CN108579670A - A method of utilizing clay dephosphorization - Google Patents
A method of utilizing clay dephosphorization Download PDFInfo
- Publication number
- CN108579670A CN108579670A CN201810419673.9A CN201810419673A CN108579670A CN 108579670 A CN108579670 A CN 108579670A CN 201810419673 A CN201810419673 A CN 201810419673A CN 108579670 A CN108579670 A CN 108579670A
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- Prior art keywords
- clay
- phosphorus
- dephosphorization
- phosphate
- absorption
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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
- B01J20/16—Alumino-silicates
-
- 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
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of method using clay dephosphorization, clay inherently has quantity big as a kind of natural minerals, cheap, the advantage that environmental protection easily recycles.The main component of clay is silica, is screened, is adsorbed to natural clay, and remaining phosphate concn is measured, it is found that its adsorbance has certain advantage compared to more other natural minerals, solve original dephosphorization adsorbent inefficiency, the higher disadvantage of cost.Using clay as adsorbent, in addition to adsorption efficiency can be improved, it can more achieve the purpose that waste recycling.
Description
Technical field
The present invention relates to dephosphorization adsorbing domains, and in particular to a method of utilizing clay dephosphorization.
Background technology
Phosphate is one of modern agriculture and the essential element of plant growth.Currently, by various mankind's activities, it is special
It is not industry and agricultural, a large amount of phosphatic waste water is discharged into water body, to cause body eutrophication, reduce water body matter
Amount, therefore the research and development of effective phosphate removal technology are extremely urgent.Common phosphate removal technology includes crystallization, and chemistry is heavy
It forms sediment, physical absorption and biological removal.In the phosphate minimizing technology about crystallization, such as calcium-phosphate crystal improving phosphorus
Hydrochlorate recycles and precipitation, however method for crystallising needs to carry out complicated and accurate control to operating condition.And chemical precipitation is then
It needs to control chemicals cost and avoids that secondary pollution, biological treatment is caused then to need control largely additional sludge yield and sludge
Remove cost.
Absorption method is becoming the most popular method of low concentration solute phosphorus in sewage disposal, mainly utilizes solid absorption
The physical absorption of agent and chemisorption performance remove the phosphorus in waste water.In phosphorus adsorbent, clay as a kind of natural minerals,
Its lower cost for material, process extension is easy and the relatively low feature of operation cost, it is made to have larger potentiality in phosphorus adsorbing domain.
Under conditions of adjusting pH value of waste water, 50% or more is reached to the dephosphorization efficiency of the phosphorus-containing wastewater of middle and high concentration.
Clay is clay mineral that is a kind of of low cost and being easy to get, and crystal structure is by Si-04Tetrahedral layer with
Al-O6Octahedral layer is by common oxonium ion by interlayer than 1：1 layer aluminosilicate constituted, the general formula of chemical composition are
Al4(Si4O10)(OH)8.The high negative electrical charge on clay surface is balanced by alkali metal and alkaline earth cation, these cations can be by
Inorganic hydroxy metal cation is substituted, and increases clay interlamellar spacing with this currently, in existing paper, and only, Huang is happy, and 2017
April in year, University Of Ningbo's journal find clay to Pb2+,Cd2+,Ni2+,Cr3+Plasma has higher removal efficiency, and not
There is document to be related to clay to phosphatic removal.Phosphorus in Domestic Wastewater with Pulverized content is about 8-15mg/L, industrial phosphorus-containing sewage phosphorus content
Higher, up to thousands of mg/L, and it is 1mg/L that the discharge standard of China's phosphorus-containing wastewater, which is 1 grade of discharge 0.5mg/L, 2 grades of discharges,.It can
See, although can quickly be removed to phosphate under certain condition using clay processing phosphorus-containing wastewater, obviously relies on pH value
Exothermic characteristic is shown as with thermodynamics so that the phosphorus adsorbance of clay itself is limited, but smaller (the average grain of clay grain diameter
2-10 μm of diameter), water absorption rate is higher (4.85%), and bulk density is smaller (2.27g/cm3), compensates for certain deficiency of itself.
Invention content
In view of the above-mentioned problems, the present invention provides more efficient, the lower dephosphorization adsorbent of cost, using clay adsorbent
As in addition to adsorption efficiency can be improved, it can more achieve the purpose that waste recycling.
For clay as natural minerals, crystal structure is by Si-04Tetrahedral layer and Al-O6Octahedral layer passes through common
Oxonium ion is by interlayer than 1：The general formula of 1 layer aluminosilicate constituted, chemical composition is Al4(Si4O10)(OH)8, to phosphate
Physical and chemical adsorption is caused, in the case where controlling its temperature and PH, enables phosphate by quick adsorption, reaches within about 75 minutes
It is adsorbed to saturation.
Technical solution provided by the invention is：
A method of using clay dephosphorization, include the following steps：
The selected of step 1) clay, grinding and pretreatment
Clay is passed through into multiple magnetic separation, ball milling and screening, obtains the clay particle of average grain diameter≤0.15mm；
Step 2) pH value is adjusted
According to the difference of clay particle surface properties, the pH value of solution containing phosphate is adjusted to certain between 2-4 using diluted acid
One numerical value, to ensure absorption that clay particle surface zeta current potentials are conducive to it to phosphorus；
Step 3) temperature is adjusted
According to the macroscopic property of clay, its adsorption temp is controlled, to ensure to be conducive to its heat release when clay adsorbs phosphorus
The progress of reaction；
Step 4) phosphorus adsorbs
Clay microparticle, stirring is added to solution containing phosphate.
Wherein, the selected of step 1) clay, grinding and pretreated specific method are：Clay is sieved with 100 mesh sieve first, is added
Water moistens, and moistening clay is placed in oscillator, is shaken 2 hours with the speed of 140r/min, is then filtered, this step two is repeated
It is secondary, to wash away extra impurity, it is subsequently placed into baking oven and is dried 5 hours with 80 DEG C, it is moisture-proof to save backup.
In step 3), control adsorption temp is 15~25 DEG C.
In step 4), clay microparticle is added to solution containing phosphate with the dosage of 2g/L with vigorous stirring, with 120r/
The rotating speed of min persistently stirs 75-120 minutes, that is, reaches the saturation absorption of phosphor in sewage.
The invention also discloses the applications using clay to the removal of phosphate from sewage.
Compared with prior art, the beneficial effects of the invention are as follows：
1, the present invention's is simple for process, at low cost, is easy to commercial Application：The method of the present invention does not include complicated chemical mistake
Journey is without the use of chemicals in addition to a small amount of diluted acid is used for adjusting PH.The method of the present invention compares ring than traditional phosphorus adsorption method
It saves greatly simplified, relevant water processing establishment to be also greatly decreased, dephosphorization cost can be substantially reduced, be convenient for commercial Application.
2, strong applicability, phosphorus adsorption rate are fast：The various Phos and majority that the method for the present invention is suitable for adsorbing in waste water have
Machine phosphorus, and it is close within 60-120 minutes adsorption saturation, saturation phosphorus adsorbance is natural compared to other up to 13.6212mg/g
Mineral all have certain advantage.
3, the method for the present invention belongs to waste recycling using clay particle as phosphorus adsorbent, of low cost and used
Clay particle can be also recycled for multiple times by recycling process, therefore have significant economic benefit and environmental benefit.
Description of the drawings
Fig. 1 is clay of the present invention at 25 DEG C, and initial phosphorus concentration is 50mg/L, in the case that dosage is 2g/L, with 120r/
The rotating speed sustained oscillation of min 75 minutes, removal rate of the clay to phosphate solution in different PH.
Fig. 2 is that the present invention adds 2g/L clay particles in 25 DEG C, the solution containing phosphate that phosphorus content is 50mg/L, with 120r/
Min sustained oscillations 210 minutes, the absorption duration curve of phosphorus.
Fig. 3 is the zeta current potentials of clay particle with the change curve of pH value.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
Step 1, the selected of clay, grinding and pretreatment
Clay is passed through into multiple magnetic separation, ball milling and screening, obtains the clay particle of average grain diameter≤0.15mm, specific method
It is：Clay is sieved with 100 mesh sieve first, water is added to moisten, moistening clay is placed in oscillator, shakes 2 with the speed of 140r/min
Hour, it then filters, repeats this step 2 time, to wash away extra impurity, it is 5 hours dry with 80 DEG C to be subsequently placed into baking oven, moisture-proof
It saves backup.
Step 2, pH value are adjusted
According to the difference of clay particle surface properties, the pH value of solution containing phosphate is adjusted to certain between 2-4 using diluted acid
One numerical value, to ensure absorption that clay particle surface zeta current potentials are conducive to it to phosphorus.
Step 3, temperature are adjusted
According to the macroscopic property of clay, its adsorption temp is controlled, to ensure to be conducive to its heat release when clay adsorbs phosphorus
The progress of reaction.
Step 4, phosphorus absorption
Clay microparticle is added to solution containing phosphate with the dosage of 2g/L with vigorous stirring, is held with the rotating speed of 120r/min
Continuous stirring 75-120 minutes reaches the saturation absorption of phosphor in sewage.
Step 5, phosphorus desorption
Soil sample after above-mentioned experiment absorption, is added saturation NaCL solution centrifuge washing 2 times (4000r/min, 5 minutes), then
KCL solution is added, shakes 24 hours, filtering measures phosphorus content in solution.
The present invention is by scanning electron microscope, specific surface area measuring instrument, the pattern of determination of infrared spectroscopy clay particle,
Specific surface area and surface group detect the zeta current potentials of clay particle using zeta potentiometers.It is using the phosphorus content of preparation
The solution containing phosphate of 50mg/L carries out phosphorus adsorption experiment, and the concentration of phosphorus is then determined by the absorption standard curve of phosphorus.The standard of phosphorus
Curve negotiating molybdenum-antimony anti-spectrophotometric method measures.
Fig. 1 is clay of the present invention at 25 DEG C, and initial phosphorus concentration is 50mg/L, in the case that dosage is 2g/L, with 120r/
The rotating speed sustained oscillation of min 75 minutes, removal rate of the clay to phosphate solution in different PH.
Fig. 2 is that the present invention adds 2g/L clay particles in 25 DEG C, the solution containing phosphate that phosphorus content is 50mg/L, with 120r/
Min sustained oscillations 210 minutes, the absorption duration curve of phosphorus.As seen from the figure, clay particle adsorbs most fast in preceding 20 minutes phosphorus, so
It is gradually slack-off afterwards, about at 75 minutes close to saturation phosphorus absorption, saturated extent of adsorption 13.6212mg/g.
Fig. 3 is the zeta current potentials of clay particle with the change curve of pH value, therefrom it can be found that clay absorption it is front and back zero
Potential point (pH value when i.e. surface zeta potential current potential is zero) is respectively pH=3.59, PH=3.77 after absorption, after absorption before adsorbing
Zero-potential point slightly moves right, and illustrates that this is adsorbed as outer layer absorption, while showing the pH when water body<When 3.59, clay particle tool
There are positive zeta current potentials.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to above real
Apply any simple modification, equivalent replacement and improvement etc. made by example, still fall within technical solution of the present invention protection domain it
It is interior.
Claims (5)
1. a kind of method using clay dephosphorization, it is characterised in that：Include the following steps：
The selected of step 1) clay, grinding and pretreatment
Clay is passed through into multiple magnetic separation, ball milling and screening, obtains the clay particle of average grain diameter≤0.15mm；
Step 2) pH value is adjusted
According to the difference of clay particle surface properties, a certain number that is adjusted to the pH value of solution containing phosphate using diluted acid between 2-4
Value, to ensure absorption that clay particle surface zeta current potentials are conducive to it to phosphorus；
Step 3) temperature is adjusted
According to the macroscopic property of clay, its adsorption temp is controlled, to ensure to be conducive to its exothermic reaction when clay adsorbs phosphorus
Progress；
Step 4) phosphorus adsorbs
Clay microparticle, stirring is added to solution containing phosphate.
2. the method according to claim 1 using clay dephosphorization, it is characterised in that：Selected, the grinding of step 1) clay
And pretreated specific method is：Clay is sieved with 100 mesh sieve first, water is added to moisten, moistening clay is placed in oscillator, with
The speed of 140r/min is shaken 2 hours, is then filtered, and is repeated this step twice, to wash away extra impurity, is subsequently placed into baking oven
It is 5 hours dry with 80 DEG C, it is moisture-proof to save backup.
3. the method according to claim 1 using clay dephosphorization, it is characterised in that：In step 3), adsorption temp is controlled
It is 15~25 DEG C.
4. the method according to claim 1 using clay dephosphorization, it is characterised in that：In step 4), with vigorous stirring
Clay microparticle is added to solution containing phosphate with the dosage of 2g/L, persistently stirs 75-120 minutes with the rotating speed of 120r/min, i.e.,
Reach the saturation absorption of phosphor in sewage.
5. the application using clay to the removal of phosphate from sewage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810419673.9A CN108579670B (en) | 2018-05-04 | 2018-05-04 | Method for removing phosphorus by using argil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810419673.9A CN108579670B (en) | 2018-05-04 | 2018-05-04 | Method for removing phosphorus by using argil |
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| CN108579670A true CN108579670A (en) | 2018-09-28 |
| CN108579670B CN108579670B (en) | 2021-03-30 |
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| CN201810419673.9A Active CN108579670B (en) | 2018-05-04 | 2018-05-04 | Method for removing phosphorus by using argil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204354A (en) * | 2019-06-18 | 2019-09-06 | 陈方鑫 | A kind of preparation of quick dephosphorization ceramic particle sorbent material |
| CN110575812A (en) * | 2019-09-25 | 2019-12-17 | 西南石油大学 | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
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| JPS62180750A (en) * | 1986-01-31 | 1987-08-08 | Sintokogio Ltd | Production of granular soil for adsorbing phosphorus compound |
| CN102190343A (en) * | 2010-03-03 | 2011-09-21 | 南京信息工程大学 | Method for adsorbing phosphate in sewage by using eggshells |
| CN106315740A (en) * | 2016-10-14 | 2017-01-11 | 安徽理工大学 | Method for phosphorous removal by utilizing high-iron fly ash |
| CN106345401A (en) * | 2016-11-03 | 2017-01-25 | 江苏开放大学 | Phosphorus adsorption material for livestock wastewater and preparation method and application thereof |
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2018
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Patent Citations (4)
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| JPS62180750A (en) * | 1986-01-31 | 1987-08-08 | Sintokogio Ltd | Production of granular soil for adsorbing phosphorus compound |
| CN102190343A (en) * | 2010-03-03 | 2011-09-21 | 南京信息工程大学 | Method for adsorbing phosphate in sewage by using eggshells |
| CN106315740A (en) * | 2016-10-14 | 2017-01-11 | 安徽理工大学 | Method for phosphorous removal by utilizing high-iron fly ash |
| CN106345401A (en) * | 2016-11-03 | 2017-01-25 | 江苏开放大学 | Phosphorus adsorption material for livestock wastewater and preparation method and application thereof |
Non-Patent Citations (4)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204354A (en) * | 2019-06-18 | 2019-09-06 | 陈方鑫 | A kind of preparation of quick dephosphorization ceramic particle sorbent material |
| CN110575812A (en) * | 2019-09-25 | 2019-12-17 | 西南石油大学 | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
| CN110575812B (en) * | 2019-09-25 | 2022-03-22 | 西南石油大学 | Environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof |
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| CN108579670B (en) | 2021-03-30 |
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