CN106311129A - Preparation method and application of efficient removing materials for interstitial water phosphate of sediments - Google Patents
Preparation method and application of efficient removing materials for interstitial water phosphate of sediments Download PDFInfo
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- CN106311129A CN106311129A CN201610798384.5A CN201610798384A CN106311129A CN 106311129 A CN106311129 A CN 106311129A CN 201610798384 A CN201610798384 A CN 201610798384A CN 106311129 A CN106311129 A CN 106311129A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention provides preparation method and application of efficient removing materials for interstitial water phosphate of sediments. Lake sediments are initiatively taken as basic materials of the materials and are subjected to calcination and alkaline washing, then the obtained material is mixed with kaolin, and mixed powder obtained is modified via ferric salt and then pore-forming agents are added for granulation and calcination shaping is peformed, and the low EPCo value and high Qmax value efficient removing materials for the interstitial water phosphate of the sediments are obtained. Concentration of the interstitial water phosphate of the sediments can be effectively cut down through the materials, and release of the phosphate of the sediments-water interfaces is restrained; desorption capacity of phosphate of the materials is weak and adsorption capacity is large, so that effective resistance and control of the materials on the sediments-water interfaces can be truly realized; the materials are low in cost, good in social and economic benefits, high in security, free of ecological risk on lake water, energy saving and environment friendly and remarkable in control effect on the sediments-water interfaces of different lakes of the Dian Lake during application.
Description
Technical field
The present invention relates to a kind of sediment interstitial water phosphate and efficiently remove preparation method and the application of material, belong to water ring
Environment pollution control field.
Background technology
Over nearly more than 30 years, due to socioeconomic development and the impact of mankind's activity, substantial amounts of xenobiotic pollutants enters lake
Moor and be enriched in deposit, make China's majority lake surface sediments suffer severe contamination.The survey showed that, and many lakes are especially
The substrate pollution of urban lakes is surprising, as in the deposit of many waters such as Taihu Lake, Dian Chi, Chaohu, total phosphorus content is up to 3000-
4000mg/kg.Deposit is not only important home to return to and the accumulation storehouse of pollution of water thing, but also is the weight of overlying water pollution
Endogenous, this is because there is sedimentation absorption and the homeostasis process of desorbing release, water body between deposit and overlying water
In phosphorus concentration be heavily dependent on the movement of this dynamic equilibrium, say, that sediment phosphorus migrates and release is depended on
The Concentraton gradient of Interstitial Water between adjacent two layers on the horizontal or vertical direction of column shaped deposit.At same vertical section, when upper
When surface sediments Interstitial Water phosphorus concentration is higher than lower floor, Phosphorus in Sediments hydrochlorate is vertically expanded between low concentration region by between high concentration region
Dissipate, define the trend that phosphate is migrated to layer deposition thing by surface deposit.On the contrary, dense when seabed sediment Interstitial Water phosphorus
When degree is higher than upper strata, phosphate is then migrated to surface deposit by layer deposition thing.Under normal circumstances, sediment interstitial water phosphoric acid
Salinity is higher than overlying water phosphate concn, it is considered that, just may cause water when the concentration of phosphorus reaches 0.02mg/L in water body
Body eutrophication.Therefore, effectively cutting down sediment interstitial water phosphate concn, controlling sediment phosphorus hydrochlorate to overlying water diffusion is
The important content that eutrophic lake internal loading controls.
Improvement and reparation to eutrophication water quality focus mostly in reducing external loadings, and in the release of Phosphorus in Sediments i.e.
Source Phosphurus release but can delay or offset the actual effect of above-mentioned measure, so the premise being effectively controlled at outside polluter
Under, the research of deposit internal loading becomes the key of pollution control of water.Soverlay technique is currently to control internal loading in situ
One of effective measures, because it is effective on endogenous Environmental capacity and less and receive extensively pass on water ecological setting impact
Note.The core of soverlay technique is to cover the selection of material in situ, and currently used more covering material has untainted bed mud, clear
Clean river sand, gravel, calcium bentonite, lime-ash, artificial zeolite, cement, also have such as calcite, flyash, geotextile or one
A little complicated man-made land sills etc..Such as, Chinese patent literature CN102775030A disclose a kind of using clean water sludge as
The method covering material, the method is by being dried the clean water sludge after dehydration, pulverize, sieve, then at the temperature of 500-600 DEG C
Lower calcination, obtains the clean water sludge of regeneration.This technology is by covering the clean water sludge of regeneration at the bottom of the pollution of water body to be repaired
Above mud so that polluted bed mud separates with overlying water physical property, on the one hand inhibit polluted bed mud endogenous pollution releasing to water body
Putting, the inorganic particle material based on metal-oxide on the other hand contained in clean water sludge also can be to the nitrogen phosphorus etc. in water body
Polluter produces and absorbs, and accelerates the migration to bed mud of the polluter in water body, is capable of counterweight to a certain extent
The water remediation of polluted river channel.
But above-mentioned technology uses the clean water sludge of waterworks as covering material, and the introducing of this xenobiotics is to water body
There is certain ecological risk in speech, and owing to the phosphate concn in water body is much smaller than the phosphate concn in clean water sludge,
Thus the phosphate in clean water sludge the most also can migrate to water body, cause above-mentioned covering material leading to its overlying water release phosphorus
Amount is big, thus this technology may effectively not remove the phosphorus in water body, that is to say, prior art still cannot use to be covered in situ
Lid technology really realizes the reparation to polluted water body, and this is a technology urgently to be resolved hurrily to those skilled in the art
A difficult problem.
Summary of the invention
The technical problem to be solved is to overcome prior art using clean water sludge as covering existing for material
The ecological risk of material own is high, the defect such as Phosphurus release risk is big, and then provide one to draw materials inexpensively, safety height, practicality
The sediment interstitial water phosphate by force and to sediment interstitial water low phosphorus hydrochlorate with stronger removal effect efficiently removes material
The preparation method of material and application.
To this end, the present invention realizes above-mentioned purpose technical scheme it is:
A kind of sediment interstitial water phosphate efficiently removes the preparation method of material, including:
(1) gathering lake sediment, freeze-dried, grinding is sieved, and obtains deposit powder body, depends on described deposit powder body
Secondary carry out roasting and alkalescence washing processes, and post-drying, obtain activated deposition thing, standby；
(2) described activated deposition thing is mixed homogeneously with Kaolin formation mixed powder, standby；
(3) iron salt solutions is used to be modified described mixed powder processing, and post-drying, standby；
(4) in the mixed powder that step (3) is modified, add pore creating material, add water infiltration after mix homogeneously, be squeezed into
Type, after molding mass is fired, obtains described sediment interstitial water phosphate and efficiently removes material.
Sintering temperature in step (1) is 450-800 DEG C, preferably 600 DEG C.
Using sodium hydrate aqueous solution to carry out washing process in step (1), the concentration of described sodium hydrate aqueous solution is
0.05-0.3mol/L, preferably 0.1mol/L.
Described kaolinic consumption accounts for the 50-90wt% of described mixed powder gross mass, preferably 50wt%.
Described iron salt solutions is 0.20mol L-1FeSO4Aqueous solution, described FeSO4Aqueous solution and described mixed powder
Mass ratio be 100:1.
The addition of described pore creating material is the 0.2-1.5wt% of described mixed powder gross mass, preferably 0.5wt%；Institute
Stating pore creating material is corn cob.
In step (4), the addition of water accounts for the 5-30wt% of described mixed powder quality, preferably 10wt%.
Sintering temperature in step (4) is 550-800 DEG C, preferably 700 DEG C.
It is the granule with 3-5mm particle diameter that described sediment interstitial water phosphate efficiently removes material.
The sediment interstitial water phosphate prepared by above-mentioned preparation method is efficiently removed material and is covered in situ as deposit
The purposes of material, the phosphate concn in described sediment interstitial water is 0.02-1.0mg/L.
The technique scheme of the present invention has the advantage that
1, sediment interstitial water phosphate of the present invention efficiently removes the preparation method of material, it is contemplated that lacustrine deposit
Thing has dual role, and it is " remittance " and " source " of phosphorus of phosphorus, owing to the source-sink transition process of deposit is difficult to control to,
Especially when the initial phosphate concentration in water body is relatively low, deposit can show phosphorus " negative adsorption " phenomenon, causes using
Deposit as phosphorus controlled-release material also exist the entrained phosphate of material self can to overlying water-soluble go out risk, it is easy to cause
The secondary pollution of water body, ecological security is poor, this most just prior art cannot directly use lake sediment to prepare phosphorus
The reason place of controlled-release material, and in order to overcome drawbacks described above, the present invention first with deposit with kaolinic mixture as base
This raw material, after modification with Fe and shaping and roasting, formed a kind of as shown in Figure 3 there is relatively low adsorption-desorption equilibrium concentration
(EPC0) and relatively high-adsorption-capacity (Qmax) sediment interstitial water phosphate efficiently remove material.Research proves, EPC0Value is with heavy
The relative size of long-pending thing-water termination soluble phosphate (SRP) content determines phosphatic migratory direction, EPC0It is worth the least,
Show by material the least to the flux of overlying water release phosphorus, and QmaxValue then reflects material to phosphatic adsorption capacity,
QmaxIt is worth the biggest, shows that material is the biggest to phosphatic adsorption capacity, it can be seen that, sediment interstitial water of the present invention
Phosphate is efficiently removed material and can really be realized effectively hindering control to what Phosphorus Exchange at Sediment-water Interface discharged, thus solves existing
The material that covers in technology ignores big caused cannot effectively the controlling of material self Phosphurus release amount because pursuing phosphorus adsorbance simply
The problem of sediment phosphorus endogenous pollution processed.
Specifically, preparation method of the present invention is by using Kaolin efficient as sediment interstitial water phosphate
That removes material prepares one of raw material, in the most available Kaolin the aluminium oxide of high-load big to phosphatic adsorbance,
The characteristic that crystallized ability is strong, greatly reduces the adsorption-desorption equilibrium concentration of material itself, improves adsorption capacity, thus has
It is beneficial to realize the phosphatic removal of low concentration in lake sediment Interstitial Water, it is achieved it is effective that Phosphorus Exchange at Sediment-water Interface discharges
Resistance control；On the other hand utilize the caking property of Kaolin self to guarantee that Phosphurus release controls the molding of material；The third aspect utilizes height
The feature that ridge soil is drawn materials inexpensively, safety is high, practical, it is possible to decrease Phosphurus release controls the production cost of material and ecological wind
Danger.Further, the preparation method of the present invention has also individually carried out calcination process to deposit, so can not only remove deposit hole
Carbonate on deposit of moisture in gap and absorption and organic matter, increase porosity and the specific surface area of deposit, have
Be beneficial to improve the deposit absorbability to phosphorus, and can also the phosphorus of more difficult movement in activated deposition thing, deposit passes through subsequently
Occur a certain degree of Mineral Transformation that the phosphorus of activation is fixed once again, advantageously reduce the internal loading amount of sediment phosphorus；
Owing to roasting can make the structure and composition of deposit change, enhance absorbability, but roasting also can cause in deposit
Phosphatic locomotivity strengthens, and based on ferrum aluminum oxidation state phosphorus in removable phosphorus, therefore the preparation method of the present invention also uses
Deposit after roasting is carried out by alkaline solution, thus can effectively reduce phosphatic background values in material, carries further
Rise material to phosphatic removal effect.
Additionally, the preparation method of the present invention also added pore creating material in the forming process of material, to utilize pore creating material to exist
Volatilization under roasting condition can make material form the characteristic of uniform tiny cavernous structure, contributes to increasing the specific surface area of material,
Thus improve the control phosphate material of the present invention adsorption capacity to phosphorus further, as shown in Fig. 4 a～4d, when phosphate initial in solution
When concentration is relatively low, material 4 is significantly higher than material 1,2 and 3 to phosphatic absorbability, and this is primarily due to material before pore-creating
The aperture of material is less, and when phosphate concn is relatively low, in reaction system, phosphatic diffusivity is more weak, it is more difficult to play material
Adsorption effect, after interpolation corn cob adds the porosity of material, the phosphate of low concentration is prone to penetrate into material internal,
Even if thus initial phosphate concn is relatively low in reaction system, the material of the present invention is the highest to phosphatic clearance.
2, sediment interstitial water phosphate of the present invention efficiently removes the preparation method of material, by by mixed powder
Granulating and forming be particle diameter be the granule of 3-5mm, by the material-paving of the present invention after contaminated deposit surface, can have
Imitate reduction bottom water body answers the disturbance to deposit of shear force and water body flow, and then advantageously reduces the phosphorus of sediment resuspension
Release.
3, sediment interstitial water phosphate of the present invention efficiently removes the preparation method of material, the final material prepared
Phosphatic adsorption capacity is reached as high as 2550mg/Kg；By by material-paving of the present invention in contaminated deposition
Thing surface, it is possible to realization effectively hinders control to Phosphorus Exchange at Sediment-water Interface release, and sediment interstitial water variable concentrations phosphate is removed
Rate is up to 92%-98%.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the specific embodiment of the invention, below will be in detailed description of the invention
The required accompanying drawing used that describes be briefly described, it should be apparent that, the accompanying drawing in describing below is some of the present invention
Embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to these
Accompanying drawing obtains other accompanying drawing.
Fig. 1 is that material 1～4 is to phosphatic absorption-desorption curve chart；
Fig. 2 is that material 1～4 is to phosphatic adsorption isotherm line chart；
Fig. 3 is that material 1～4 is to phosphatic adsorption-desorption equilibrium concentration (EPC0) and adsorption capacity (Qmax) figure；
Fig. 4 a～4d represents material 1～4 pairs of sediment interstitial water variable concentrations phosphatic removal effect figures respectively.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme is clearly and completely described, it is clear that described enforcement
Example is a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill
The every other embodiment that personnel are obtained under not making creative work premise, broadly falls into the scope of protection of the invention.
As long as additionally, technical characteristic involved in invention described below difference embodiment does not just constitute conflict each other
Can be combined with each other.
Deposition feedstock in following embodiment picks up from Dian Chi 24 ° 53 ' 55.31 " N and 102 ° 40 ' 35.92 " E, with Dian Chi
The quality meter of deposit, the loss on ignition of described Phosphorus in Sediment of Dianchi Lake is 20.23wt%, contains in described Phosphorus in Sediment of Dianchi Lake
The SiO of 30.07wt%2, the Al of 23.93wt%2O3, the Fe of 20.51wt%2O3, 0.32wt% CaO, 0.93wt% MgO,
The Na of 0.18wt%2The K of O, 3.08wt%2The TiO of O and 0.75wt%2；
Kaolin is purchased from Zhengzhou West Germany profit chemical plant；
Muffle furnace is purchased from Germany's Na Bore Muffle furnace, model: L5/11/P330+.
Embodiment 1
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 2h of 450 DEG C by described deposit powder body, uses 0.2mol/L after being cooled to room temperature
Sodium hydrate aqueous solution carry out washing process, and be evaporated in being placed on air dry oven, obtain activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
75wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 0.2wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 20wt% of described mixed powder quality, and
After be squeezed into graininess, molding mass, in 550 DEG C of roasting 2h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 3-5mm efficient
Remove material.
Embodiment 2
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 1h of 550 DEG C by described deposit powder body, uses 0.05mol/ after being cooled to room temperature
The sodium hydrate aqueous solution of L carries out washing process, and is evaporated in being placed on air dry oven, obtains activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
60wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 0.8wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 30wt% of described mixed powder quality, and
After be squeezed into graininess, molding mass, in 800 DEG C of roasting 2h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 3-4mm efficient
Remove material.
Embodiment 3
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 2h of 600 DEG C by described deposit powder body, uses 0.1mol/L after being cooled to room temperature
Sodium hydrate aqueous solution carry out washing process, and be evaporated in being placed on air dry oven, obtain activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
50wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 0.5wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 10wt% of described mixed powder quality, and
After be squeezed into graininess, molding mass, in 700 DEG C of roasting 2h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 4-5mm efficient
Remove material 4.
Embodiment 4
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 1h of 800 DEG C by described deposit powder body, uses 0.15mol/ after being cooled to room temperature
The sodium hydrate aqueous solution of L carries out washing process, and is evaporated in being placed on air dry oven, obtains activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
80wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 1.0wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 5wt% of described mixed powder quality, then
Being squeezed into graininess, molding mass, in 600 DEG C of roasting 1h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 3-5mm and efficiently goes
Except material.
Embodiment 5
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 1h of 700 DEG C by described deposit powder body, uses 0.3mol/L after being cooled to room temperature
Sodium hydrate aqueous solution carry out washing process, and be evaporated in being placed on air dry oven, obtain activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
90wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 1.0wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 15wt% of described mixed powder quality, and
After be squeezed into graininess, molding mass, in 650 DEG C of roasting 3h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 3-4mm efficient
Remove material.
Embodiment 6
Sediment interstitial water phosphate described in the present embodiment is efficiently removed material and is prepared by the following method:
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, is placed in the Muffle kiln roasting 1h of 650 DEG C by described deposit powder body, uses 0.25mol/ after being cooled to room temperature
The sodium hydrate aqueous solution of L carries out washing process, and is evaporated in being placed on air dry oven, obtains activated deposition thing, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described activation
Deposit and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
50wt%, standby；
(3) FeSO of 0.2mol/L is utilized4Described mixed powder is modified processing by aqueous solution, described FeSO4Aqueous solution
Being 100:1 with the mass ratio of described mixed powder, and be evaporated in being placed on air dry oven, it is standby that taking-up is cooled to room temperature；
(4) adding corn cob in the mixed powder that step (3) is modified, the addition of corn cob is described mixed powder
The 0.6wt% of gross mass；Adding water infiltration after mix homogeneously, the addition of water accounts for the 10wt% of described mixed powder quality, and
After be squeezed into graininess, molding mass, in 750 DEG C of roasting 3h, i.e. prepares the sediment interstitial water phosphate that particle diameter is 3-5mm efficient
Remove material.
Comparative example 1
Collection lake sediment is raw material, after freeze-dried, grinding is sieved, obtains the granularity deposition not less than 100 mesh
Powder, is placed in described deposit powder body the Muffle kiln roasting 2h of 600 DEG C, i.e. prepares material 1.
Comparative example 2
(1) gathering lake sediment is raw material, after freeze-dried, grinding is sieved, obtains granularity and sinks not less than 100 purposes
Long-pending powder, standby；
(2) taking Kaolin, drying, grinding are sieved, and obtain granularity and are not less than 100 mesh kaolin powders, by described deposition
Powder and kaolin powder are thoroughly mixed to form mixed powder in proportion, and described kaolinic consumption accounts for mixed powder gross mass
50wt%, standby；
(3) described mixed powder being added water infiltration, the addition of water accounts for the 10wt% of described mixed powder quality, then squeezes
Being pressed into graininess, molding mass, in 700 DEG C of roasting 2h, i.e. prepares material 2.
Comparative example 3
Collection lake sediment is raw material, after freeze-dried, grinding is sieved, obtains the granularity deposition not less than 100 mesh
Powder, is placed in the Muffle kiln roasting 2h of 600 DEG C by described deposit powder body, uses 0.1mol/L's after being cooled to room temperature
Sodium hydrate aqueous solution carries out washing process, and is evaporated in being placed on air dry oven, obtains material 3.
Experimental example
The present invention is respectively provided with material 1～4 and tests the experiment of phosphatic absorption-desorption and Adsorption thermodynamics, simultaneously
By simulation sediment interstitial water concentration to investigate material 1～4 pairs of phosphatic removal effects of sediment interstitial water variable concentrations.
1, absorption-desorption experiment
Configuring close to sediment interstitial water phosphorus concentration scope under the natural conditions of lake is 0～1.0mg/L (to be i.e. respectively provided with
Be 0,0.02,0.05,0.10,0.20,0.30,0.50 and 1.0mg/L) water sample；Weigh material dry sample 0.5g to be centrifuged in 100mL
Guan Zhong, is separately added into the water sample solution of the above-mentioned variable concentrations of 50mL, and the 24h (200rpm) that vibrates under 25 DEG C of environment is flat to absorption
Weighing apparatus；Take out centrifuge tube, centrifugal 15min under 5000rpm, take supernatant and obtained filtrate by 0.45 μm filter membrane sucking filtration, measure SRP dense
Degree；Take appropriate filtrate in 25mL color comparison tube, be settled to 25mL with distilled water, add 10% ascorbic acid of 0.5mL, shake up,
Adding 1mL molybdate solution after 30s fully to mix, develop the color 15min, makees reference with ultra-pure water, and colorimetric under 700nm wavelength is surveyed
Determine phosphorus concentration in solution.
Calculated by experimental data, it is thus achieved that material 1～4 as shown in Figure 1 is to phosphatic absorption-desorption curve；Profit again
Use linear distribution model fitting operation, it is thus achieved that material 1～4, to phosphatic adsorption-desorption equilibrium concentration, is shown in Fig. 3, wherein, line
Property equation is as follows:
Q=b+KdC
EPC0=(-b)/Kd
In above formula, Q is that material is to phosphatic equilibrium adsorption capacity, mg/kg；C is balance solution concentration, mg/L；EPC0For
Adsorption-desorption equilibrium concentration, KdFor linear distribution factor.
From figure 3, it can be seen that EPC0Showing as material 1 < material 2 < material 3 < material 4, that is to say, deposit is through 600
The EPC of the material of gained after DEG C roasting0Maximum, for 0.027mg/L；Deposit is mixed with Kaolin 1:1 in mass ratio is incorporated in 700
The EPC of the material formed after DEG C roasting0For 0.012mg/L, improve than deposit material of gained after 600 DEG C of roastings
1.3 again；The EPC of the material that deposit is formed successively after 600 DEG C of roastings and 0.1mol/L NaOH aqueous cleaning0For
0.0037mg/L, improves 6.4 times than deposit material of gained after 600 DEG C of roastings, the material that the embodiment of the present invention 3 prepares
The EPC of 40For 0.0016mg/L, improve 16.6 times than deposit material of gained after 600 DEG C of roastings.As can be seen here, according to
The material that the method for the invention prepares has less EPC0Value.
2, Adsorption thermodynamics experiment
The phosphate concn scope of test solution is 0～15mg/L (to be i.e. respectively set to 0,0.5,1.0,2.0,5.0,8.0
And 15.0mg/L)；Weigh material dry sample 0.5g in 100mL centrifuge tube, be separately added into the KH of 50mL variable concentrations series2PO4Molten
Liquid, the 24h (200rpm) that vibrates under 25 DEG C of environment is to adsorption equilibrium；Taking out centrifuge tube, under 5000rpm, centrifugal 15min, takes
Clear liquid is obtained filtrate by 0.45 μm filter membrane sucking filtration, measures SRP concentration；Take appropriate filtrate in 25mL color comparison tube, use distilled water constant volume
To 25mL, adding 10% ascorbic acid of 0.5mL, shake up, add 1mL molybdate solution and fully mix after 30s, develop the color 15min,
Reference is made with ultra-pure water, colorimetric under 700nm wavelength, measure phosphorus concentration in solution.
Calculated by experimental data, it is thus achieved that material 1～4 as shown in Figure 2 is to phosphatic adsorption isotherm；Recycling
Langmuir model fitting operation, it is thus achieved that material 1～4, to phosphatic adsorption capacity, is shown in Fig. 3, wherein, Langmuir model side
Journey is as follows:
Q=Qmax×C/(Kd+C)
In formula: Q is sample ammonia-nitrogen balance adsorbance, mg/kg；QmaxMaximal absorptive capacity, mg/kg；C is balance solution ammonia nitrogen
Concentration, mg/L.
From figure 3, it can be seen that QmaxShowing as material 2 < material 1 < material 4 < material 3, that is to say, deposit is through 600 DEG C
The material formed after roasting and deposit mix the material formed after being incorporated in 700 DEG C of roastings with Kaolin 1:1 in mass ratio
The Q of materialmaxIt is worth the most relatively low, by contrast, deposit institute's shape after 600 DEG C of roastings and 0.1mol/L NaOH aqueous cleaning successively
The Q of the material 4 that the material become and the embodiment of the present invention 3 preparemaxValue significantly improves.Thus illustrate, deposit is carried out alkalescence
Washing is to improve material QmaxThe necessary technology means of value.
3, material 1～4 pairs of sediment interstitial water variable concentrations phosphatic removal effect experiments
Take Dian Chi 0-20cm bed mud, after 5000r/min is centrifuged 5-30min, takes supernatant and pass through 0.45 μm microporous filter membrane,
Obtain sediment interstitial water, utilize phosphate standard storing solution that sediment interstitial water is configured to phosphate concn and be respectively
0.02, the Interstitial Water solution of 0.05,0.1,0.2,0.3,0.5 and 1mg/L, by material 1～4 according to water: the mass ratio of material is
The ratio mixing of 100:1, then at 25 DEG C, mixing vibration 16-24h in 200r/min constant temperature oscillator, tests and is calculated
Material 1～4 pairs of phosphatic removal effects of sediment interstitial water variable concentrations, result is as shown in Fig. 4 a～4d.
From Fig. 4 a～4d, material 4 removal effect phosphatic to Interstitial Water is best, is 0.02-to phosphate concn
In the Interstitial Water of 1mg/L, the clearance of phosphorus has reached 92%-99%, is secondly material 3, to Interstitial Water removal rate of phosphate is
89%-95%, and material 1 is worst to Interstitial Water phosphate removal effect.Thus absolutely prove, according to the method for the invention system
The material obtained has the phosphatic removal effect of optimal Interstitial Water.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right
For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or
Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. a sediment interstitial water phosphate efficiently removes the preparation method of material, it is characterised in that including:
(1) gathering lake sediment, freeze-dried, grinding is sieved, and obtains deposit powder body, enters described deposit powder body successively
Row roasting and alkalescence washing process, and post-drying, obtain activated deposition thing, standby；
(2) described activated deposition thing is mixed homogeneously with Kaolin formation mixed powder, standby；
(3) iron salt solutions is used to be modified described mixed powder processing, and post-drying, standby；
(4) in the mixed powder that step (3) is modified, add pore creating material, after mix homogeneously, add water infiltration, extruded, become
After shaped material is fired, obtains described sediment interstitial water phosphate and efficiently remove material.
Sediment interstitial water phosphate the most according to claim 1 efficiently removes the preparation method of material, it is characterised in that
Sintering temperature in step (1) is 450-800 DEG C, preferably 600 DEG C.
Sediment interstitial water phosphate the most according to claim 1 and 2 efficiently removes the preparation method of material, and its feature exists
In, step (1) use sodium hydrate aqueous solution carry out washing process, the concentration of described sodium hydrate aqueous solution is 0.05-
0.3mol/L, preferably 0.1mol/L.
4. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-3, its
Being characterised by, described kaolinic consumption accounts for the 50-90wt% of described mixed powder gross mass, preferably 50wt%.
5. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-4, its
Being characterised by, described iron salt solutions is 0.20mol L-1FeSO4Aqueous solution, described FeSO4Aqueous solution and described mixed powder
Mass ratio be 100:1.
6. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-5, its
Being characterised by, the addition of described pore creating material is the 0.2-1.5wt% of described mixed powder gross mass, preferably 0.5wt%；Institute
Stating pore creating material is corn cob.
7. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-6, its
Being characterised by, in step (4), the addition of water accounts for the 5-30wt% of described mixed powder quality, preferably 10wt%.
8. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-7, its
Being characterised by, the sintering temperature in step (4) is 550-800 DEG C, preferably 700 DEG C.
9. the preparation method of material is efficiently removed according to the sediment interstitial water phosphate described in any one of claim 1-8, its
Being characterised by, it is the granule with 3-5mm particle diameter that described sediment interstitial water phosphate efficiently removes material.
10. the sediment interstitial water phosphate prepared by the preparation method described in any one of claim 1-9 efficiently removes material
As the purposes of deposit situ capping materials, the phosphate concn in described sediment interstitial water is 0.02-1.0mg/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108311095A (en) * | 2018-03-16 | 2018-07-24 | 锡林郭勒职业学院 | A kind of preparation method and applications of flyash defluorinating agent |
| CN114700033A (en) * | 2020-12-07 | 2022-07-05 | 中国环境科学研究院 | Nitrogen and phosphorus control and aquatic plant habitat restoration material and preparation method and application thereof |
| CN114700034A (en) * | 2020-12-07 | 2022-07-05 | 中国环境科学研究院 | Nitrogen-controlling and aquatic plant habitat repairing material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811811A (en) * | 2010-05-10 | 2010-08-25 | 南京师范大学 | Method for inhibiting release of substrate sludge nutritive salt of eutrophic water body |
| CN102674562A (en) * | 2012-06-04 | 2012-09-19 | 中国科学院生态环境研究中心 | Material and method for repairing polluted water and bottom mud |
| CN104445627A (en) * | 2014-11-26 | 2015-03-25 | 中国环境科学研究院 | Lake endogenesis control brick and use method thereof |
| CN104549173A (en) * | 2015-02-06 | 2015-04-29 | 中国环境科学研究院 | Preparation method and application of phosphorus-adsorbing material used in sewage |
| CN104891742A (en) * | 2015-06-03 | 2015-09-09 | 广州贝山环保科技有限公司 | Ecological-chemical method for controlling release of shallow-water deposit phosphorus and application |
-
2016
- 2016-08-31 CN CN201610798384.5A patent/CN106311129B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811811A (en) * | 2010-05-10 | 2010-08-25 | 南京师范大学 | Method for inhibiting release of substrate sludge nutritive salt of eutrophic water body |
| CN102674562A (en) * | 2012-06-04 | 2012-09-19 | 中国科学院生态环境研究中心 | Material and method for repairing polluted water and bottom mud |
| CN104445627A (en) * | 2014-11-26 | 2015-03-25 | 中国环境科学研究院 | Lake endogenesis control brick and use method thereof |
| CN104549173A (en) * | 2015-02-06 | 2015-04-29 | 中国环境科学研究院 | Preparation method and application of phosphorus-adsorbing material used in sewage |
| CN104891742A (en) * | 2015-06-03 | 2015-09-09 | 广州贝山环保科技有限公司 | Ecological-chemical method for controlling release of shallow-water deposit phosphorus and application |
Non-Patent Citations (3)
| Title |
|---|
| WANG H ET AL.: ""Efficiency of sediment Amentdment with Zirconium-Modified Kaolin Clay to control Phosphorus Release from Sediments in Heavily Pollted Rivers"", 《EUROPE PMC》 * |
| 师路远: ""百花湖沉积物氮、磷释放的原位覆盖控制研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 胡秀芳等: ""掺杂黏土矿物对沉积物吸持磷能力的影响"", 《中国海洋大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108311095A (en) * | 2018-03-16 | 2018-07-24 | 锡林郭勒职业学院 | A kind of preparation method and applications of flyash defluorinating agent |
| CN114700033A (en) * | 2020-12-07 | 2022-07-05 | 中国环境科学研究院 | Nitrogen and phosphorus control and aquatic plant habitat restoration material and preparation method and application thereof |
| CN114700034A (en) * | 2020-12-07 | 2022-07-05 | 中国环境科学研究院 | Nitrogen-controlling and aquatic plant habitat repairing material and preparation method and application thereof |
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