CN108793400A - A kind of denitrogenation dephosphorizing composite material and preparation method and application - Google Patents
A kind of denitrogenation dephosphorizing composite material and preparation method and application Download PDFInfo
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- CN108793400A CN108793400A CN201810604847.9A CN201810604847A CN108793400A CN 108793400 A CN108793400 A CN 108793400A CN 201810604847 A CN201810604847 A CN 201810604847A CN 108793400 A CN108793400 A CN 108793400A
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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
- C02F3/28—Anaerobic digestion processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
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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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of denitrogenation dephosphorizing composite material and preparation method and applications, and wherein denitrogenation dephosphorizing composite material is obtained by being rich in magnesium salts waste liquid, dolime, desulfurated plaster and iron sulfide mixing post-processing.Denitrogenation dephosphorizing composite material of the present invention is used for the structure infiltration dam on irrigation canals and ditches, river, or it is handled for artificial swamp infiltration, water flows through filtrate with filter type, material slow release calcium ion and hydroxyl, it acts on forming precipitation of hydroxyapatite to go phosphorus micro in water removal, water outlet phosphorus concentration to reach four class standard of surface water body with the phosphorus in water；It is nitrogen that the microorganism of material granule surface and internal void attachment converts nitrate nitrogen and ammonia nitrogen under anoxic conditions.
Description
Technical field
The present invention relates to a kind of denitrogenation dephosphorizing composite material and preparation method and applications, belong to sewage disposal technology neck
Domain.
Background technology
With the aggravation of water pollution, eutrophication generally occurs for China's surface water body.It is great that country sets up water pollution control
Special project is studied, and input huge fund carries out municipal sewage treatment Facilities Construction, improves the handling rate of city domestic sewage.However,
City domestic sewage processing at present generally uses oxic activated sludge process, but total nitrogen in Aerobic biological process water outlet, total
The concentration of phosphorus still respectively reaches 20-35mg/L, 0.3-3.0mg/L, is 10-50 times of water body in lake second standard.Many feelings
Sanitary sewage is difficult to stably reach country-level emission standard A by two stage treatment under condition, need increase advanced treating facility with
Ensure standard water discharge.Even if sanitary sewage disposal reaches standard of drainage, but for the water body of eutrophication, needs to waste water
Carry out the ecological environment that tightened up denitrogenation dephosphorizing just can guarantee water body.As landscape water etc. especially after sanitary sewage disposal
Realize that waste water reclaiming, sewage treatment plants secondary treatment yielding water need further denitrogenation dephosphorizing that could meet waste water reclaiming
Application requirement.
Lime precipitation, molysite deposition method or the aluminium salt precipitation method are generally used in the processing of Coal Gas Washing Cycling Water phosphorus.In neutral pH
The lower calcium phosphate solubility product precipitated of value is larger, controls higher pH value to ensure to precipitate dephosphorization and is discharged lower phosphorus concentration, no
Only cause reagent consumption amount excessive, and water outlet pH value is excessively high, can not meet emission request.Thus use lime treatment low phosphorus
It can not achieve the desired results.When phosphorus concentration is very low in water, iron, aluminium ion and phosphate radical form colloidal sol, it is difficult to usually used
Sedimentation basin calcium phosphate precipitation is separated from the water out.In order to improve precipitation phosphor-removing effect, it is necessary to add far more than precipitation phosphorus
The precipitating reagent of required dosage causes iron, aluminum metal ion dosage big.
Have many scholars both at home and abroad to be studied in terms of absorption method dephosphorization, common dephosphorization adsorbent mainly have zeolite,
The natural mineral matters such as calcite, bentonite, Concave-convex clay rod, vermiculite, red mud, flyash and solid waste, these materials pair
Phosphorus has certain suction-operated, but adsorption capacity is low, and regeneration is relatively difficult.In order to improve the adsorption capacity of dephosphorization adsorbent,
Many scholars carry out the preparation research except phosphorus composite material, including with debirs make the metals such as carrier loaded La, Ce, Fe from
Son is carrier loaded La, Al, Fe with mineral such as quartz sand, montmorillonite, attapulgite, zeolites and prepares modified adsorbent, these are multiple
Closing adsorbent has higher dephosphorization suction-operated.From the point of view of domestic and international result of study, above-mentioned composite material has preferably absorption
The reason of effect is adsorbent surface active component Fe3+、Al3+、La3+、Ce3+Hydroxide has stronger chemistry with phosphate radical
Bonding action.It is high with rare-earth element modified sorbing material dephosphorization efficiency, but it is expensive, and the foreground of popularization and application is little.
Cheap efficient dephosphorization adsorbent still has to be developed.
Invention content
The present invention is to avoid above-mentioned existing deficiencies in the technology, it is desirable to provide a kind of denitrogenation dephosphorizing composite wood
Material and its preparation method and application.
Denitrogenation dephosphorizing composite material of the present invention is by being rich in magnesium salts waste liquid, dolime, desulfurated plaster and iron vulcanization
Object is measured mixing post-processing and is obtained according to the ratio.
The magnesium salts waste liquid that is rich in includes the waste liquid rich in magnesium sulfate, or the waste liquid rich in magnesium sulfate and magnesium chloride；Institute
It states rich in magnesium ion mass concentration >=1% in magnesium salts waste liquid.
The dolime be the dolomite of dolomite mass content >=90% is fired at 800-1000 DEG C it is white
Marble decomposes completely, and water resolution is added to become powdery；
The desulfurated plaster is with desulfurated plaster (i.e. desulfurization method of limestone-gypsum product) for raw material, dry simultaneously to crushed
The powder obtained after 100 mesh sieve.
The iron sulfide be by pyrite content more than 70% Colloid form pyrite ore or magnetic iron ore content be more than
80% ore reduction and the powder sieved with 100 mesh sieve, or pyrite, magnetic iron ore concentrate for mining industry flotation acquisition
The content of powder, harmful heavy metal is less than 0.1%.
The rate of charge rich in magnesium salts waste liquid and dolime is to be rich in magnesium salts waste liquid in Mg and dolime
Ca is counted, molar ratio 2:1-1:2；The mass ratio of desulfurated plaster and dolime is 5:1-1:10；Iron sulfide be rich in magnesium
The rate of charge of bisulfate waste liquor is by S in iron sulfide and is rich in magnesium salts waste liquid in terms of Mg, molar ratio 2:1-1:2.
Desulfurated plaster can be substituted with the anhydrite for crushing and sieving with 100 mesh sieve in raw material.
The preparation method of denitrogenation dephosphorizing composite material of the present invention is to will be enriched in magnesium salts waste liquid, dolime, desulfurated plaster
And iron sulfide measures mixing according to the ratio, is shaped to spherical or rod-shpaed particle, diameter 2-20mm, then in environment temperature and sky
Reaction consolidation 2-10 days are stood under gas atmosphere, water spray elution removal dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
Or desulfurated plaster is calcined at 500-800 DEG C be changed into dead plaster first, then by each component by matching
Proportion mixes, and is shaped to spherical or rod-shpaed particle, then a diameter of 2-20mm is stood anti-under environment temperature and air atmosphere
It should consolidate 2-10 days, water spray elution removal dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
The application process of denitrogenation dephosphorizing composite material of the present invention, be by the denitrogenation dephosphorizing composite material be used for irrigation canals and ditches,
Structure infiltration dam on river, or handled for artificial swamp infiltration, water flows through filtrate, material slow release calcium with filter type
Phosphorus in ion and hydroxyl, with water acts on forming precipitation of hydroxyapatite to go phosphorus micro in water removal, water outlet phosphorus concentration to reach
To four class standard of surface water body；The microorganism of material granule surface and internal void attachment converts nitrate nitrogen under anoxic conditions
It is nitrogen with ammonia nitrogen.
Denitrogenation dephosphorizing composite material of the present invention has the beneficial effect that the following aspects：
1, the component in dolomite ash reacts to form new object phase gypsum and shepardite with magnesium salt solution, has played cementing work
With, do not need outer adding additives, just easily obtain the granular materials with higher-strength.
2, magnesia in material of the present invention, shepardite slow mechanism dissolved release hydroxyl maintain the pH value of Pore Solution 9-10 it
Between, gypsum, anhydrite slow mechanism dissolved maintain calcium ion concentration 30-80mg/L in water, promote phosphorus micro in water in granular materials
It is fixed in outer surface and internal void.
3, microorganism converts nitrate and ammonia using the iron sulfide in ammonia nitrogen and material as electron donor under anoxic conditions
Nitrogen is nitrogen, and synkaingenesis iron hydroxide has solid phosphorus effect.
Specific implementation mode
The non-limiting examples of the present invention are described below.
Embodiment 1：
The preparation method of denitrogenation dephosphorizing composite material is as follows in the present embodiment：
1, raw material
Rich in magnesium salts waste liquid：Waste liquid of the selection rich in magnesium sulfate, magnesium ion mass concentration 4.5%；
Dolime：High-quality dolomite is fired to dolomite in 900 DEG C to decompose completely, water resolution is added to become powdery；
Desulfurated plaster：With desulfurated plaster (i.e. desulfurization method of limestone-gypsum product) for raw material, drying simultaneously crushed 100 mesh
The powder obtained after sieve；
Iron sulfide：By the Colloid form pyrite ore reduction of pyrite content 75% and the powder that sieves with 100 mesh sieve；
2, it matches
Rate of charge rich in magnesium salts waste liquid and dolime to be rich in magnesium salts waste liquid in Mg and dolime in terms of Ca,
Molar ratio is 1:1；The mass ratio of desulfurated plaster and dolime is 2:1；Iron sulfide and the rate of charge for being rich in magnesium salts waste liquid
In terms of by S in iron sulfide and rich in Mg in magnesium salts waste liquid, molar ratio 2:1.
3, it prepares
It will be enriched in magnesium salts waste liquid, dolime, desulfurated plaster and iron sulfide and measure mixing according to the ratio, be shaped to spherical
Or rod-shpaed particle, diameter 2-20mm, reaction consolidation 2 days are then stood under environment temperature and air atmosphere, water spray elution is gone
Except dissolving salt, that is, obtain graininess denitrogenation dephosphorizing composite material.
4, it applies
Denitrogenation dephosphorizing composite material manufactured in the present embodiment is used for Performance of Constructed Wetlands Substrates, water flows through filter with filter type
Material, the phosphorus in material slow release calcium ion and hydroxyl, with water act on that form precipitation of hydroxyapatite micro in water removal to go
Phosphorus, it is nitrogen that the microorganism of material granule surface and internal void attachment converts nitrate nitrogen and ammonia nitrogen under anoxic conditions.
It is discharged phosphorus concentration and is less than 0.2mg/L, ammonia nitrogen concentration is less than 1.50mg/L, and COD concentration is less than 20mg/L, reaches III class of surface water body
Standard.
Embodiment 2：
The preparation method of denitrogenation dephosphorizing composite material is as follows in the present embodiment：
1, raw material
Rich in magnesium salts waste liquid：Waste liquid of the selection rich in magnesium sulfate, magnesium ion mass concentration 3%；
Dolime：High-quality dolomite is fired to dolomite in 800-1000 DEG C to decompose completely, water resolution is added to become
Powdery；
Desulfurated plaster：With desulfurated plaster (i.e. desulfurization method of limestone-gypsum product) for raw material, drying simultaneously crushed 100 mesh
The powder obtained after sieve；
Iron sulfide：The magnetic iron ore concentrate powder that mining industry flotation obtains；
2, it matches
Rate of charge rich in magnesium salts waste liquid and dolime to be rich in magnesium salts waste liquid in Mg and dolime in terms of Ca,
Molar ratio is 2:1；The mass ratio of desulfurated plaster and dolime is 1:1；Iron sulfide and the rate of charge for being rich in magnesium salts waste liquid
In terms of by S in iron sulfide and rich in Mg in magnesium salts waste liquid, molar ratio 1:1.
3, it prepares
It will be enriched in magnesium salts waste liquid, dolime, desulfurated plaster and iron sulfide and measure mixing according to the ratio, be shaped to spherical
Or rod-shpaed particle, diameter 5mm, reaction consolidation 10 days, water spray elution removal are then stood under environment temperature and air atmosphere
Dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
4, it applies
Denitrogenation dephosphorizing composite material manufactured in the present embodiment is used for structure infiltration filtrate, material slow release on irrigation canals and ditches
Phosphorus in calcium ion and hydroxyl, with water acts on forming precipitation of hydroxyapatite to remove phosphorus micro in water removal, material granule table
It is nitrogen that the microorganism of face and internal void attachment converts nitrate nitrogen and ammonia nitrogen under anoxic conditions.Water outlet phosphorus concentration is less than
0.2mg/L, ammonia nitrogen concentration are less than 1.50mg/L, and COD concentration is less than 20mg/L, reaches III class standard of surface water body.
Embodiment 3：
The preparation method of denitrogenation dephosphorizing composite material is as follows in the present embodiment：
1, raw material
Rich in magnesium salts waste liquid：Waste liquid of the selection rich in magnesium sulfate, magnesium ion mass concentration 3%；
Dolime：High-quality dolomite is fired to dolomite in 800-1000 DEG C to decompose completely, water resolution is added to become
Powdery；
Desulfurated plaster：Desulfurated plaster is dried, 500-800 DEG C of calcining is changed into anhydrite, and crushing obtains after sieving with 100 mesh sieve
Powder；
Iron sulfide：The magnetic iron ore concentrate powder that mining industry flotation obtains；
2, it matches
Rate of charge rich in magnesium salts waste liquid and dolime to be rich in magnesium salts waste liquid in Mg and dolime in terms of Ca,
Molar ratio is 1:2；The mass ratio of desulfurated plaster and dolime is 1:2；Iron sulfide and the rate of charge for being rich in magnesium salts waste liquid
In terms of by S in iron sulfide and rich in Mg in magnesium salts waste liquid, molar ratio 2:1.
3, it prepares
It will be enriched in magnesium salts waste liquid, dolime, desulfurated plaster and iron sulfide and measure mixing according to the ratio, be shaped to spherical
Or rod-shpaed particle, diameter 10mm, reaction consolidation 10 days, water spray elution removal are then stood under environment temperature and air atmosphere
Dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
4, it applies
Denitrogenation dephosphorizing composite material manufactured in the present embodiment is used for structure infiltration dam, material slow release calcium in creek
Phosphorus in ion and hydroxyl, with water acts on forming precipitation of hydroxyapatite to go to phosphorus micro in water removal, material granule surface
It is nitrogen to convert nitrate nitrogen and ammonia nitrogen under anoxic conditions with the microorganism of internal void attachment.Water outlet phosphorus concentration is less than
0.2mg/L, ammonia nitrogen concentration are less than 1.50mg/L, and COD concentration is less than 20mg/L, reaches III class standard of surface water body.
Claims (7)
1. a kind of denitrogenation dephosphorizing composite material, it is characterised in that：Be by be rich in magnesium salts waste liquid, dolime, desulfurated plaster with
And iron sulfide mixing post-processing obtains.
2. denitrogenation dephosphorizing composite material according to claim 1, it is characterised in that：
The magnesium salts waste liquid that is rich in includes the waste liquid rich in magnesium sulfate, or the waste liquid rich in magnesium sulfate and magnesium chloride；The richness
Magnesium ion mass concentration >=1% in waste liquid containing magnesium salts；
The dolime is that the dolomite of dolomite mass content >=90% is fired to dolomite at 800-1000 DEG C
It decomposes completely, water resolution is added to become powdery；
The desulfurated plaster be using desulfurated plaster as raw material, it is dry and crush sieve with 100 mesh sieve after the powder that obtains；
The iron sulfide be by pyrite content more than 70% Colloid form pyrite ore or magnetic iron ore content be more than 80%
Ore reduction and the powder that sieves with 100 mesh sieve, or be pyrite, magnetic iron ore concentrate powder that mining industry flotation obtains, have
The content of evil heavy metal is less than 0.1%.
3. denitrogenation dephosphorizing composite material according to claim 1 or 2, it is characterised in that：
The rate of charge rich in magnesium salts waste liquid and dolime to be rich in magnesium salts waste liquid in terms of Mg and Ca in dolime,
Molar ratio is 2:1-1:2；The mass ratio of desulfurated plaster and dolime is 5:1-1:10；Iron sulfide be rich in magnesium salts waste liquid
Rate of charge by S in iron sulfide with rich in Mg in magnesium salts waste liquid in terms of, molar ratio 2:1-1:2.
4. denitrogenation dephosphorizing composite material according to claim 2, it is characterised in that：
The desulfurated plaster is substituted with the anhydrite for crushing and sieving with 100 mesh sieve.
5. the preparation method of any denitrogenation dephosphorizing composite material in a kind of claim 1-4, it is characterised in that：
It will be enriched in magnesium salts waste liquid, dolime, desulfurated plaster and iron sulfide and measure mixing according to the ratio, be shaped to spherical or stick
Then shape particle, diameter 2-20mm stand reaction consolidation 2-10 days, water spray elution removal under environment temperature and air atmosphere
Dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
6. the preparation method of any denitrogenation dephosphorizing composite material in a kind of claim 1-4, it is characterised in that：
Desulfurated plaster is calcined at 500-800 DEG C first and is changed into dead plaster, then each component is measured to mixing according to the ratio,
It is shaped to spherical or rod-shpaed particle, then a diameter of 2-20mm stands reaction consolidation 2- under environment temperature and air atmosphere
10 days, water spray elution removal dissolving salt obtains graininess denitrogenation dephosphorizing composite material.
7. the application of any denitrogenation dephosphorizing composite material in a kind of claim 1-4, it is characterised in that：
The denitrogenation dephosphorizing composite material is used for the structure infiltration dam on irrigation canals and ditches, river, or at artificial swamp infiltration
Reason, water flow through filtrate with filter type, and the phosphorus in material slow release calcium ion and hydroxyl, with water acts on forming hydroxyapatite
It precipitates that phosphorus micro in water removal, water outlet phosphorus concentration is gone to reach four class standard of surface water body；Material granule surface and internal holes
The microorganism of gap attachment converts nitrate nitrogen under anoxic conditions and ammonia nitrogen is nitrogen.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279377A (en) * | 2020-09-30 | 2021-01-29 | 国河环境研究院(南京)有限公司 | Preparation method of wetland filler for purifying black and odorous water body and water purifying device using filler |
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Application publication date: 20181113 |
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| RJ01 | Rejection of invention patent application after publication |