CN108579670B - Method for removing phosphorus by using argil - Google Patents
Method for removing phosphorus by using argil Download PDFInfo
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- CN108579670B CN108579670B CN201810419673.9A CN201810419673A CN108579670B CN 108579670 B CN108579670 B CN 108579670B CN 201810419673 A CN201810419673 A CN 201810419673A CN 108579670 B CN108579670 B CN 108579670B
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- Environmental & Geological Engineering (AREA)
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- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method for removing phosphorus by using argil, which has the advantages of large quantity, low price, environmental protection and easy circulation when the argil is used as a natural mineral. The main component of the pottery clay is silicon dioxide, natural pottery clay is screened and adsorbed, and the concentration of residual phosphate is measured, so that the adsorption capacity of the pottery clay has certain advantages compared with other natural minerals, and the defects of low efficiency and high cost of the original phosphorus removal adsorbent are overcome. The argil is used as the adsorbent, so that the adsorption efficiency can be improved, and the aim of treating wastes with processes of wastes against one another can be fulfilled.
Description
Technical Field
The invention relates to the field of phosphorus removal adsorption, in particular to a method for removing phosphorus by using argil.
Background
Phosphate is one of the essential elements for modern agriculture and plant growth. At present, a large amount of phosphate-containing wastewater is discharged into a water body through various human activities, particularly industry and agriculture, thereby causing eutrophication of the water body and reducing the quality of the water body, and thus research and development of an effective phosphate removal technology is urgently needed. Common phosphate removal techniques include crystallization, chemical precipitation, physical adsorption and biological removal. In phosphate removal processes involving crystallization, such as calcium-phosphate crystals are used to improve phosphate recycling and precipitation, however, the crystallization process requires complex and delicate control of the operating conditions. Chemical precipitation requires control of chemical costs and avoidance of secondary pollution, while biological treatment requires control of substantial additional sludge production and sludge removal costs.
The adsorption method is becoming the most common method for removing low-concentration solute phosphorus in sewage treatment, and mainly utilizes the physical adsorption and chemical adsorption performance of a solid adsorbent to remove phosphorus in wastewater. In the phosphorus adsorbent, argil is used as a natural mineral, and has the characteristics of low material cost, easy process expansion and low operation cost, so that the argil has great potential in the field of phosphorus adsorption. Under the condition of adjusting the pH value of the wastewater, the phosphorus removal efficiency of the wastewater containing phosphorus with medium and high concentration reaches more than 50 percent.
The argil is a low-cost and easily available clay mineral with a crystal structure of Si-04Tetrahedral layer and Al-O6The octahedral layers are separated by a common oxygen ion in an interlayer ratio of 1: 1, the chemical composition of the layered aluminosilicate is Al4(Si4O10)(OH)8. At present, the existing papers only have yellow and pleasant, 4 months in 2017 and the university report of Ningbo that the pottery clay is discovered to have Pb-free2+,Cd2+,Ni2+,Cr3+The plasma has a high removal efficiency and there is no literature on phosphate removal by china clay. The phosphorus content in domestic sewage is about 8-15mg/L, the phosphorus content in industrial phosphorus-containing sewage is higher and can reach thousands of mg/L, and the discharge standard of phosphorus-containing wastewater in China is 0.5mg/L for grade 1 discharge and 1mg/L for grade 2 discharge. Therefore, although the argil is used for treating the phosphorus-containing sewage to quickly remove phosphate under certain conditions, the argil is obviously dependent on pH value and thermodynamic property to show heat release, so that the phosphorus adsorption capacity of the argil is limited, the argil has small particle size (the average particle size is 2-10 mu m), high water absorption (4.85%), and small volume density (2.27g/cm3), and certain defects of the argil are made up.
Disclosure of Invention
Aiming at the problems, the invention provides the phosphorus removal adsorbent with higher efficiency and lower cost, and the purpose of treating wastes with processes of wastes against one another can be achieved by adopting the ceramic adsorbent to improve the adsorption efficiency.
Argil as natural mineral with crystal structure of Si-04Tetrahedral layer and Al-O6The octahedral layers are separated by a common oxygen ion in an interlayer ratio of 1: 1, the chemical composition of the layered aluminosilicate is Al4(Si4O10)(OH)8Physically and chemically adsorbing phosphate, and controlling its temperature and pH to make phosphate be quickly absorbedFast adsorption, about 75 minutes to reach saturation adsorption.
The technical scheme provided by the invention is as follows:
a method for removing phosphorus by using argil comprises the following steps:
step 1) clay concentration, grinding and pretreatment
Carrying out magnetic separation, ball milling and screening on argil for multiple times to obtain argil particles with the average particle size of less than or equal to 0.15 mm;
step 2) pH adjustment
According to different surface properties of the argil particles, the pH value of the phosphorus-containing solution is adjusted to a certain value between 2 and 4 by using dilute acid so as to ensure that the zeta potential on the surface of the argil particles is favorable for adsorbing phosphorus;
step 3) temperature regulation
According to the thermodynamic property of the argil, the adsorption temperature is controlled to ensure that the argil is favorable for carrying out an exothermic reaction when adsorbing phosphorus;
step 4) phosphorus adsorption
Adding clay microparticles into the phosphorus-containing solution, and stirring.
Wherein, the concrete method for the selection, grinding and pretreatment of the argil in the step 1) comprises the following steps: firstly, sieving argil with a 100-mesh sieve, adding water for wetting, placing the wetted argil in an oscillator, oscillating for 2 hours at the speed of 140r/min, then carrying out suction filtration, repeating the steps twice to wash off redundant impurities, then placing the argil in an oven to dry for 5 hours at the temperature of 80 ℃, and storing the argil in a moisture-proof manner for later use.
In the step 3), the adsorption temperature is controlled to be 15-25 ℃.
In the step 4), adding argil microparticles into the phosphorus-containing solution in an adding amount of 2g/L under vigorous stirring, and continuously stirring at a rotating speed of 120r/min for 75-120 minutes to achieve saturated adsorption of phosphorus in the sewage.
The invention also discloses application of argil in removing phosphate in sewage.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention has simple process and low cost, and is easy for industrial application: the method of the present invention does not involve complicated chemical processes and does not require the use of chemicals except a small amount of dilute acid to adjust the pH. Compared with the traditional phosphorus adsorption method, the method of the invention has the advantages of greatly simplified links, greatly reduced related water treatment facilities, greatly reduced phosphorus removal cost and convenient industrial application.
2. The applicability is strong, the phosphorus adsorption speed is fast: the method is suitable for adsorbing various inorganic phosphorus and most organic phosphorus in the wastewater, the adsorption saturation can be approached within 60-120 minutes, the adsorption capacity of the saturated phosphorus can reach 13.6212mg/g, and the method has certain advantages compared with other natural minerals.
3. The method of the invention utilizes argil particles as a phosphorus adsorbent, belongs to the field of waste treatment by waste, has low cost, and can recycle the used argil particles for many times through the recycling process, thereby having remarkable economic benefit and environmental benefit.
Drawings
FIG. 1 shows the removal rate of phosphate solution by kaolin at different pH values, with the initial phosphorus concentration of 50mg/L and the addition of 2g/L, continuously shaking at 120r/min for 75 minutes.
FIG. 2 is a graph showing the duration of phosphorus adsorption by adding 2g/L of clay particles to a phosphorus-containing solution having a phosphorus content of 50mg/L at 25 ℃ and shaking the mixture at 120r/min for 210 minutes.
FIG. 3 is a graph of zeta potential of clay particles as a function of pH.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Step 1, selecting, grinding and pretreating argil
Carrying out magnetic separation, ball milling and screening on argil for multiple times to obtain argil particles with the average particle size of less than or equal to 0.15mm, wherein the specific method comprises the following steps: firstly, sieving argil with a 100-mesh sieve, adding water for wetting, placing the wetted argil in an oscillator, oscillating for 2 hours at the speed of 140r/min, then carrying out suction filtration, repeating the step for 2 times to wash off redundant impurities, then placing the argil in an oven to dry for 5 hours at the temperature of 80 ℃, and storing the argil in a moisture-proof manner for later use.
According to different surface properties of the argil particles, the pH value of the phosphorus-containing solution is adjusted to a certain value between 2 and 4 by using dilute acid so as to ensure that the zeta potential on the surface of the argil particles is favorable for adsorbing phosphorus.
Step 3, temperature regulation
According to the thermodynamic property of the argil, the adsorption temperature is controlled to ensure that the argil is favorable for the exothermic reaction when the argil adsorbs phosphorus.
Adding argil microparticles into the phosphorus-containing solution with 2g/L of dosage under vigorous stirring, and continuously stirring for 75-120 minutes at the rotating speed of 120r/min to achieve the saturated adsorption of phosphorus in the sewage.
Step 5, desorption of phosphorus
And adding a saturated NaCL solution into the soil sample adsorbed by the experiment, centrifugally washing for 2 times (4000r/min for 5 minutes), adding a KCL solution, shaking for 24 hours, filtering, and determining the content of phosphorus in the solution.
The appearance, the specific surface area and the surface groups of the pottery clay particles are measured by a scanning electron microscope, a specific surface area determinator and an infrared spectrometer, and the zeta potential of the pottery clay particles is detected by a zeta potential meter. The phosphorus adsorption experiment is carried out by using the prepared phosphorus-containing solution with the phosphorus content of 50mg/L, and then the concentration of phosphorus is determined by the phosphorus absorption standard curve. The standard curve for phosphorus was determined by molybdenum-antimony anti-spectrophotometry.
FIG. 1 shows the removal rate of phosphate solution by kaolin at different pH values, with the initial phosphorus concentration of 50mg/L and the addition of 2g/L, continuously shaking at 120r/min for 75 minutes.
FIG. 2 is a graph showing the duration of phosphorus adsorption by adding 2g/L of clay particles to a phosphorus-containing solution having a phosphorus content of 50mg/L at 25 ℃ and shaking the mixture at 120r/min for 210 minutes. As can be seen from the figure, the phosphorus adsorption of the kaolin particles was the fastest in the first 20 minutes and then gradually slowed down, and the adsorption was close to the saturated phosphorus adsorption at about 75 minutes, and the saturated adsorption amount was 13.6212 mg/g.
Fig. 3 is a graph showing the zeta potential of the kaolin particles according to the pH value, from which it can be found that the zero potential points before and after adsorption of the kaolin (i.e. the pH value at which the surface zeta potential is zero) are respectively pH 3.59 before adsorption, pH 3.77 after adsorption, and the zero potential point after adsorption moves slightly to the right, indicating that the adsorption is outer layer adsorption, and simultaneously showing that the kaolin particles have positive zeta potential when the pH of the water body is less than 3.59.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (1)
1. A method for removing phosphorus by using argil is characterized by comprising the following steps: the method comprises the following steps:
step 1) clay concentration, grinding and pretreatment
Carrying out magnetic separation, ball milling and screening on argil for multiple times to obtain argil particles with the average particle size of less than or equal to 0.15 mm;
step 2) pH adjustment
According to different surface properties of the argil particles, the pH value of the phosphorus-containing solution is adjusted to a certain value between 2 and 4 by using dilute acid so as to ensure that the zeta potential on the surface of the argil particles is favorable for adsorbing phosphorus;
step 3) temperature regulation
According to the thermodynamic property of the argil, the adsorption temperature is controlled to ensure that the argil is favorable for carrying out an exothermic reaction when adsorbing phosphorus;
step 4) phosphorus adsorption
Adding clay microparticles into the phosphorus-containing solution, and stirring;
the concrete method for the selection, grinding and pretreatment of the argil in the step 1) comprises the following steps: firstly, sieving argil with a 100-mesh sieve, adding water for wetting, placing the wetted argil in an oscillator, oscillating for 2 hours at the speed of 140r/min, then carrying out suction filtration, repeating the steps twice to wash off redundant impurities, then placing the argil in an oven to dry for 5 hours at the temperature of 80 ℃, and carrying out damp-proof preservation for later use;
in the step 3), the adsorption temperature is controlled to be 15-25 ℃;
in the step 4), adding argil microparticles into the phosphorus-containing solution in an adding amount of 2g/L under vigorous stirring, and continuously stirring at a rotating speed of 120r/min for 75-120 minutes to achieve saturated adsorption of phosphorus in the sewage.
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| CN110204354A (en) * | 2019-06-18 | 2019-09-06 | 陈方鑫 | A kind of preparation of quick dephosphorization ceramic particle sorbent material |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
- 2018-05-04 CN CN201810419673.9A patent/CN108579670B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Title |
|---|
| 人工湿地除磷基质筛选及其吸附机理研究;赵桂瑜;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20070615(第06期);正文第2.2节，第3.1.2.1节，第3.1.2.3节，表3.1，第3.2.2.1节（1），第3.2.2.3节 * |
| 改性陶土颗粒吸附砷的实验研究;赵莹等;《水资源保护》;20120330;第28卷(第2期);第72-76页 * |
| 陶土－粉煤灰基吸附性陶瓷基体的制备及其吸附性能;徐姗姗等;《北京化工大学学报( 自然科学版)》;20120720;第39卷(第4期);第42-46页 * |
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