CN110040919B - Ground phosphate rock-phosphate composite phosphorus-containing passivator and preparation method and application thereof - Google Patents
Ground phosphate rock-phosphate composite phosphorus-containing passivator and preparation method and application thereof Download PDFInfo
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- CN110040919B CN110040919B CN201910317394.6A CN201910317394A CN110040919B CN 110040919 B CN110040919 B CN 110040919B CN 201910317394 A CN201910317394 A CN 201910317394A CN 110040919 B CN110040919 B CN 110040919B
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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
- C02F11/004—Sludge detoxification
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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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a phosphorite powder-phosphate composite phosphorus-containing passivator and a preparation method and application thereof. The optimal mass ratio of the powdered rock phosphate and the calcium superphosphate for preparing the composite phosphorus-containing passivator is 3:0.2, mixing the powdered rock phosphate-phosphate composite phosphorus-containing passivator and the treated sludge according to the mass ratio of 8:20-30 parts of the sludge are uniformly mixed and passivated to achieve the effect of treating the heavy metals in the sludge. Compared with the existing passivator for treating heavy metals in sludge, the passivator has the characteristics of simple preparation, convenient operation and lower cost, can reduce the biological effectiveness and the ecological toxicity of Cu, Zn and Pb in the sludge to the greatest extent, and provides a new way for resource utilization of the sludge.
Description
Technical Field
The invention relates to the technical field of passivation treatment of heavy metals in sludge, and particularly relates to a powdered rock phosphate-phosphate composite phosphorus-containing passivator and a preparation method and application thereof.
Background
With the increase of sewage treatment capacity, the treatment and disposal of sludge becomes more and more urgent. Especially, heavy metals in the sludge become key factors for restricting the utilization of the sludge, and if the heavy metals in the sludge are not treated in time, the heavy metals can be converted or migrated in natural environment through a series of physical changes or biochemical changes, so that the environment is obviously affected, and the problem of heavy metal pollution in the treated sludge is very slow. Powdered rock phosphate is widely applied to passivation and restoration of heavy metal contaminated soil at present, and the powdered rock phosphate is applied to tannery sludgePb, Cu and Zn have good fixing effect, but when excessive powdered rock phosphate is used alone for passivation and restoration, the pH is reduced, and the ecological toxicity and the bioavailability of Zn are increased, and in addition, PO is used4 3-The multi-stage dissociation of (2) causes the precipitation of the metal phosphate to be redissolved. This in turn does not achieve a good passivation effect. Superphosphate belongs to water-soluble quick-acting phosphate fertilizer, is a phosphate fertilizer directly prepared by decomposing phosphorite with sulfuric acid, and because the grade of the superphosphate is low, the sale cost of unit active ingredients is high, and along with the increase of the yield of high-concentration phosphate fertilizer, the proportion of the superphosphate used in the phosphate fertilizer alone is continuously reduced.
Disclosure of Invention
The invention aims to overcome the problems of the powdered rock phosphate and the calcium superphosphate in the process of single passivation, and provides a powdered rock phosphate-phosphate composite phosphorus-containing passivator, which adopts the following technical scheme for realizing the purposes of the invention:
a powdered rock phosphate-phosphate composite phosphorus-containing passivator is prepared from neutral ammonium citrate solution as solvent and powdered rock phosphate as solute through mixing, filtering to obtain filtrate, adding soluble phosphate to the filtrate, oscillating, baking and grinding.
A preparation method of a powdered rock phosphate-phosphate composite phosphorus-containing passivator comprises the following steps:
1) grinding the ground phosphate rock and the calcium superphosphate respectively at the temperature of 20-25 ℃, sieving the ground phosphate rock and the calcium superphosphate by a 80-mesh sieve, and taking undersize products;
2) putting the ground phosphate rock into a triangular flask, adding a neutral ammonium citrate solution with the concentration of 200g/L which is preheated to 65 ℃, tightly plugging the solution by using a rubber stopper, shaking and mixing the solution, putting the solution into a water bath, keeping the temperature in the flask at 65 ℃, shaking the solution once every 5 minutes, and removing the bottle after one hour to obtain a mixed solution;
3) adopting a water system microporous filter membrane with the diameter of 50mm and the aperture of 0.45 mu m, and performing air suction filtration on the mixed solution by using a needle type head filter to obtain clear filtrate;
4) adding soluble phosphate into the filtrate, mixing uniformly, oscillating at 60 ℃, drying at 40 ℃ and grinding the solid into powder to obtain the powdered rock phosphate-phosphate composite phosphorus-containing passivator.
Preferably, in the above preparation method, the soluble phosphate is calcium superphosphate.
Preferably, in the preparation method, step 2), the solid-to-liquid ratio of the powdered rock phosphate: the ammonium citrate solution is 10g to 1L.
Preferably, in the preparation method, the powdered rock phosphate-phosphate composite phosphorus-containing passivating agent in step 4) is prepared from the following components in percentage by mass: soluble phosphate is 3: 0.05-0.4.
An application of phosphorus ore powder-phosphate composite phosphorus-containing passivator in passivating heavy metals in sludge.
Preferably, in the application, the phosphorite powder-phosphate composite phosphorus-containing passivator is added into the dewatered sludge, and the mixture is uniformly mixed and stirred for passivation.
Preferably, in the above application, the water content of the dewatered sludge is 7-9%.
Preferably, the application comprises the following steps of (1) mixing the powdered rock phosphate and the phosphate composite phosphorus-containing passivating agent in mass ratio: the sludge is 8: 20-30.
The invention has the beneficial effects that:
(1) the preparation raw material of the phosphorite powder-phosphate composite phosphorus-containing passivator is convenient and easy to obtain, and has low cost due to low price.
(2) The preparation process of the phosphorite powder-phosphate composite phosphorus-containing passivator is simple to operate, the conditions are easy to master, and the product can be directly used for passivating sludge without steps of retreatment and the like, so that the preparation cost is reduced, and the operation steps are simplified.
(3) The phosphorite powder-phosphate composite phosphorus-containing passivator can effectively reduce the biological effectiveness and the ecological toxicity of Cu, Zn and Pb in sludge, and maximize the passivation effect of composite phosphate on the sludge.
(4) The phosphorite powder-phosphate composite phosphorus-containing passivator provides a new treatment way for the treatment of heavy metals in sludge, and the sludge passivated by the phosphorite powder-phosphate composite phosphorus-containing passivator can realize resource utilization.
Drawings
FIG. 1 shows the effect of different ground phosphate-superphosphate ratios on the total copper content ratio of different forms in the examples.
FIG. 2 shows the effect of different ground phosphate-superphosphate ratios on the total zinc content ratio in different forms in the examples.
FIG. 3 shows the effect of different ground phosphate-superphosphate ratios on the total lead content ratio of different forms in the examples.
FIG. 4 shows the effect of Y1 and Y2 on the ratio of copper in total amount in different forms.
FIG. 5 shows the effect of Y1 and Y2 on the ratio of different forms of zinc in the total amount.
FIG. 6 shows the effect of Y1 and Y2 on the ratio of different forms of lead in the total amount.
Detailed Description
Example 1A phosphorus ore powder-calcium superphosphate composite phosphorus-containing passivating agent
The preparation method comprises the following steps:
1. pretreatment:
grinding the ground phosphate rock at 20-25 ℃, sieving with a 80-mesh sieve, and taking undersize products.
Grinding calcium phosphate at 20-25 deg.C, sieving with 80 mesh sieve, and collecting the undersize product.
2. Preparing the powdered rock phosphate-calcium superphosphate composite phosphorus-containing passivator:
3g of the ground phosphate rock is weighed and placed in a triangular flask, 300mL of 200g/L neutral ammonium citrate solution which is preheated to 65 ℃ is added and tightly plugged by a rubber stopper, the mixture is shaken and mixed, then the mixture is placed in a water bath, the temperature in the flask is kept at 65 ℃, the mixture is shaken once every 5 minutes, and after one hour, the mixture is removed from the flask to obtain a mixed solution. And (3) filtering the mixed solution by using a water system microporous filter membrane with the diameter of 50mm and the pore diameter of 0.45 mu m through a needle head filter to obtain clear filtrate. And adding 0.2g of calcium superphosphate into the filtrate, uniformly mixing, oscillating at 60 ℃, drying at the low temperature of 40 ℃, and grinding the solid into powder to obtain the powdered rock phosphate-calcium superphosphate composite phosphorus-containing passivating agent.
Example 2 application of phosphorus ore powder-calcium superphosphate composite phosphorus-containing passivator in passivation of heavy metals in sludge
Dewatering the sludge by a belt filter press to ensure that the water content of the sludge is 7-9 percent, grinding the sludge and sieving the sludge by a sieve of 80 meshes, weighing 10g of the treated sludge, adding 3.2g of the prepared ground phosphate rock-calcium superphosphate composite phosphorus-containing passivator into the sludge, stirring the mixture by a magnetic stirrer for 10-20min at the stirring speed of 50-60r/min, placing the mixture into a polytetrafluoroethylene bottle after uniformly stirring, and passivating the mixture for 7 days at the ambient temperature of 20-25 ℃. Analyzing exchangeable state, reducible state, oxidizable state and residue state of the sample by adopting a modified BCR method, wherein the content w of heavy metal M in the sludge is milligram per kilogram (mg/kg), and is calculated according to the following formula:
in the formula: c, checking the content value of M on a calibration curve, wherein the unit is mg/L;
C0checking the numerical value of the content of M in the blank test solution on a calibration curve, wherein the unit is mg/L;
v is the numerical value of the volume of the test solution with constant volume, and the unit is mL;
m is the numerical value of the weight of the weighed sample, and the unit is g;
f is the value of the water content of the sample, expressed in decimal.
As can be seen from fig. 1, 2 and 3, the addition of calcium superphosphate to the powdered rock phosphate can significantly increase the content of metal in sludge in a residue state.
Example 3 influence of the quality ratio of ground phosphate rock to superphosphate on passivation of heavy metals
The preparation conditions of the phosphorite powder-calcium superphosphate composite phosphorus-containing passivator are as follows: 3g of the ground phosphate rock is weighed and placed in a triangular flask, 300mL of 200g/L neutral ammonium citrate solution which is preheated to 65 ℃ is added and tightly plugged by a rubber stopper, the mixture is shaken and mixed, then the mixture is placed in a water bath, the temperature in the flask is kept at 65 ℃, the mixture is shaken once every 5 minutes, and after one hour, the mixture is removed from the flask to obtain a mixed solution. And (3) filtering the mixed solution by using a water system microporous filter membrane with the diameter of 50mm and the pore diameter of 0.45 mu m through a needle head filter to obtain clear filtrate. 0.05g, 0.1g, 0.2g and 0.4g of pretreated calcium superphosphate are respectively added into the filtrate to be uniformly mixed, the mixture is oscillated at 60 ℃, the solid is ground into powder after being dried at the low temperature of 40 ℃, and the phosphorite powder-calcium superphosphate composite phosphorus-containing passivator with the mass ratio of the phosphorite powder to the calcium superphosphate of 3:0, 3:0.05, 3:0.1, 3:0.2 and 3:0.4 is prepared.
Respectively taking 3.2g of 5 groups of phosphate rock powder-superphosphate composite phosphorus-containing passivator, respectively uniformly mixing with 10g of sludge with the water content of 7-9%, placing the mixture in a polytetrafluoroethylene bottle for passivation for 7 days, analyzing a sample by adopting an improved BCR method, and drawing the calculated data of exchangeable state, reducible state, oxidizable state and residue state of copper, zinc and lead.
The results are shown in figure 1, when the mass ratio of the ground phosphate rock to the calcium superphosphate is 3: under the condition of 0.2, the effective state content of Cu in the sludge is reduced to 18.4 percent at most, and the residue state content is increased to 19.2 percent at most.
The results are shown in fig. 2, when the mass ratio of the phosphate rock powder to the calcium superphosphate is 3: under the condition of 0.2, the effective state content of Zn in the sludge is reduced to 10.6 percent at most, and the residue state content is increased to 11.3 percent at most.
The results are shown in fig. 3, where the mass ratio of ground phosphate to calcium superphosphate is 3: at 0.2, the available state content of Pb in the sludge was reduced to 6.8% and the residue state content was increased to 7.6%.
In conclusion, when the mass ratio of the phosphate rock powder to the calcium superphosphate is 3: under the condition of 0.2, the phosphorus mineral powder-calcium superphosphate composite phosphorus-containing passivating agent in the sludge passivates the sludge, so that the biological effectiveness and the ecological toxicity of Cu, Zn and Pb in the sludge are reduced to the maximum extent, and the passivating effect is optimal. Therefore, the optimum mass ratio of the phosphate rock powder to the calcium superphosphate is 3: 0.2.
EXAMPLE 4 comparison of different preparation methods of powdered rock phosphate-calcium superphosphate composite phosphorus-containing passivator
The preparation method comprises the following steps: 3g of the ground phosphate rock is weighed and placed in a triangular flask, 300mL of 200g/L neutral ammonium citrate solution which is preheated to 65 ℃ is added and tightly plugged by a rubber stopper, the mixture is shaken and mixed, then the mixture is placed in a water bath, the temperature in the flask is kept at 65 ℃, the mixture is shaken once every 5 minutes, and after one hour, the mixture is removed from the flask to obtain a mixed solution. And (3) filtering the mixed solution by using a water system microporous filter membrane with the diameter of 50mm and the pore diameter of 0.45 mu m through a needle head filter to obtain clear filtrate. 0.2g of calcium superphosphate is added to the filtrate, mixed evenly, shaken at 60 ℃, dried at 40 ℃ and ground into powder to prepare the powdered rock phosphate-phosphate composite phosphorus-containing passivator which is marked as Y1.
The second preparation method comprises the following steps: 3g of the processed ground phosphate rock and 0.2g of calcium superphosphate are weighed and put into a magnetic stirrer to be stirred for 10-20min, the stirring speed is controlled at 50-60r/min, and the ground phosphate rock-phosphate composite phosphorus-containing passivator is obtained after uniform mixing and is marked as Y2.
Respectively and uniformly mixing Y1 and Y2 with 10g of sludge with the water content of 7-9%, placing the mixture in a polytetrafluoroethylene bottle for passivation for 7 days, analyzing a sample by adopting an improved BCR method, and drawing the calculated exchangeable state, reducible state, oxidizable state and residue state data of copper, zinc and lead.
As a result, as shown in FIG. 4, after passivating the sludge with Y1 and Y2, respectively, the content of Cu in the sludge in the residual state under Y1 was increased by 21.1% compared to that under Y2.
As a result, as shown in FIG. 5, after passivating the sludge with Y1 and Y2, respectively, the Zn residue content in the sludge was increased by 16.2% under Y1 compared to Y2.
As a result, as shown in FIG. 6, after passivating the sludge with Y1 and Y2, respectively, the content of Pb in the sludge in the residual state was increased by 11.7% under Y1 compared to Y2.
In conclusion, compared with the simple mixing of the powdered rock phosphate and the phosphate (Y2), the preparation method of the powdered rock phosphate-phosphate composite phosphorus-containing passivator (Y1) has better passivation effect on heavy metals in sludge, can effectively reduce the biological effectiveness and the ecological toxicity of Cu, Zn and Pb in the sludge, and enables the passivation effect of the composite phosphate on the sludge to be larger.
Claims (4)
1. The application of the phosphorite powder-phosphate composite phosphorus-containing passivator in passivating heavy metals in sludge is characterized in that the method comprises the following steps: adding the powdered rock phosphate-phosphate composite phosphorus-containing passivator into the dewatered sludge, mixing and stirring uniformly for passivating; the water content of the dewatered sludge is 7-9%; according to the mass ratio, the ground phosphate rock-phosphate composite phosphorus-containing passivator comprises the following components: sludge =8: 20-30; the phosphorite powder-phosphate composite phosphorus-containing passivator takes neutral ammonium citrate solution as a solvent and phosphorite powder as a solute, the neutral ammonium citrate solution and the phosphate powder are mixed to obtain a solution, then the solution is filtered to obtain a filtrate, soluble phosphate is added into the filtrate, the filtrate is uniformly oscillated and then dried and ground into powder, and the powder is the phosphorite powder-phosphate composite phosphorus-containing passivator;
the preparation method of the phosphorite powder-phosphate composite phosphorus-containing passivator comprises the following steps:
1) grinding the ground phosphate rock and the soluble phosphate respectively at the temperature of 20-25 ℃, sieving the ground phosphate rock and the soluble phosphate by a 80-mesh sieve, and taking undersize;
2) putting the ground phosphate rock into a triangular flask, adding a neutral ammonium citrate solution with the concentration of 200g/L which is preheated to 65 ℃, tightly plugging the solution by using a rubber stopper, shaking and mixing the solution, putting the solution into a water bath, keeping the temperature in the flask at 65 ℃, shaking the solution once every 5 minutes, and removing the bottle after one hour to obtain a mixed solution;
3) adopting a water system microporous filter membrane with the diameter of 50mm and the aperture of 0.45 mu m, and performing air suction filtration on the mixed solution by using a needle type head filter to obtain clear filtrate;
4) adding soluble phosphate into the filtrate, mixing uniformly, oscillating at 60 ℃, drying at 40 ℃ and grinding the solid into powder to obtain the powdered rock phosphate-phosphate composite phosphorus-containing passivator.
2. Use according to claim 1, characterized in that the soluble phosphate is calcium superphosphate.
3. The application of the method as claimed in claim 1, wherein in the step 2), the ratio of ground phosphate rock to solid-to-liquid is as follows: the ammonium citrate solution is 10g to 1L.
4. The application of the phosphorus ore powder-phosphate composite phosphorus-containing passivator as set forth in the step 4) is characterized in that the mass ratio of the phosphorus ore powder: soluble phosphate =3: 0.05-0.4.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879522A (en) * | 2010-07-28 | 2010-11-10 | 杭州电子科技大学 | Repair method for lead zinc ore combined contamination soil |
| CN103756682A (en) * | 2014-01-13 | 2014-04-30 | 东南大学 | Solidifying agent of repairing high-concentration multiple heavy metal polluted site and preparation and application methods thereof |
| CN109201724A (en) * | 2018-08-17 | 2019-01-15 | 西南科技大学 | A kind of method that Uranium tailings uranium and association heavy-metal contaminated soil are repaired in phosphorus-containing compound passivation |
| CN109517600A (en) * | 2018-11-26 | 2019-03-26 | 北京南科大蓝色科技有限公司 | It is a kind of for the soil-repairing agent and its application method of heavy metal pollution and application |
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- 2019-04-19 CN CN201910317394.6A patent/CN110040919B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879522A (en) * | 2010-07-28 | 2010-11-10 | 杭州电子科技大学 | Repair method for lead zinc ore combined contamination soil |
| CN103756682A (en) * | 2014-01-13 | 2014-04-30 | 东南大学 | Solidifying agent of repairing high-concentration multiple heavy metal polluted site and preparation and application methods thereof |
| CN109201724A (en) * | 2018-08-17 | 2019-01-15 | 西南科技大学 | A kind of method that Uranium tailings uranium and association heavy-metal contaminated soil are repaired in phosphorus-containing compound passivation |
| CN109517600A (en) * | 2018-11-26 | 2019-03-26 | 北京南科大蓝色科技有限公司 | It is a kind of for the soil-repairing agent and its application method of heavy metal pollution and application |
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