CN111632577A - Ammonium oxalate modified phosphate tailing adsorbing material, preparation method and application - Google Patents
Ammonium oxalate modified phosphate tailing adsorbing material, preparation method and application Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an ammonium oxalate modified phosphate tailing adsorbing material for repairing heavy metal polluted water and soil, a preparation method and application thereof. The preparation method of the material comprises the following steps: mixing the pretreated phosphorus tailings with an ammonium oxalate solution, reacting the mixture at 25-35 ℃ for 4-8 days, drying at 90-100 ℃ for 6-48 hours until the mixture is completely dried, cooling to room temperature, and grinding to obtain the phosphorus tailings. The preparation method of the material has the advantages of simple process, simple required equipment and low preparation cost. The ammonium oxalate modified phosphate tailings not only can adsorb heavy metal ions such as lead, copper, cadmium, zinc, nickel and the like in a solution to treat water pollution, but also can passivate heavy metals such as lead, cadmium and the like in heavy metal polluted soil, reduce the effectiveness of the heavy metals, improve the physical and chemical properties of the soil, and have wide application prospects.
Description
Technical Field
The invention belongs to the technical field of heavy metal pollution treatment and restoration, and particularly relates to an ammonium oxalate modified phosphate tailing adsorbing material for restoring heavy metal polluted water and soil, a preparation method and application thereof.
Background
With the rapid development of industrialization and urbanization, human activities such as industrial wastewater, waste residues and exhaust emission, metal mining and smelting, pesticide and pesticide use and the like cause a large amount of heavy metals to enter water and soil, resulting in heavy metal pollution. Heavy metal pollution has high toxicity, durability and nondegradable property, and can pose serious threats to the ecological environment and human health. At present, the common methods for repairing the heavy metal polluted water body and the soil comprise a chemical adsorption method and a chemical passivation method, and the physical and chemical properties of the water body or the soil are mainly adjusted by applying a repairing material, so that the occurrence form of the heavy metal is changed, and the heavy metal is subjected to a series of reactions such as ion exchange, adsorption, precipitation, oxidation reduction and the like to be converted to a more stable form, thereby reducing the migration and bioavailability of the heavy metal and finally achieving the purpose of reducing the heavy metal pollution risk. The key factor for improving the heavy metal pollution remediation effect is the use of efficient remediation materials.
The phosphate tailings are natural minerals, contain a large amount of elements such as phosphorus, calcium, magnesium and the like, are partially modified in a phosphating process flow, have the characteristics of large specific surface area, rich pores and the like, are typical phosphorus-containing mineral materials, and are suitable for being used as heavy metal pollution repair materials. China phosphorite is rich in resources, a large amount of phosphorus tailings are generated along with phosphorite mining every year, a large amount of elements such as phosphorus and the like are remained in the phosphorus tailings, phosphorus exists in a stable form, meanwhile, the mineral structure of the phosphorus tailings is stable, surface functional groups are few, and the direct use of the phosphorus tailings as a repair material can hardly achieve a good pollution repair effect. In order to better utilize the phosphorus tailings, the modification of the phosphorus tailings by using a chemical modification method, a thermal modification method, an organic modification method and the like to improve the heavy metal adsorption performance of the phosphorus tailings has been studied. Compared with the organic acid modification in the existing research, the ammonium oxalate modification method can activate phosphorus in the phosphate tailings, load oxygen-containing functional groups on the surface of the phosphate tailings, further promote the activation and release of phosphorus, optimize the pore structure of the phosphate tailings, enhance the adsorption and precipitation capacity of the phosphate tailings on heavy metals, and simultaneously, the ammonium oxalate modification can not significantly reduce the pH value of the material, so that the ammonium oxalate modified phosphate tailings serving as a modifier has good application prospects. There are currently few studies on this aspect and some problems still remain. For example, the invention patent of the patent publication No. CN 102559198A discloses oxalic acid activated phosphate rock powder for treating soil polluted by heavy metals of copper, lead and cadmium, and after the powder is applied to the soil, the effects of passivating the heavy metals and increasing the soil fertility can be achieved under a lower application amount, but the repair mechanism is single, and the repair efficiency is not enough to meet the treatment requirement of higher concentration. The document "activation of powdered rock phosphate by organic acid and removal of copper in solution" shows that the pH value of powdered rock phosphate is reduced by oxalic acid modification, and the lower the pH value of the powdered rock phosphate modified by oxalic acid is, the lower the adsorption amount of copper is, so that the excessively low pH value after oxalic acid modification may affect the adsorption performance of apatite on heavy metals.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and an application approach of an ammonium oxalate modified phosphate tailing adsorbing material for repairing heavy metal polluted water and soil.
The preparation method of the ammonium oxalate modified phosphate tailing adsorbing material provided by the invention comprises the following steps:
(1) phosphorus tailings pretreatment
Collecting phosphorus tailings obtained after the phosphorus ore flotation process, air-drying, grinding and crushing by using a ball mill, sieving by using a 50-100-mesh nylon sieve, and taking first undersize to obtain phosphorus tailings powder;
(2) preparation of ammonium oxalate modified phosphate tailing adsorbing material
And (2) mixing the phosphate tailing powder obtained in the step (1) with an ammonium oxalate solution, standing in a constant-temperature incubator for constant-temperature reaction, drying at 90-100 ℃, cooling to room temperature, grinding through a 50-100-mesh nylon sieve, and taking the first undersize to obtain the ammonium oxalate modified phosphate tailing adsorbing material.
In the step (1), the content of the phosphate tailings P2O5 is in the range of 10-30%, and the preferred content is 18%.
In the step (2), the concentration of ammonium oxalate is in the range of 0.1-1 mol.L-1, preferably 0.5 mol.L-1.
In the step (2), the solid-to-liquid ratio of the phosphate tailings to the ammonium oxalate solution is 1g:5mL-20mL, preferably 1g:10 mL.
In the step (2), the mixture of the phosphorus tailings and the ammonium oxalate solution is kept still in a constant temperature incubator, the temperature required by the constant temperature reaction is 25-35 ℃, the reaction time is 6-8 days, and the reaction is preferably carried out for 6 days at 28 ℃.
The ammonium oxalate modified phosphate tailing adsorbing material provided by the invention is prepared by the method. The material has the following applications: the method is used for repairing heavy metal polluted water or soil, and is characterized in that the polluted water is single lead, copper, cadmium, zinc and nickel polluted water or water polluted by multiple heavy metals such as lead, copper, zinc, nickel and the like in a composite mode, and the polluted soil is single cadmium polluted soil or lead and cadmium polluted soil in a composite mode.
The application of the ammonium oxalate modified phosphate tailing adsorbing material provided by the invention has the beneficial effects that:
1. the modified phosphate tailing material is prepared by taking industrial waste phosphate rock tailings as a raw material and utilizing the combined action of oxalate and ammonium provided by ammonium oxalate, the preparation method is simple, the equipment is simple, the preparation cost is low, the pH value of the material is not obviously reduced by ammonium oxalate modification, and the resource utilization of the waste is realized.
2. The oxalic acid modified phosphate tailing material provided by the invention can efficiently adsorb and remove heavy metals in a solution, not only can adsorb lead, copper, cadmium, zinc, nickel and the like which exist in the solution singly, but also has a good adsorption effect on lead, copper, zinc, nickel and the like which exist in the solution compositely.
3. The ammonium oxalate modified phosphate tailing adsorbing material provided by the invention can obviously reduce the content of effective states such as heavy metal lead, cadmium and the like in the composite heavy metal polluted soil, improves the physical and chemical properties of the soil, has short treatment time, stable passivation effect and wide application range, and is an efficient and environment-friendly heavy metal polluted soil repairing material.
Drawings
FIG. 1 is a scanning electron microscope atlas of phosphate tailings before and after modification by ammonium oxalate;
FIG. 2 shows the adsorption capacity of the ammonium oxalate modified phosphate tailing adsorbing material for lead, copper, cadmium, zinc and nickel which exist singly;
FIG. 3 shows the adsorption amount of the ammonium oxalate modified phosphate tailing adsorbing material on lead, copper, zinc and nickel which are present in a composite manner;
FIG. 4 shows the effect of ammonium oxalate modified phosphate tailing adsorbing material on the passivation of cadmium in soil polluted by neutral cadmium;
FIG. 5 shows the passivation effect of ammonium oxalate modified phosphate tailing adsorbing material on lead in acid lead-cadmium combined polluted soil;
FIG. 6 shows the passivation effect of ammonium oxalate modified phosphate tailing adsorbing material on cadmium in acidic lead-cadmium combined polluted soil;
FIG. 7 is a graph showing the effect of ammonium oxalate modified phosphate tailing adsorption material on the available phosphorus content of soil contaminated by neutral cadmium;
FIG. 8 shows the influence of ammonium oxalate modified phosphate tailing adsorbing materials on the content of available phosphorus in the acid lead-cadmium combined polluted soil.
Detailed Description
The ammonium oxalate modified phosphate rock tailings and the preparation method and application thereof proposed by the present invention are specifically described below, but the present invention is not limited thereto.
Example 1 preparation of ammonium oxalate modified phosphate tailing adsorbent Material
And collecting the phosphate tailings to prepare the ammonium oxalate modified phosphate tailing adsorbing material. The specific operation is as follows:
(1) phosphorus tailings pretreatment
Collecting flotation process phosphate tailings obtained after phosphate rock mining, grinding and crushing by using a ball mill after air drying, sieving by using a 100-mesh nylon sieve, and taking first undersize to obtain phosphate tailing powder (F).
(2) Preparation of ammonium oxalate modified phosphate tailing adsorbing material
And (2) placing 25.00 g of the phosphate tailing powder obtained in the step (1) into a 500 mL plastic wide-mouth bottle, adding 250 mL of ammonium oxalate solution with the concentration of 0.5 mol.L < -1 > according to the solid-to-liquid ratio (W: V) of 1:10, turning and uniformly mixing, standing in a constant-temperature incubator for constant-temperature reaction at 28 ℃ for 6 days, taking out, drying at 95 ℃ for 24 hours until the material is dried, grinding through a 100-mesh nylon sieve, and taking out the first sieve underflow to obtain the ammonium oxalate modified phosphate tailing adsorbing material (CF).
The surface morphology change of the phosphate tailing material before and after modification is observed through a scanning electron microscope atlas, and the result is shown in figure 1. As shown in FIG. 1, the phosphate tailing powder contains a large amount of blocky crystals on the surface, and has a compact structure and a rough surface. After the ammonium oxalate is modified, the blocky crystal structure on the surface of the ammonium oxalate modified phosphate tailing adsorbing material is changed, the surface is smoother, and loose flaky crystal structures are distributed, so that the ammonium oxalate changes the mineral structure of the phosphate tailing, and the material properties are obviously changed.
The pH, the effective phosphorus content and the cation exchange capacity of the phosphate tailings before and after the ammonium oxalate modification are shown in table 1, the effective phosphorus content and the cation exchange capacity of the ammonium oxalate modified phosphate tailing adsorbing material after the modification are obviously increased, and the effective phosphorus content is increased by about 10 times compared with that before the modification, which indicates that the phosphorus in the phosphate tailings is effectively activated and released. And meanwhile, the pH values of the materials before and after modification are basically consistent, which shows that the pH value of the phosphate tailing material is not obviously reduced by ammonium oxalate modification.
TABLE 1 pH, available phosphorus content and cation exchange Capacity of phosphate tailings before and after ammonium oxalate modification
| Material | F | CF |
| pH | 7.63±0.03 | 7.65±0.01 |
| Effective phosphorus content (g.kg)-1） | 0.12±0.01 | 1.05±0.01 |
| Cation exchange Capacity (cmol. L)-1） | 2.20±0.12 | 4.61±0.28 |
Example 2 adsorption Effect of ammonium oxalate modified phosphate tailing adsorbing Material on singly existing lead, copper, cadmium, Zinc and Nickel
Using 0.01 mol.L < -1 > sodium nitrate solution as a solvent to respectively prepare single heavy metal solutions with lead ion, copper ion, zinc ion and nickel ion concentration of 1000 mg.L < -1 > and cadmium ion concentration of 500 mg.L < -1 >, and adjusting the pH =5 of the solutions. The ammonium oxalate modified phosphate tailing adsorbing material prepared in the example 1 is accurately weighed and placed in a 15 mL centrifuge tube, a certain volume of single heavy metal solution of lead, copper, cadmium, zinc and nickel is respectively added according to the solid-to-liquid ratio of 1:500, and the centrifuge tube is placed at the temperature of 25 ℃ and under the condition of 180 r.min < -1 > and is oscillated for 48 hours.
As shown in FIG. 2, the adsorption amounts of the ammonium oxalate modified phosphate tailing adsorbing material to lead ions, copper ions, cadmium ions, zinc ions and nickel ions in a single heavy metal solution are 274 mg g < -1 >, 229 mg g < -1 >, 120mg g < -1 >, 177mg g < -1 > and 120mg g < -1 >, respectively, which shows that the obtained ammonium oxalate modified phosphate tailing adsorbing material has good adsorption capacity to lead ions, copper ions, cadmium ions, zinc ions and nickel ions.
Example 3 adsorption Effect of ammonium oxalate modified phosphate tailing adsorbing Material on Complex contaminated lead, copper, Zinc and Nickel
And (3) preparing a composite heavy metal solution with the concentration of lead ions, copper ions, zinc ions and nickel ions of 1000 mg.L < -1 > by using 0.01 mol.L < -1 > of sodium nitrate solution as a solvent, and adjusting the pH =5 of the solution. The ammonium oxalate modified phosphate tailing adsorbing material prepared in the example 1 is accurately weighed and placed in a 15 mL centrifuge tube, a certain volume of composite heavy metal solution is added according to the solid-to-liquid ratio of 1:500, and the centrifuge tube is placed at the temperature of 25 ℃ and under the condition of 180 r.min < -1 > and is oscillated for 48 hours.
As shown in FIG. 3, the adsorption amounts of the ammonium oxalate modified phosphate tailing adsorbing material to lead ions, copper ions, zinc ions and nickel ions in the composite heavy metal solution are 89 mg g < -1 >, 86 mg g < -1 >, 27 mg g < -1 > and 28 mg g < -1 >, respectively, which indicates that the obtained ammonium oxalate modified phosphate tailing adsorbing material can simultaneously adsorb lead ions, copper ions, zinc ions, nickel ions and the like in the heavy metal composite solution.
Example 4 passivation effect of ammonium oxalate modified phosphate tailing adsorbing material on cadmium in soil polluted by neutral cadmium
The embodiment is a passivation effect of ammonium oxalate modified phosphate tailing adsorbing material on cadmium in neutral cadmium-polluted soil (soil A), and the passivation effect of cadmium after the ammonium oxalate modified phosphate tailing adsorbing material prepared in the embodiment 1 is added into the neutral cadmium-polluted soil and cultured for 20 days comprises the following steps:
the soil A to be tested is collected from surface soil (0-20 cm) of a certain farmland, the soil is naturally air-dried and then screened by a 2 mm sieve for later use, and the cadmium content in the soil A to be tested exceeds a risk screening value by referring to 'soil environmental quality agricultural land soil pollution risk management and control Standard (trial)' (GB 15618-.
The ammonium oxalate-modified phosphate tailing adsorbing material prepared in example 1 was added to the soil a to be tested by a soil culture experiment. 30 g of test soil A is placed in a centrifugal tube, the ammonium oxalate modified phosphate tailing adsorbing material prepared in the example 1 is added into the test soil A according to the mass ratio of 1% to 5%, and after uniform mixing, ultrapure water is added to keep the water content at 100% of the field water holding capacity.
mm acetic acid buffer solution method ( leaching toxicity leaching method samples after 20 days of culture, naturally air-dries soil samples, grinds 2 sieves, adopts "solid waste HJ/T300-2007), and the cadmium available state content in the soil A is analyzed and determined.
The harm of heavy metal in soil to the environment is related to the content of effective heavy metal, and the reduction of the content of the effective heavy metal shows that the bioavailability and the mobility of the heavy metal are weakened, so that the method is a key investigation index for passivation and restoration of heavy metal pollution in soil.
The passivation effect of the ammonium oxalate modified phosphate tailing adsorbing material on cadmium in the soil polluted by the neutral cadmium is shown in figure 4. The result shows that after 1% and 5% of ammonium oxalate modified phosphate tailing adsorbing materials are added into the neutral cadmium polluted soil, the cadmium effective state content in the neutral cadmium polluted soil treated by the ammonium oxalate modified phosphate tailing adsorbing materials is obviously reduced, the soil cadmium effective state content is respectively reduced by 18% and 36%, and the ammonium oxalate modified phosphate tailing adsorbing materials can effectively passivate cadmium in the neutral cadmium polluted soil.
Example 5 passivation effect of ammonium oxalate modified phosphate tailing adsorbing material on lead and cadmium in acidic lead-cadmium combined polluted soil
The embodiment is the passivation effect of the ammonium oxalate modified phosphate tailing adsorbing material on lead and cadmium in acidic lead-cadmium composite polluted soil (soil B), the soil B to be tested is collected from surface soil (0-20 cm) of a certain farmland, the soil is naturally dried and then screened for later use after being dried, and the content of lead and cadmium in the soil B to be tested exceeds a risk control value by referring to soil pollution risk control standard (trial) for soil environmental quality agricultural land (GB 15618-.
The soil culture experiment and the method for analyzing and measuring the content of the effective states of lead and cadmium in the soil are the same as the example 4.
The passivation effects of the ammonium oxalate modified phosphate tailing adsorbing material on lead and cadmium in the acid lead-cadmium combined polluted soil are shown in fig. 5 and fig. 6 respectively. The result shows that after 1% and 5% of ammonium oxalate modified phosphate tailing adsorbing materials are added into the acid lead-cadmium composite polluted soil, the effective lead content and the effective cadmium content in the acid lead-cadmium composite polluted soil treated by the ammonium oxalate modified phosphate tailing adsorbing materials are remarkably reduced, the effective lead content in the soil is respectively reduced by 43% -63%, the effective cadmium content in the soil is respectively reduced by 13% -45%, and the ammonium oxalate modified phosphate tailing adsorbing materials can effectively passivate lead and cadmium in the acid lead-cadmium composite polluted soil.
Example 6 influence of ammonium oxalate modified phosphate tailing adsorbing Material on the content of available phosphorus in heavy Metal contaminated soil
In this example, the content of available phosphorus in soil is influenced by the ammonium oxalate modified phosphate tailing adsorbing material after 20 days of action on neutral cadmium contaminated soil (soil a) and acidic lead-cadmium contaminated soil (soil B), the content of available phosphorus is increased, and heavy metals are precipitated in the soil, and the content of available phosphorus in the soil is analyzed and determined by using a sodium bicarbonate leaching-inductively coupled plasma emission spectrometer assay method by using soil samples collected after 20 days of soil culture in examples 4 and 5.
The effect of the ammonium oxalate modified phosphate tailing adsorbing material on the content of available phosphorus in the soil a and the soil B after 20 days of culture is shown in fig. 7 and 8. The results show that after 1% and 5% of ammonium oxalate modified phosphate tailing adsorbing materials are added into soil A and soil B, the content of available phosphorus in neutral and acid heavy metal polluted soil treated by the ammonium oxalate modified phosphate tailing adsorbing materials is obviously increased, the content of available phosphorus in neutral cadmium polluted soil is increased by 56% -105%, and the content of available phosphorus in acid lead cadmium polluted soil is increased by 3% -65%.
Claims (9)
1. A preparation method of an ammonium oxalate modified phosphate tailing adsorbing material is characterized by comprising the following steps:
(1) pretreatment of phosphate tailings: collecting phosphorus tailings obtained by the phosphorus ore dressing process, air-drying, grinding and crushing by using a ball mill, sieving by using a 50-100 mesh nylon sieve, and taking first undersize to obtain phosphorus tailings powder;
(2) preparation of ammonium oxalate modified phosphate tailing adsorbing material: and (2) mixing the phosphate tailing powder obtained in the step (1) with an ammonium oxalate solution, standing in a constant-temperature incubator for constant-temperature reaction, drying at 90-100 ℃, cooling to room temperature, grinding through a 50-100-mesh nylon sieve, and taking the first undersize to obtain the ammonium oxalate modified phosphate tailing adsorbing material.
2. The method for preparing the ammonium oxalate modified phosphate tailing adsorbing material as claimed in claim 1, is characterized in that: the phosphorus tailings P in the step (1)2O5The content of (B) is 10-30%, preferably 18%.
3. The method for preparing the ammonium oxalate modified phosphate tailing adsorbing material as claimed in claim 1, is characterized in that: the concentration of the ammonium oxalate solution in the step (2) is 0.1-1 mol.L-1Preferably 0.5 mol. L-1。
4. The method for preparing the ammonium oxalate modified phosphate tailing adsorbing material as claimed in claim 1, is characterized in that: the solid-to-liquid ratio of the phosphorus tailings powder to the ammonium oxalate solution in the step (2) is 1g:5mL-20mL, and preferably 1g:10 mL.
5. The method for preparing the ammonium oxalate modified phosphate tailing adsorbing material as claimed in claim 1, is characterized in that: and (3) standing in the step (2), wherein the temperature required by the constant-temperature reaction in the constant-temperature incubator is 25-35 ℃, the reaction time is 6-8 days, and the reaction is preferably carried out for 6 days at 28 ℃.
6. The ammonium oxalate modified phosphate tailing adsorbing material prepared by the preparation method of any one of claims 1 to 5.
7. The use of the ammonium oxalate modified phosphate tailing adsorbing material as defined in claim 6 for adsorbing lead, copper, cadmium, zinc, nickel and the like.
8. The use of the ammonium oxalate modified phosphate tailing adsorbing material as defined in claim 6 for repairing heavy metal polluted water or soil.
9. The use of the ammonium oxalate modified phosphate tailing adsorbing material as defined in claim 8 for repairing heavy metal polluted water or soil, wherein the ammonium oxalate modified phosphate tailing adsorbing material is characterized in that: the polluted water body is singly polluted by lead, copper, cadmium, zinc and nickel or is compositely polluted by a plurality of heavy metals such as lead, copper, zinc, nickel and the like, and the polluted soil is singly polluted by cadmium or compositely polluted by lead and cadmium.
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