CN113871129B - Preparation method and application of liquid magnetic fluid - Google Patents
Preparation method and application of liquid magnetic fluid Download PDFInfo
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
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- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method of liquid magnetic fluid, which adopts ionic liquid to carry out Fe treatment 3 O 4 The hydroxyapatite composite magnetic nano material is modified, a hydrophobic organic solvent is added after drying, and the mixture is uniformly stirred and mixed in an equal volume to prepare liquid magnetic fluid, the liquid magnetic fluid is applied to be used as a heavy metal adsorbent, the removal effect of the liquid magnetic fluid on heavy metal reaches more than 95%, the preparation is simple, and the high-efficiency extraction and collection of valuable component heavy metal can be realized while the treatment cost of heavy metal pollution is reduced; has better market value and popularization and application prospect.
Description
Technical Field
The invention belongs to the technical field of pollutant purification and separation, and particularly relates to a preparation method and application of liquid magnetic fluid.
Background
With the development of modern industry, agriculture and city, heavy metal pollution caused by human factors is far more than natural factors. The problem of heavy metal pollution in water bodies in China is very remarkable, and the pollution rate of the bottom materials of rivers, lakes and reservoirs is as high as 80.1 percent. In recent years, the pollution degree of heavy metal exceeding cross section of river basin slices of ten large river basins such as yellow river, huai river, pinghuajiang river and Liaohe is super V class. The urban river has 35.11 percent of river reach with total mercury exceeding the class III water standard of surface water, 18.46 percent of river reach with total cadmium exceeding the class III water standard, and 25 percent of river reach with a standard exceeding sample of total lead. The total amount of heavy metal pollutants carried into the sea from rivers such as Yangtze river, zhujiang river and yellow river is about 3.4 ten thousand t, and the pollution hazard to the ocean water is huge. The lead standard exceeding rate in the offshore sea water sampling sample of the whole country reaches 62.9%, and the maximum value exceeds 490 times of the standard of the sea water; the exceeding rate of copper is 25.9%, and the content of mercury and cadmium is also exceeding. In addition, cadmium is more investigated and researched in soil heavy metal pollution in China. Cadmium pollution in China is common, and relates to 11 provinces and cities; and secondly mercury, zinc, chromium, etc. The background value of the soil cadmium in China is 0.010-1.8 mg/kg, and the average value is 0.163mg/kg. The zinc content of the soil in China is 3-709 mg/kg, the median value is 100mg/kg, the cadmium and zinc content in the contaminated soil are increased by times, for example, the cadmium content in a heavy metal contaminated area in the Shanghai reaches 3-5 mg/kg, how to regulate and control the cadmium content, and the treatment of heavy metal pollution becomes an important factor for restricting the improvement of the living standard of people in China, and the prevention and control of the heavy metal pollution are particularly important.
However, the heavy metal stabilizer widely used at present only has the functions of solidifying and stabilizing the heavy metal, and cannot thoroughly remove and recycle the heavy metal, and the material cannot be recycled. The magnetic adsorption material has excellent recycling performance, however, the single-domain magnetic nano particles often generate agglomeration phenomenon, the performance on a macroscopic scale is related to the interaction tightness degree among the nano particles, and the agglomeration of the microscopic particles further influences the macroscopic performance of the whole magnetic nano material such as mechanics, magnetism, electricity and the like, so that the large-scale application of the magnetic adsorption material is limited. Therefore, in order to obtain a magnetic adsorption material with excellent properties, avoiding agglomeration of magnetic nanoparticles is an indispensable prerequisite. The invention provides Fe with liquid magnetic fluid coated by functional ionic liquid 3 O 4 The hydroxyapatite composite magnetic nano material is dispersed in a hydrophobic organic solvent to form a colloid solution with fluidity and magnetism, and the colloid solution is used as a very stable suspension of ferromagnetic particles, and has the magnetism of a solid magnetic material, the fluidity and viscosity of common fluid and the like. Especially compared with the common magnetic material, the surfactant coating provides short-distance steric hindrance and inter-particle electrostatic repulsion for the magnetic medium in the magnetic fluid, so that the magnetic nano particles are prevented from agglomerating, can stably exist for a long time, are easy to recycle and reuse, and have wide application prospects in heavy metal pollution adsorption and utilization.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of liquid magnetic fluid, which adopts ionic liquid to carry out Fe 3 O 4 Modification of hydroxyapatite composite magnetic nanomaterialAdding a hydrophobic organic solvent, and mixing the mixture in an equal volume to prepare liquid magnetic fluid; the stable adsorption efficiency of the liquid magnetic fluid on various heavy metals in water and gas is more than 95%.
The Fe is 3 O 4 The hydroxyapatite composite magnetic nano material is prepared by mixing a nano material with a nano material 2 Under protection, feCl is added according to the mass ratio of 1:1-3 2 •4H 2 O and FeCl 3 •6H 2 O is dissolved in deionized water, stirred at 800-1300 rpm, and 25% NH is added 4 Slowly dripping an OH solution until the pH value of the solution is 10, heating at 60-80 ℃ for reaction for 30-60 min, separating a reaction product by a permanent magnet, repeatedly washing with deionized water until the pH value of a washing solution is 7, dispersing the washed reaction product in the deionized water to obtain a suspension with the mass concentration of 10-15%, dripping a citric acid solution with the mass concentration of 0.1mol/L and the volume of 5% of the suspension, ultrasonically mixing for 20-30 min, and dripping Ca (NO) with the volume of 8-12% of the suspension in 30-60 min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 Then reacting for 1-2 hours at 80-90 ℃, cooling the mixture to room temperature and aging overnight; and (3) separating the formed dark brown precipitate by using a permanent magnet, repeatedly washing with deionized water until the pH value of the supernatant is 7, and calcining at 300-400 ℃ for 1-3 hours after vacuum drying.
The Ca (NO) 3 ) 2 And (NH 4) 2 HPO 4 In the aqueous solution of (2) in a volume ratio of 1:1, 33.7mmol/L Ca (NO) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Mixing the solutions.
The ionic liquid is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1- (2-hydroxyethyl) -3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1, 3-dimethylimidazole hexafluorophosphate or 1-butyl-3-methylimidazole p-toluenesulfonate; ionic liquid and Fe 3 O 4 The mass ratio of the hydroxyapatite composite magnetic nano material is 2-5:1, and the modification is spin steaming treatment for 20-30 min at the temperature of 80-100 ℃ at 200-600 rpm.
The hydrophobic organic solvent is oleic acid, chloralkyl ester, dimethyl carbonate or diethyl carbonate.
The invention further aims to apply the liquid magnetic fluid prepared by the preparation method of the liquid magnetic fluid to be used as a heavy metal adsorbent, adsorption is carried out under the action of a magnetic field of 0.04-40 mT, after heavy metal adsorption is finished, solid-liquid separation is carried out under the condition of an external magnetic field of 0.1-0.2T, heavy metal on the solid is resolved and recovered at the temperature of 90-100 ℃ by adopting 5% HCl, the regenerated magnetic nano material is precipitated in a magnetic field of 30+ -5 mT in a magnetic sedimentation mode, and the regenerated magnetic nano material is dried and reused after being washed for 2-3 times, so that secondary pollution is reduced.
The method has the advantages and technical effects that:
(1) The liquid magnetic fluid is simple to prepare, has the advantages of coexistence of multiple performances of magnetic adsorption, chemical adsorption and physical adsorption, has good heavy metal adsorption stability effect, and can achieve the purification effect of more than 95 percent on heavy metals;
(2) The liquid magnetic fluid has magnetism, good moving performance and dispersion property, and is convenient for the regeneration and recovery and the secondary utilization of materials;
(3) The method can reduce the treatment cost of heavy metal pollution and simultaneously realize high-efficiency extraction and collection of valuable component heavy metals; has better market value and popularization and application prospect.
Detailed Description
The technical solution of the present invention will be further described with reference to the specific examples, but the scope of the present invention is not limited to the above.
Example 1: the preparation of the liquid magnetic fluid and the treatment of heavy metal polluted sewage, the sewage is manually prepared, in particular to Cu with the concentration of 200mg/L prepared by anhydrous copper sulfate 2+ Solution, pH adjusted to = 6;
（1）Fe 3 O 4 preparation of HAP composite magnetic nanomaterial
At N 2 Under protection, feCl is added according to the mass ratio of 1:2 2 •4H 2 O and FeCl 3 •6H 2 O was dissolved in 200mL of deionized water, stirred at 1000rpm, and 25%NH 4 Slowly dripping OH solution until the pH of the solution is 10, heating at 60 ℃ for reaction for 60min, separating out reaction products by using permanent magnets, repeatedly washing with deionized water until the pH of washing liquid is 7, dispersing the washed reaction products in the deionized water to obtain suspension with the mass concentration of 10%, dripping citric acid solution with the mass concentration of 0.1mol/L and the volume of 5% of the suspension, ultrasonically mixing for 30min, and then dripping Ca (NO) with the volume of 10% of the suspension within 30min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 (33.7 mmol/L Ca (NO) in a volume ratio of 1:1) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Solution mixing), and then after 2 hours of reaction at 80 ℃, the mixture was cooled to room temperature and aged overnight; separating the formed dark brown precipitate by using a permanent magnet, repeatedly washing with deionized water until the pH value of the supernatant is 7, drying in vacuum, and calcining at 400 ℃ for 1h to obtain the product;
(2) Fe is added according to the mass ratio of 1:2 3 O 4 Adding the hydroxyapatite composite magnetic nano material into 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, and performing rotary steaming at 200rpm and 80 ℃ for 30min; then adding oleic acid with the same volume, and stirring and uniformly mixing at 600rpm to prepare liquid magnetic fluid;
(3) Mixing the prepared liquid magnetic fluid with heavy metal-containing wastewater according to the volume ratio of 1g to 1L, treating at room temperature under the action of a magnetic field of 1mT, and along with the reaction time, the liquid magnetic fluid is used for Cu 2+ The adsorption of (2) is in an ascending trend, the adsorption capacity of the first 1.6h is in direct proportion to the time, the speed is reduced after 1.6h, the maximum adsorption capacity is reached in 2.4h, and the maximum adsorption capacity is about 190mg/g;
(4) After heavy metal adsorption is completed, solid-liquid separation is carried out under the condition of an external magnetic field of 0.1T, the solid is resolved by 5% HCl at 95 ℃, the heavy metal is collected, the regenerated magnetic nano material is washed for 2 times by water and then dried at 60 ℃ for reuse, and secondary pollution is reduced.
Example 2: the preparation of the liquid magnetic fluid and the treatment of heavy metal polluted sewage are carried out by manually preparing the sewage, in particular to the concentration of 1 prepared by nickel chloride hexahydrateNi 00mg/L 2+ Solution, regulating pH to 7;
（1）Fe 3 O 4 preparation of HAP composite magnetic nanomaterial
At N 2 Under protection, feCl is added according to the mass ratio of 1:1 2 •4H 2 O and FeCl 3 •6H 2 O was dissolved in 200mL of deionized water, stirred at 800rpm, and 25% NH was added 4 Slowly dripping OH solution until the pH of the solution is 10, heating at 70 ℃ for reaction for 40min, separating out reaction products by using permanent magnets, repeatedly washing with deionized water until the pH of washing liquid is 7, dispersing the washed reaction products in the deionized water to prepare suspension with the mass concentration of 15%, dripping citric acid solution with the mass concentration of 0.1mol/L and the volume of 5% of the suspension into the suspension, ultrasonically mixing for 30min, and then dripping Ca (NO) with the volume of 8% of the suspension into the suspension within 60min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 (33.7 mmol/L Ca (NO) in a volume ratio of 1:1) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Solution mixing), and then after reacting at 90 ℃ for 1h, the mixture was cooled to room temperature and aged overnight; separating the formed dark brown precipitate with permanent magnet, repeatedly washing with deionized water until the pH of the supernatant is 7, vacuum drying, and calcining at 300 ℃ for 3h to obtain the product;
(2) Mixing 1-butyl-1-methylpyrrolidine trifluoro methanesulfonate and Fe in a mass ratio of 3:1 3 O 4 Mixing the hydroxyapatite composite magnetic nano material, and performing rotary steaming at 600rpm and 100 ℃ for 20min; then adding equal volume of chloralkyl ester, stirring and uniformly mixing at 1200rpm to obtain liquid magnetic fluid;
(3) Mixing the prepared liquid magnetic fluid with heavy metal-containing wastewater according to the volume ratio of 1g to 1L, treating at room temperature under the action of a 5mT magnetic field, and along with the reaction time, making the liquid magnetic fluid correspond to Ni 2+ The adsorption of the catalyst is in an ascending trend, the adsorption rate is relatively high in the first 1.5 hours, the adsorption equilibrium is reached in 2 hours, and the maximum adsorption capacity is about 98mg/g;
(4) After heavy metal adsorption is completed, solid-liquid separation is carried out under the condition of an external magnetic field of 0.1T, the solid is resolved by 5% HCl at 95 ℃, the heavy metal is collected, the regenerated magnetic nano material is washed for 2 times by water and then dried at 60 ℃ for reuse, and secondary pollution is reduced.
Example 3: the preparation of the liquid magnetic fluid and the application thereof in the treatment of heavy metal-containing sewage, wherein the sewage is derived from a certain tailing leaching solution, the content of heavy metal Fe in the sewage is 40mg/L, the content of As is 5.9mg/L, and the pH is 6.5, and the specific operation is As follows:
（1）Fe 3 O 4 preparation of HAP composite magnetic nanomaterial: at N 2 Under protection, feCl is added according to the mass ratio of 1:3 2 •4H 2 O and FeCl 3 •6H 2 O was dissolved in 200mL of deionized water, stirred at 1200rpm, and 25% NH was added 4 Slowly dripping the OH solution until the pH value of the solution is 10, heating at 80 ℃ for reaction for 30min, separating out a reaction product by using a permanent magnet, repeatedly washing with deionized water until the washing liquid is obtained, dispersing the washed reaction product in the deionized water to obtain a suspension with the mass concentration of 12%, dripping a citric acid solution with the mass concentration of 0.1mol/L and the volume concentration of 5% of the suspension into the suspension, ultrasonically mixing for 25min, and then dripping Ca (NO) containing 11% of the volume of the suspension into the suspension within 40min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 (33.7 mmol/L Ca (NO) in a volume ratio of 1:1) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Solution mixing), then after reacting at 85 ℃ for 1.5 hours, the mixture was cooled to room temperature and aged overnight; separating the formed dark brown precipitate with permanent magnet, repeatedly washing with deionized water until the pH of the supernatant is 7, vacuum drying, and calcining at 350deg.C for 2 hr;
(2) Mixing 1- (2-hydroxyethyl) -3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and Fe in a mass ratio of 4:1 3 O 4 Mixing the hydroxyapatite composite magnetic nano material, and performing rotary steaming at 400rpm and 90 ℃ for 25min; then adding the dimethyl carbonate with the same volume, and stirring and uniformly mixing at 800rpm to prepare liquid magnetic fluid;
(3) Mixing the prepared liquid magnetic fluid with soil containing heavy metals according to the ratio of 1g to 1L, and treating for 120min at 30 ℃ under the action of a magnetic field of 10 mT; after heavy metal adsorption is completed, solid-liquid separation is carried out under the condition of an external magnetic field of 0.1T, and the concentration of Fe in the treated sewage is 0.05mg/L and As is not detected;
(4) The separated magnetically-aggregated polymer is subjected to heavy metal analysis at 95 ℃ by 5% HCl, the heavy metal is collected, the regenerated magnetic nano material is washed for 2 times by water and then dried at 60 ℃ for reuse, and secondary pollution is reduced.
Example 4: the liquid magnetic fluid targeting heavy metal stabilizer and the treatment of the aerosol containing heavy metal, wherein the concentration of Cr in the aerosol is 102.4 mu g/m 3 Cd concentration is 35.8 mu mg/m 3 ；
（1）Fe 3 O 4 Preparation of HAP composite magnetic nanomaterial: at N 2 Under protection, feCl is added according to the mass ratio of 1:1 2 •4H 2 O and FeCl 3 •6H 2 O was dissolved in 200mL of deionized water, stirred at 800rpm, and 25% NH was added 4 Slowly dripping OH solution until the pH of the solution is 10, heating at 70 ℃ for reaction for 40min, separating out reaction products by using permanent magnets, repeatedly washing with deionized water until the pH of washing liquid is 7, dispersing the washed reaction products in the deionized water to prepare suspension with the mass concentration of 15%, dripping citric acid solution with the mass concentration of 0.1mol/L and the volume of 5% of the suspension into the suspension, ultrasonically mixing for 30min, and then dripping Ca (NO) with the volume of 8% of the suspension into the suspension within 60min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 (33.7 mmol/L Ca (NO) in a volume ratio of 1:1) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Solution mixing), and then after reacting at 90 ℃ for 1h, the mixture was cooled to room temperature and aged overnight; separating the formed dark brown precipitate with permanent magnet, repeatedly washing with deionized water until the pH of the supernatant is 7, vacuum drying, and calcining at 300 ℃ for 3h to obtain the product;
(2) Mixing 1-butyl-1-methylpyrrolidine trifluoro methanesulfonate and Fe in a mass ratio of 5:1 3 O 4 Mixing the hydroxyapatite composite magnetic nano material, and performing rotary steaming at 600rpm and 100 ℃ for 20min; then adding an equal volume of the chloroalkyl esterStirring and uniformly mixing at 1200rpm to obtain liquid magnetic fluid;
(3) The liquid-gas ratio is 1g to 10m 3 Introducing heavy metal-containing gas into the prepared liquid magnetic fluid, controlling the reaction time to be 30min under the action of a 40mT magnetic field, and controlling the Cr concentration in the outlet gas after the reaction to be 5 mu g/m 3 The Cd concentration was not detected;
(4) After heavy metal adsorption is completed, the adsorbed heavy metal is resolved by 5% HCl at 95 ℃, the heavy metal is collected, the regenerated magnetic nano material is washed for 2 times by water and then dried at 60 ℃ for reuse, and secondary pollution is reduced.
Claims (3)
1. A preparation method of liquid magnetic fluid is characterized in that: ion liquid is adopted for Fe 3 O 4 The hydroxyapatite composite magnetic nano material is modified, then a hydrophobic organic solvent is added, and the mixture is stirred and mixed uniformly in an equal volume to prepare liquid magnetic fluid;
the ionic liquid is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1- (2-hydroxyethyl) -3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1, 3-dimethylimidazole hexafluorophosphate or 1-butyl-3-methylimidazole p-methylbenzenesulfonate; ionic liquid and Fe 3 O 4 The mass ratio of the hydroxyapatite composite magnetic nano material is 2-5:1, and the modification is spin steaming treatment for 20-30 min at the temperature of 80-100 ℃ at 200-600 rpm;
the hydrophobic organic solvent is oleic acid, chloroalkyl ester, dimethyl carbonate or diethyl carbonate;
the Fe is 3 O 4 The hydroxyapatite composite magnetic nano material is prepared by mixing a nano material with a nano material 2 Under protection, feCl is added according to the mass ratio of 1:1-3 2 •4H 2 O and FeCl 3 •6H 2 O is dissolved in deionized water, stirred at 800-1300 rpm, and 25% NH is added 4 Slowly dripping the OH solution until the pH value of the solution is 10, heating at 60-80 ℃ for reaction for 30-60 min, separating out reaction products by using permanent magnets, repeatedly washing with deionized water until the pH value of washing liquid is 7, and dispersing the washed reaction products in the deionized water to prepare the permanent magnet-type permanent magnet-magnet permanent magnet-type permanent magnet-magnet magnetic heaterObtaining a suspension with the mass concentration of 10% -15%, dripping a citric acid solution with the mass concentration of 0.1mol/L and the volume of 5% of the suspension, carrying out ultrasonic mixing for 20-30 min, and then dripping Ca (NO) containing 8% -12% of the volume of the suspension in 30-60 min under the stirring condition 3 ) 2 And (NH 4) 2 HPO 4 Then reacting for 1-2 hours at 80-90 ℃, cooling the mixture to room temperature and aging overnight; and (3) separating the formed dark brown precipitate by using a permanent magnet, repeatedly washing with deionized water until the pH value of the supernatant is 7, and calcining at 300-400 ℃ for 1-3 hours after vacuum drying.
2. A method of preparing a liquid magnetic fluid according to claim 1, wherein: contains Ca (NO) 3 ) 2 And (NH 4) 2 HPO 4 In the aqueous solution of (2) in a volume ratio of 1:1, 33.7mmol/L Ca (NO) 3 ) 2 Solution and 20mmol/L (NH 4) 2 HPO 4 Mixing the solutions.
3. Use of a liquid magnetic fluid produced by the method of producing a liquid magnetic fluid according to any one of claims 1-2 as a heavy metal adsorbent, characterized in that: the adsorption is carried out under the action of a magnetic field of 0.6-60 mT, after the heavy metal adsorption is completed, solid-liquid separation is carried out under the condition of an external magnetic field of 0.1-0.2T, and the heavy metal on the solid is resolved and recovered at the temperature of 90-100 ℃ by adopting 5% HCl.
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| CN101703917A (en) * | 2009-11-25 | 2010-05-12 | 湖南大学 | Magnetic nano hydroxyapatite adsorbent, preparation and application thereof |
| CN104549127B (en) * | 2015-01-29 | 2017-05-31 | 宁波大学 | Magnetic coupling hydroxyapatite nano particulate and its preparation method and application |
| CN105903069A (en) * | 2016-06-28 | 2016-08-31 | 扬州大学 | One-step synthesis method of hydroxyapatite/ferriferrous oxide composite material |
| CN106622176A (en) * | 2017-01-03 | 2017-05-10 | 华南理工大学 | Preparation method of polysorbate-hydroxyapatite nano composite material for rural drinking water treatment |
| WO2019106178A1 (en) * | 2017-11-30 | 2019-06-06 | Solvay Sa | Hydroxyapatite composite for use in removal of contaminants from effluents and methods of making |
| CN113371782B (en) * | 2021-06-19 | 2022-05-31 | 昆明理工大学 | Material for filtering leaching solution in phosphogypsum slag yard |
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