.
The present invention solves technical problem, adopts the following technical scheme that：
The present invention discloses the preparation method except phosphorus composite material first comprising two ways：
Mode one：It is described except phosphorus composite material is prepared as follows：
Using magnesium salts waste liquid of the magnesium ion mass concentration not less than 5% as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, 1mm sieves was crushed, then at 600~800 DEG C
Calcining makes dolomite partially or completely decompose, and obtains thermal activation dolomite；Then according to mass ratio 1：1, it is white in the thermal activation
Yun Yanzhong adds water that its resolution, products therefrom crushing is made to sieve with 100 mesh sieve, and obtains raw material B；
By the raw material A and the raw material B, according to the oxidation that dissociates in magnesium ion in raw material A and the thermal activation dolomite
The molar ratio of calcium is 5:1~1:1 carries out dispensing, is uniformly mixed, and obtains mixture；
The mixture is shaped to uniform ball-type or rod-shpaed particle immediately, then diameter exists within the scope of 1~20mm
2~10 days are stood at room temperature, that is, obtains graininess and removes phosphorus composite material；Or compaction moulding in mold is added in the mixture and is
Then ornamental slab for paving the floor shape stands 7~10 days at room temperature, that is, obtain ornamental slab for paving the floor shape and remove phosphorus composite material.
Mode two：It is described except phosphorus composite material is prepared as follows：
Using magnesium salts waste liquid of the magnesium ion mass concentration not less than 5% as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, 1mm sieves was crushed, then 600~1000
DEG C calcining makes dolomite decompose completely, obtains thermal activation dolomite；Then according to mass ratio 1：1, in the thermal activation dolomite
In plus water make its resolution, products therefrom crushing sieves with 100 mesh sieve, and obtains raw material B；
Selection calcium sulfate crushing sieves with 100 mesh sieve, as raw material C；
By the raw material A, the raw material B and raw material C, according to free calcium oxide in magnesium ion in raw material A and raw material B
Molar ratio be 5:1~1:1, the mass ratio of raw material C and raw material B is 5:1~1:1 carries out dispensing, is uniformly mixed, is mixed
Material；
The mixture is shaped to uniform ball-type or rod-shpaed particle immediately, then diameter exists within the scope of 1~20mm
Standing 5~10 angels at room temperature, it completes consolidation, that is, obtains graininess and remove phosphorus composite material；Or mold is added in the mixture
Middle compaction moulding is ornamental slab for paving the floor shape, then stands 7~10 days at room temperature, that is, obtains ornamental slab for paving the floor shape and remove phosphorus composite material.
Specifically, the magnesium salts waste liquid is the waste liquid of containing magnesium sulfate, or it is the waste liquid simultaneously containing magnesium sulfate and magnesium chloride.
Specifically, the calcium sulfate is the anhydrite ore that calcium sulphate content is not less than 80%, or it is dead plaster
Waste material, or be desulfurated plaster, or for by desulfurated plaster in the anhydrous gypsum being changed into not less than 400 DEG C of temperature lower calcinations.
The invention also discloses what above-mentioned preparation method was obtained to remove phosphorus composite material and its application process：It is removed described in
Phosphorus composite material is laid in water process column, processing pond, artificial swamp or riverbed, and pending water is flowed through in a manner of seepage flow
Described to remove phosphorus composite material, the phosphorus composite material that removes is as reactivity porous media material slow release calcium ion and hydroxyl
Base promotes low phosphorus in water to form calcium phosphorus precipitation, to make phosphorus concentration in water reach four class standard of surface water body.
One of the characteristic that dolomite has is that fractional decomposition can occur：Calcite and side are decomposed into when dolomite decomposition first
Magnesite (see formula (1)), then calcite is further broken into calcium oxide.The first step mainly occurs calcining 600-800 DEG C of section
It decomposes, is converted into calcite and magnesia.Due to the relatively low second step of calcination temperature decompose it is incomplete, thus obtain periclase+
Calcium oxide+calcite mixture phase, the wherein ratio of calcite/calcium oxide depend on calcining manners, temperature and material in high temperature
Area's residence time.When calcination temperature is higher than 800 DEG C, dolomite decomposes completely is changed into calcium oxide and magnesia (see formula (2)).
CaMg(CO3)2------CaCO3+MgO+CO2 (1)
CaMg(CO3)2------CaO+MgO+2CO2 (2)
Dolomite is calcined at a proper temperature, makes its decomposed, obtains periclase+calcium oxide+calcite combination,
Or decompose obtain periclase+calcium oxide combination completely, as thermal activation dolomite.
Add water resolution that the calcium oxide in thermal activation dolomite can be made to be changed into calcium hydroxide, and magnesia therein is basic
Hold mode is constant.
Present invention thermal activation dolomite handles magnesium salts waste liquid, while obtaining and removing phosphorus composite material.In magnesium salts waste liquid magnesium from
Son, sulfate ion are reacted with the thermal activation dolomite of resolution, obtain shepardite+calcium sulfate composite wood with granule strength
Material or shepardite+calcium sulfate+calcite composite material (see formula (3)).
MgSO4+MgO+Ca(OH)2+2H2O------CaSO4·2H2O+Mg(OH)2 (3)
Research shows that calcium ion concentration has a major impact the removal effect of phosphorus in Pore Solution, it is contemplated that dephosphorization material needs
Higher calcium and magnesium ratio, raw material C calcium sulfate is added in two kinds of raw materials of A, B, raw material C is sent out in the chemical reaction of two kinds of raw materials of AB
The function of cementing material has been waved, obtained with granule strength, met to meet as the material or intensity of infiltration filtrate requirement and make
To be laid with the building materials that ornamental slab for paving the floor requires.
The content higher of magnesia, magnesium hydroxide, is primarily suitable at fast filtering mode in material prepared by mode one
It is applied when managing waste water, phosphate micro in water can be fixed under the hydraulic detention time of very little.For example, sanitary sewage is into one
Walk deep phosphorous removal processing.Addition carrys out calcium sulfate in material prepared by mode two, reduces magnesia, magnesium hydroxide content, more
The filtration media for being suitable for shallow filter system uses.
Beneficial effects of the present invention are embodied in：
1, dispose and be utilized magnesium salts waste liquid, such as the halogen of the magnesium salt solution of chemical synthesis process generation, salt chemical engineering industry
Water, magnesium method flue gas desulphurization waste liquid, are all high concentration salt solutions, are the wastes that enterprise is difficult to dispose, it is useless that the present invention realizes magnesium salts
The recycling of liquid.
2, have the function of from the magnesium ion in cementation and formation, magnesium salts waste liquid, oxygen in sulfate ion and thermal activation dolomite
Change calcium reaction and generate new object phase, and magnesia therein is promoted to be hydrolyzed to magnesium hydroxide, while cementing calcium sulfate powder obtains
Obtain the cellular solid with higher-strength.
3, prepared material is the sustained release source of calcium ion and hydroxyl, the pH value of shepardite water steady in a long-term in composite material
9 or so, calcium sulfate is sustained source as calcium ion, provides the calcium ion of precipitation phosphorus, shepardite and calcium sulfuric acid steadily in the long term
Salt synergistic effect promotes low phosphorus precipitation in water to fix, and ensures that water outlet phosphorus concentration reaches four class standard of surface water body.
4, the present invention is the study found that different calcium sulfate has different rate of dissolutions, and gypsum dissolution is most fast, and anhydrite is molten
Solution is most slow, and the anhydrous gypsum rate of dissolution that desulfurated plaster calcines formation at 400 DEG C or more is between steam curing, and
And rate of dissolution is increased with calcination temperature, the crystallinity of dead plaster improves, and rate of dissolution reduces.For identical ABC tri-
Kind raw material proportioning, due to calcium sulfate type used difference, composite material using effect is different.Gypsum dissolution speed is fast, consumes
Soon, it is suitable for Removal of Phosphorus in Wastewater under Thief zone rate；Anhydrite solution rate is low, consumption is slow, is suitable under low penetration rate,
Dephosphorization application especially in wet land system.Therefore, can be different according to hydraulic detention time when filtration process, it selects by different
The material that calcium sulphate component is constituted.It is shaped to larger particles, the cladding of newborn shepardite can also slow down to a certain extent
The dissolving of gypsum reaches the coupling of material release calcium ion and hydroxyl ion precipitation phosphorus.
5, granular composite material prepared by the present invention has larger particles grain size as filler, to larger
Intergranular pore；Or the ornamental slab for paving the floor shape material prepared builds the water process filtration system of required hole by laying bricks or stones, hole can be by the side of building by laying bricks or stones
Formula artificial adjustment.Solve the problems, such as that wetland osmosis system blocks.On the other hand, as with the porous of reactivity
Dielectric material has and phosphorus is properly promoted to precipitate fixed reactivity, efficiently fixes phosphorus, while shepardite, gypsum or hard
Gypsum slow mechanism dissolved is provided for a long term newborn hole, this helps to prevent the blocking of water treatment system to occur.
Description of the drawings
Fig. 1 be thermal activation dolomite obtained by 600 DEG C of calcining dolomites in embodiment 1 (curve a), to thermal activation dolomite into
Row resolution gained resolution product (curve b) and (XRD diagram of curve c) that phosphorus composite material is removed with two kinds of raw materials preparation gained of A+B
Spectrum；It is labeled as in figure：B- shepardites, Cc- calcites, D- dolomites, G- gypsum, L- calcium oxide, Pe- periclases.
Fig. 2 be thermal activation dolomite obtained by 800 DEG C of calcining dolomites in embodiment 2 (curve a), to thermal activation dolomite into
Row resolution gained resolution product (curve b) and (XRD diagram of curve c) that phosphorus composite material is removed with two kinds of raw materials preparation gained of A, B
Spectrum；It is labeled as in figure：B- shepardites, G- gypsum, L- calcium oxide, Pe- periclases, Po- calcium hydroxides.
Fig. 3 be thermal activation dolomite obtained by 600 DEG C of calcining dolomites in embodiment 3 (curve a), to thermal activation dolomite into
Row resolution gained resolution product (curve b) and (XRD of curve c) that phosphorus composite material is removed with tri- kinds of raw materials preparation gained of A+B+C
Collection of illustrative plates；It is labeled as in figure：A- anhydrite, B- shepardites, Cc- calcites, D- dolomites, G- gypsum, L- calcium oxide, the side Pe-
Magnesite.
Fig. 4 is the photo that embodiment 3 removes phosphorus composite material with the graininess of tri- kinds of compound preparations of raw material of ABC；
The XRD spectrum of 500 DEG C of calcining desulfurated plaster products therefroms in Fig. 5 embodiments 5；
Fig. 6 is the SEM image of 500 DEG C of calcining desulfurated plaster products therefroms in embodiment 5.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1：
The present embodiment is prepared as follows except phosphorus composite material：
Using the magnesium sulfate waste liquid that magnesium ion mass concentration is 6% as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then calcined at 600 DEG C
1h makes dolomite decompose substantially.XRD diagram spectral curve (see Fig. 1 a) is as can be seen that the dolomitic composition of thermal activation is mainly square magnesium
Stone, calcite, calcium oxide have a small amount of dolomite to remain；Then according to mass ratio 1：1, in thermal activation dolomite plus water makes it
Resolution, the XRD spectrum of products therefrom is shown in Fig. 1 b curves, it can be seen that its form be mainly periclase, calcite, calcium hydroxide,
Dolomite is crushed and is sieved with 100 mesh sieve, and raw material B is obtained；
By raw material A and raw material B, the molar ratio according to magnesium ion in raw material A and free calcium oxide in thermal activation dolomite is
1:1 carries out dispensing, is uniformly mixed, and obtains mixture；Mixture is shaped to the spherical particles of diameter 2mm immediately, then in room
Temperature is lower to stand 10 days, that is, obtains graininess and remove phosphorus composite material.C can be seen that its composition is mainly periclase, Fang Xie from Fig. 1
Stone, shepardite, gypsum, dolomite.
It is pending the present embodiment except phosphorus composite material is seated in the simulation water process column of Ф 30cm, high 100mm
Phosphorous water prepares (phosphorus concentration 2mg/L) with tap water, and the above upflow filtration mode is handled, hydraulic detention time 60min, is discharged phosphorus
Concentration reaches four class standard of surface water body.
Embodiment 2：
The present embodiment is prepared as follows except phosphorus composite material：
Using magnesium ion mass concentration be 9%, contain magnesium sulfate simultaneously and the waste liquid of magnesium chloride is as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then calcined at 800 DEG C
1h makes dolomite decompose completely, obtains the thermal activation dolomite being made of calcium oxide, periclase, and XRD spectrum is shown in that a is bent in Fig. 2
Line, it can be seen that consisting of calcium oxide, periclase；
Then according to mass ratio 1：1, in thermal activation dolomite plus water makes its resolution, the XRD spectrum of products therefrom see Fig. 2
Middle b curves, it can be seen that consisting of calcium hydroxide, shepardite, periclase form, the complete aquation of calcium oxide is calcium hydroxide,
Part periclase aquation is shepardite；It is crushed and is sieved with 100 mesh sieve, obtain raw material B；
By raw material A and raw material B, the molar ratio according to magnesium ion in raw material A and free calcium oxide in thermal activation dolomite is
1:1 carries out dispensing, is uniformly mixed, and obtains mixture；Mixture is shaped to the spherical particles of diameter 3mm immediately, then in room
Temperature is lower to stand 10 days, that is, obtains graininess and remove phosphorus composite material.C can be seen that consisting of shepardite, gypsum from Fig. 2.
It is pending the present embodiment except phosphorus composite material is seated in the simulation water process column of Ф 30cm, high 100mm
Phosphorous water prepares (phosphorus concentration 2mg/L) with tap water, and the above upflow filtration mode is handled, hydraulic detention time 30min, is discharged phosphorus
Concentration reaches four class standard of surface water body.
Embodiment 3：
The present embodiment is prepared as follows except phosphorus composite material：
Using magnesium ion mass concentration be 9%, contain magnesium sulfate simultaneously and the waste liquid of magnesium chloride is as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then calcined at 600 DEG C
1h makes dolomite decompose substantially, obtains the thermal activation being made of main periclase, calcite, calcium oxide, a small amount of residual dolomite
Dolomite (Fig. 3 a)；Then according to mass ratio 1：1, in thermal activation dolomite plus water makes its resolution, composition be mainly：Water magnesium
Stone, calcite, calcium hydroxide, remains dolomite at periclase on a small quantity, and products therefrom crushing sieves with 100 mesh sieve, and obtains raw material B (figures
3b)；
The anhydrite ore of calcium sulphate content 95% is selected, crushing sieves with 100 mesh sieve, as raw material C；
By raw material A, raw material B and raw material C, the molar ratio according to free calcium oxide in magnesium ion in raw material A and raw material B is 5:
1, the mass ratio of raw material C and raw material B is 3:1 carries out dispensing, is uniformly mixed, and obtains mixture (Fig. 3 c), main group becomes：Admant
Cream, calcite, remains dolomite at shepardite on a small quantity；Mixture is shaped to the spherical particles of diameter 5mm immediately, then in room
Temperature is lower to stand its completion consolidation of 10 angels, that is, obtains graininess and remove phosphorus composite material, as shown in Figure 4.The dephosphorization material
It being seated in the simulation water process column of Ф 30cm high 100mm, pending phosphorous water prepares (phosphorus concentration 2mg/L) with tap water,
The above upflow filtration mode is handled, hydraulic detention time 20h, and water outlet phosphorus concentration reaches four class standard of surface water body.
Embodiment 4：
The present embodiment is prepared as follows except phosphorus composite material：
Using magnesium ion mass concentration be 9%, contain magnesium sulfate simultaneously and the waste liquid of magnesium chloride is as raw material A；
The dolomite for selecting dolomite mass percentage 95% was crushed 1mm sieves, and 20min is then calcined at 900 DEG C makes
Dolomite decomposes completely, obtains the thermal activation dolomite being made of calcium oxide, periclase；Then according to mass ratio 1：1, it is living to heat
Change in dolomite plus water makes its resolution, the complete aquation of calcium oxide be calcium hydroxide, part periclase aquation is shepardite, gained production
Object crushing sieves with 100 mesh sieve, and obtains raw material B；It selects desulfurated plaster, crushing to sieve with 100 mesh sieve, obtains raw material C；
By raw material A, raw material B and raw material C, the molar ratio according to free calcium oxide in magnesium ion in raw material A and raw material B is 4:
1, the mass ratio of raw material C and raw material B is 3:1 carries out dispensing, is uniformly mixed, and obtains mixture；Mixture is shaped to immediately straight
The spherical particles of diameter 5mm, then standing 5 angels at room temperature, it completes consolidation, that is, obtains graininess and remove phosphorus composite material.Removing
Phosphate material is seated in the simulation water process column of Ф 30cm high 100mm, and pending phosphorous water prepares (phosphorus concentration with tap water
2mg/L), the above upflow filtration mode is handled, hydraulic detention time 60min, and water outlet phosphorus concentration reaches four class standard of surface water body.
Embodiment 5：
The present embodiment is prepared as follows except phosphorus composite material：
Using magnesium ion mass concentration be 9%, contain magnesium sulfate simultaneously and the waste liquid of magnesium chloride is as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then calcined at 700 DEG C
20min makes dolomite substantially completely decompose, and obtains the thermal activation dolomite being made of calcium oxide, periclase, calcite；Then it presses
According to mass ratio 1：1, into thermal activation dolomite plus water makes its resolution, calcium oxide aquation become calcium hydroxide, part periclase water
Shepardite is turned to, products therefrom crushing sieves with 100 mesh sieve, and obtains raw material B；
Desulfurated plaster, 500 DEG C of calcining 1h, crushing is selected to sieve with 100 mesh sieve, obtain raw material C, XRD and see respectively with SEM spectrum
Fig. 5, Fig. 6.
By raw material A, raw material B and raw material C, the molar ratio according to free calcium oxide in magnesium ion in raw material A and raw material B is 4:
1, the mass ratio of raw material C and raw material B is 1:1 carries out dispensing, is uniformly mixed, and obtains mixture；Mixture is shaped to immediately straight
The spherical particles of diameter 5mm, then standing 5 angels at room temperature, it completes consolidation, that is, obtains graininess and remove phosphorus composite material.
Dephosphorization material is seated in the simulation water process column of Ф 30cm high 100mm, pending phosphorous water tap water
It prepares (phosphorus concentration 2mg/L), the above upflow filtration mode is handled, hydraulic detention time 5h, and water outlet phosphorus concentration reaches surface water body
Four class standards.
Claims (9)
1. a kind of preparation method except phosphorus composite material, it is characterised in that include the following steps：
Using magnesium salts waste liquid of the magnesium ion mass concentration not less than 5% as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then calcined at 600~800 DEG C
So that dolomite is partially or completely decomposed, obtains thermal activation dolomite；Then according to mass ratio 1：1, in the thermal activation dolomite
In plus water make its resolution, products therefrom crushing sieves with 100 mesh sieve, and obtains raw material B；
The raw material A is uniformly mixed with the raw material B, obtains mixture；The mixture is shaped to uniform ball immediately
Then type or rod-shpaed particle, diameter stand 2~10 days at room temperature within the scope of 1~20mm, that is, it is compound to obtain graininess dephosphorization
Material；Or it is ornamental slab for paving the floor shape that compaction moulding in mold, which is added, in the mixture, then stands 7~10 days at room temperature, that is, obtains
It obtains ornamental slab for paving the floor shape and removes phosphorus composite material.
2. preparation method according to claim 1, it is characterised in that：
The magnesium salts waste liquid is the waste liquid of containing magnesium sulfate, or is the waste liquid simultaneously containing magnesium sulfate and magnesium chloride.
3. preparation method according to claim 1, it is characterised in that：
The adding proportion of the raw material A and the raw material B, according to free in magnesium ion in raw material A and the thermal activation dolomite
The molar ratio computing of calcium oxide is 5:1~1:1.
4. any application except phosphorus composite material prepared by claim 1-3, it is characterised in that：
By described except phosphorus composite material is laid in water process column, processing pond, artificial swamp or riverbed, by pending water with
Seepage flow mode removes phosphorus composite material described in flowing through, described except phosphorus composite material is as reactivity porous media material slow release
Calcium ion and hydroxyl promote low phosphorus in water to form calcium phosphorus precipitation, to make phosphorus concentration in water reach four category of surface water body
It is accurate.
5. a kind of preparation method except phosphorus composite material, it is characterised in that include the following steps：
Using magnesium salts waste liquid of the magnesium ion mass concentration not less than 5% as raw material A；
It selects dolomite mass percentage to be not less than 95% dolomite, was crushed 1mm sieves, and was then forged at 600~1000 DEG C
Burning makes dolomite decompose completely, obtains thermal activation dolomite；Then according to mass ratio 1：1, add in the thermal activation dolomite
Water makes its resolution, products therefrom crushing sieve with 100 mesh sieve, and obtains raw material B；
Selection calcium sulfate crushing sieves with 100 mesh sieve, as raw material C；
The raw material A, the raw material B are uniformly mixed with the raw material C, obtain mixture；The mixture is molded immediately
For uniform ball-type or rod-shpaed particle, diameter is within the scope of 1~20mm, and then standing 5~10 angels at room temperature, it is completed admittedly
Knot obtains graininess and removes phosphorus composite material；Or it is ornamental slab for paving the floor shape that compaction moulding in mold, which is added, in the mixture, is then existed
7~10 days are stood at room temperature, that is, obtains ornamental slab for paving the floor shape and removes phosphorus composite material.
6. preparation method according to claim 5, it is characterised in that：
The magnesium salts waste liquid is the waste liquid of containing magnesium sulfate, or is the waste liquid simultaneously containing magnesium sulfate and magnesium chloride.
7. preparation method according to claim 5, it is characterised in that：
The calcium sulfate is the anhydrite ore that calcium sulphate content is not less than 80%, or is dead plaster waste material, or is de-
Sulphur gypsum, or for by desulfurated plaster in the anhydrous gypsum being changed into not less than 400 DEG C of temperature lower calcinations.
8. preparation method according to claim 5, it is characterised in that：
The adding proportion of the raw material A and the raw material B according to free calcium oxide in magnesium ion in raw material A and raw material B mole
Than being calculated as 5:1~1:The mass ratio of 1, raw material C and raw material B are 5:1~1:1.
9. any application except phosphorus composite material prepared by claim 5-8, it is characterised in that：
By described except phosphorus composite material is laid in water process column, processing pond, artificial swamp or riverbed, by pending water with
Seepage flow mode removes phosphorus composite material described in flowing through, described except phosphorus composite material is as reactivity porous media material slow release
Calcium ion and hydroxyl promote low phosphorus in water to form calcium phosphorus precipitation, to make phosphorus concentration in water reach four category of surface water body
It is accurate.
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| CN201810604848.3A Pending CN108658194A (en) | 2018-06-13 | 2018-06-13 | A kind of preparation method and applications except phosphorus composite material |
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Cited By (2)
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| CN111203173A (en) * | 2020-01-16 | 2020-05-29 | 陈赫然 | Phosphorus removal material based on collophanite tailings and preparation and application methods thereof |
| CN111517439A (en) * | 2020-04-30 | 2020-08-11 | 陈赫然 | Compound phosphorus removal material based on collophanite and application method thereof |
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Cited By (2)
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| CN111203173A (en) * | 2020-01-16 | 2020-05-29 | 陈赫然 | Phosphorus removal material based on collophanite tailings and preparation and application methods thereof |
| CN111517439A (en) * | 2020-04-30 | 2020-08-11 | 陈赫然 | Compound phosphorus removal material based on collophanite and application method thereof |
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