WO2024051103A1 - Procédé de récupération de phosphogypse - Google Patents

Procédé de récupération de phosphogypse Download PDF

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Publication number
WO2024051103A1
WO2024051103A1 PCT/CN2023/077685 CN2023077685W WO2024051103A1 WO 2024051103 A1 WO2024051103 A1 WO 2024051103A1 CN 2023077685 W CN2023077685 W CN 2023077685W WO 2024051103 A1 WO2024051103 A1 WO 2024051103A1
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WIPO (PCT)
Prior art keywords
phosphogypsum
slurry
washing
acidolysis
tank
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PCT/CN2023/077685
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English (en)
Chinese (zh)
Inventor
王浩
李长东
阮丁山
王威
郑海洋
丁代俊
Original Assignee
宜昌邦普循环科技有限公司
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024051103A1 publication Critical patent/WO2024051103A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C04B11/266—Chemical gypsum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/0445—Synthetic gypsum, e.g. phosphogypsum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/143—Calcium-sulfate
    • C04B22/144—Phosphogypsum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/65—Chroma (C*)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the field of recycling, and specifically relates to a method for recycling phosphogypsum.
  • Phosphogypsum is the main by-product produced during the wet production of phosphoric acid. Its main component is calcium sulfate dihydrate. For every ton of phosphoric acid produced (calculated as P 2 O 5 ), approximately 4.5 to 5.5 tons of phosphogypsum by-products are produced. The composition of phosphogypsum is complex. In addition to calcium sulfate, there are also incompletely decomposed phosphate rock, phosphoric acid, silica, fluoride, metal cation precipitation, acid insoluble matter, organic matter remaining in the gypsum, etc. At present, the annual emission of phosphogypsum in my country is about 70 million tons, and the stock has exceeded 500 million tons. Therefore, the resource utilization of phosphogypsum has attracted much attention. Relevant reports show that the current comprehensive utilization rate of phosphogypsum resources is less than 30%, and large amounts of phosphogypsum are still stored in direct stacks.
  • phosphogypsum As phosphogypsum continues to accumulate, the storage capacity of the slag yard gradually shrinks. The accumulation of phosphogypsum not only occupies a large amount of land resources, but the soluble impurities in it seep through with rainwater, which will cause serious environmental pollution. Therefore, pretreatment of phosphogypsum to improve the quality and economic value of phosphogypsum is the key to solving the problem of phosphogypsum.
  • the current treatment methods for phosphogypsum include lime neutralization, water washing, flotation, flash burning, etc.
  • the cost of flotation equipment reagents is high and uneconomical; the flash burning method has a small processing capacity; the lime neutralization method can eliminate soluble phosphorus and fluorine elements, but the phosphorus element still remains in the gypsum, resulting in a waste of phosphorus resources.
  • the water washing method can effectively remove soluble impurities and recover some water-soluble phosphorus elements, but it is still unable to process insoluble phosphorus, which accounts for nearly twice as much as water-soluble phosphorus in phosphogypsum, and the proportion of water-soluble substances in phosphogypsum is low. , water washing and purification will not significantly increase the calcium sulfate dihydrate content.
  • one of the objects of the present invention is to provide a method for recovering phosphogypsum.
  • the second object of the present invention is to provide a kind of phosphogypsum.
  • the third object of the present invention is to provide an application of phosphogypsum in building materials.
  • the fourth object of the present invention is to provide a phosphogypsum recovery system.
  • a first aspect of the present invention provides a method for recovering phosphogypsum, which includes the following steps:
  • the carbonate is a soluble carbonate or a mixture of soluble carbonate and insoluble carbonate.
  • the soluble carbonate in the present invention can dissociate the calcium sulfate crystals in the phosphogypsum, thereby releasing the impurities contained in the calcium phosphate crystals and achieving the purpose of purifying the phosphogypsum.
  • the soluble carbonate is at least one of sodium carbonate and potassium carbonate.
  • the mass percentage of soluble carbonate is greater than 40%.
  • the insoluble carbonate is calcium carbonate.
  • the particle size of the calcium carbonate is no larger than 60 mesh.
  • the particles of calcium carbonate are larger than 60 mesh, calcium sulfate coating is likely to occur during the slow decomposition of calcium carbonate, resulting in incomplete reaction and affecting the purity of the final product.
  • the mass ratio of the phosphogypsum to the carbonate is (4-9):1; further preferably, the mass ratio of the phosphogypsum to the carbonate is (7-9):1.
  • the acid liquid used in the primary acidolysis step is at least one of nitric acid and sulfuric acid; further preferably, the acid liquid used in the primary acidolysis step is sulfuric acid.
  • the amount of sulfuric acid (calculated as pure sulfuric acid) is 18% to 22% of the mass of phosphogypsum.
  • the amount of sulfuric acid (calculated as pure sulfuric acid) is 6% to 8% of the mass of phosphogypsum.
  • the acid liquid used in the secondary acidolysis step is at least one of nitric acid and sulfuric acid; further preferably, the acid liquid used in the secondary acidolysis step is sulfuric acid.
  • the sulfuric acid added in the present invention has two destinations. One part reacts with calcium salt to form calcium sulfate precipitate and remains in the gypsum to improve the grade of gypsum. The remaining part returns to the phosphoric acid device with the lotion to reduce the sulfuric acid consumption of the phosphoric acid device.
  • the sulfuric acid is sulfuric acid with a mass fraction of 30% to 50%; further preferably, the sulfuric acid is sulfuric acid with a mass fraction of 35% to 45%.
  • the temperature of the primary acid hydrolysis is 25 to 90°C.
  • the temperature of the secondary acidolysis is 65-85°C.
  • the second acidolysis time is 1 to 2 hours.
  • the step of mixing phosphogypsum and carbonate for primary acidolysis is as follows: mixing phosphogypsum, carbonate and water to prepare slurry A, and then passing acid liquid from the bottom of slurry A and stirring to obtain slurry A containing Foam slurry; further preferably, the step of mixing phosphogypsum and carbonate for primary acidolysis is specifically: mixing phosphogypsum, carbonate and water to prepare slurry A, and then passing the acid solution from the bottom of slurry A And stir, the acid solution addition time is 15 to 50 minutes, and a foam-containing slurry is obtained.
  • the generated carbon dioxide gas can be hydraulically cut into fine particles to obtain Foamy slurry.
  • the acidolysis of the residual phosphate rock and the decomposition of the carbonate are carried out simultaneously, and carbon dioxide gas is generated.
  • the carbon dioxide gas is cut by hydraulic power (vigorous stirring) to generate fine foam, and the generated fine foam is mixed with the The reaction slurry is fully contacted and collides or adheres to separate the organic impurities from the phosphogypsum.
  • the stirring rate is 300-1000r/min; further preferably, the stirring rate is 300-600r/min; Still further preferably, the stirring rate is 300-500r/min; more preferably, the stirring rate is 350-500r/min.
  • the solid content of the slurry A is 30% to 50%.
  • the temperature of the slurry A is 25 to 90°C.
  • the recovery method further includes the step of letting the primary acid hydrolysis product stand. During the standing process, the primary acid hydrolysis product will separate into layers, with the upper layer being scum containing organic matter.
  • the step of removing the scum is as follows: using a scraper to scrape off the scum layer, and then filtering the scum layer.
  • the solid obtained by the filtration is decolorized residue, and the liquid obtained by the filtration is recovered for use in phosphogypsum. and carbonate to prepare slurry A.
  • the washing adopts a countercurrent washing method.
  • the countercurrent washing has a level of 3 to 5; further preferably, the countercurrent washing has a level of 4.
  • the discharge liquid of the next stage of counter-current washing is used as the washing liquid of the previous stage of counter-current washing.
  • the filter press step specifically includes: transporting the liquid obtained in the filter press step to the phosphoric acid production workshop as a raw material for phosphoric acid production, and preparing the solid obtained in the filter press step into slurry B and then filtering.
  • the solid content of the slurry B is 30% to 50%.
  • a second aspect of the present invention provides a phosphogypsum, which is produced by the method provided by the first aspect of the present invention.
  • the water-soluble phosphorus content in the phosphogypsum is not higher than 0.02%; further preferably, the water-soluble phosphorus content in the phosphogypsum is not higher than 0.016%.
  • the total phosphorus content in the phosphogypsum is not higher than 0.2%; further preferably, the total phosphorus content in the phosphogypsum is not higher than 0.14%.
  • the fluorine content in the phosphogypsum is not higher than 0.04%; further preferably, the fluorine content in the phosphogypsum is not higher than 0.018%.
  • the magnesium content in the phosphogypsum is not higher than 0.02%; further preferably, the magnesium content in the phosphogypsum is not higher than 0.009%.
  • the sodium content in the phosphogypsum is not higher than 0.04%; further preferably, the sodium content in the phosphogypsum is not higher than 0.019%.
  • the iron content in the phosphogypsum is not higher than 0.06%; further preferably, the iron content in the phosphogypsum is not higher than 0.04%.
  • the potassium content in the phosphogypsum is not higher than 0.04%; further preferably, the potassium content in the phosphogypsum is not higher than 0.025%.
  • the aluminum content in the phosphogypsum is not higher than 0.03%; further preferably, the aluminum content in the phosphogypsum Not higher than 0.01%.
  • the whiteness of the phosphogypsum is 70-90; further preferably, the whiteness of the phosphogypsum is 77-90; still more preferably, the whiteness of the phosphogypsum is 77-80.
  • the organic carbon content in the phosphogypsum is not higher than 0.03%; further preferably, the organic carbon content in the phosphogypsum is not higher than 0.014%.
  • a third aspect of the invention provides an application of phosphogypsum in building materials.
  • the building material is building plaster.
  • a fourth aspect of the present invention provides a phosphogypsum recovery system.
  • the recovery system is used to implement the phosphogypsum recovery method provided by the first aspect of the present invention.
  • the recovery system includes an acidolysis device, a square tank, Formation tank, filtration system and counter-current washing device.
  • the bottom of the acidolysis device is provided with a first acid liquid inlet.
  • the acidolysis device is connected to a square tank.
  • a scraper is provided on the square tank.
  • the square tank is connected to the formation tank.
  • the formation tank is provided with a second acid liquid inlet, the formation tank is connected to the filtration system, and the solid outlet of the filtration system is connected to the countercurrent washing device.
  • Phosphogypsum and carbonate are mixed and acidolyzed once in the acidolysis device, and then transported to a square tank.
  • the scum is removed by a scraper on the square tank, and then a second acidolysis is performed in the formation tank.
  • Purified phosphogypsum is obtained after pressure filtration through a filtration device and washing through a countercurrent washing device.
  • the mixture of phosphogypsum and carbonate in the present invention is transported to the acidolysis device after slurrying, and then the acid liquid is introduced from the first acid liquid inlet at the bottom of the acidolysis device, thereby realizing primary acidification in the acidolysis device.
  • Decomposition the product after one acidolysis is transported to a square tank, and left to stratify in the square tank.
  • the top of the square tank is a scum layer containing organic matter
  • the bottom of the square tank is the phosphogypsum slurry after one acidolysis.
  • the scraper machine on the tank scrapes off the scum layer, and the slurry after scraping off the scum is transported from the bottom of the square tank to the formation tank, and the acid liquid is introduced into the formation tank through the second acid inlet on the formation tank. , perform secondary acidolysis in the formation tank, and the product after the secondary acidolysis is passed into the filtration system for filtration, and then the solids filtered by the filtration system are washed countercurrently using a countercurrent washing device.
  • the first acid liquid inlet is connected to an acid liquid storage device.
  • the second acid liquid inlet is connected to an acid liquid storage device.
  • the filtration system includes a filter press device, a slurry adjusting device and a filtering device.
  • the filter press device is connected to the formation tank, the liquid outlet of the filter press device is connected to the phosphoric acid production system, and the solid outlet of the filter press device is connected to the conditioning tank.
  • the slurry device is connected, the slurry adjusting device is connected with the filter device, and the solid outlet of the filter device is connected with the countercurrent washing device.
  • the secondary acid hydrolysis product in the formation tank is transported to the filter press device for filtering.
  • the liquid after filtering by the filter press device is transported to the phosphoric acid production system through the liquid outlet to recover the phosphorus component in the phosphogypsum.
  • the phosphorus component is recovered It can then be used to produce phosphoric acid.
  • the solids after filtering by the filter press device are transported to the slurry adjustment device through the solid outlet on the filter press device for slurry adjustment. After the slurry is adjusted, the slurry is transported to the filter device for filtration. The solids filtered by the filter device are washed by the countercurrent washing device.
  • the recovery system further includes a pulp mixer, and the pulp mixer is connected to the acidolysis device.
  • the slurry mixing machine is used to slurry the mixture of phosphogypsum and carbonate.
  • the pulp mixer is connected to the liquid outlet of the filter device.
  • the liquid filtered by the filtration device is transported to the pulp mixing machine to be used as liquid for pulp mixing.
  • the pulp mixer is connected to a water source.
  • the filter device is a belt filter device.
  • the pulp adjusting device is connected to a water source.
  • the square tank is connected to a filter press, and the liquid outlet of the filter press is connected to a pulp mixer.
  • the scraper on the square tank scrapes the scum layer into the filter press for filtering.
  • the liquid when filtered by the filter press is transported to the pulp mixer through the discharge port of the filter press to be used as liquid for pulp mixing.
  • the solid produced by the filter press is decolorized residue.
  • the counter-current washing device has a washing level of 3 to 6 levels; further preferably, the counter-current washing device has a washing level of 4 levels.
  • the countercurrent washing device includes a first-level countercurrent washing area, a second-level countercurrent washing area, a third-level countercurrent washing area and a fourth-level countercurrent washing area.
  • the washing liquid inlet of the first-level counter-current washing zone is connected to the liquid outlet and the water source of the second-level counter-current washing zone respectively.
  • the liquid discharge port of the first-level countercurrent washing zone is connected to the pulp adjusting device.
  • the washing liquid inlet of the second-level counter-current washing zone is connected to the liquid outlet and the water source of the third-level counter-current washing zone respectively.
  • the washing liquid inlet of the third-stage counter-current washing zone is connected to the liquid outlet and the water source of the fourth-stage counter-current washing zone respectively.
  • the washing liquid inlet of the four-stage countercurrent washing zone is connected to a water source.
  • the water source is a process water source.
  • the beneficial effects of the present invention are: after the phosphogypsum recovery method in the present invention recovers the phosphogypsum, the contents of various impurities in the phosphogypsum are significantly reduced compared with before treatment, and the soluble phosphorus of the phosphogypsum is reduced. to less than 0.016%, the total phosphorus dropped to about 0.1%, the pH of the gypsum leachate increased from 1 to 2 to 6 to 7, the gypsum leachate can be discharged directly without treatment, and the contents of Mg, Na, Fe, K, Al and organic carbon were all the same. It has been greatly reduced. The whiteness of gypsum has increased from 22.71 to about 78.
  • the degree of purification of gypsum is much higher than that of conventional washing and acid hydrolysis processes.
  • the quality index of the treated phosphogypsum is better than the relevant requirements of the building gypsum powder standard. It can be Directly used as building plaster.
  • the recovery method in the present invention can realize the recovery of phosphorus in phosphogypsum, and the recovered phosphorus components are directly transported to the phosphoric acid production workshop for use in the production of phosphoric acid.
  • the waste liquid produced by filtration, washing and filter pressing in this recycling method can be recycled and reused, which improves the utilization rate of raw materials, reduces the treatment cost of waste liquid, and saves production costs.
  • the recycling system in the present invention has a high degree of automation, low labor intensity, simple equipment, low equipment cost, and easy maintenance. Automatic recycling of phosphogypsum can be realized, and the waste liquid during the recycling process can be directly recycled, resulting in high raw material utilization.
  • Figure 1 is a schematic flow chart of the recovery method of phosphogypsum in Examples 1 to 4 of the present invention.
  • Figure 2 is a schematic structural diagram of the recovery system in Embodiment 6 of the present invention.
  • Figure 3 is a schematic structural diagram of a countercurrent washing device in Embodiment 6 of the present invention.
  • Examples 1 to 4 to determine the component content of purified phosphogypsum are the quinoline phosphomolybdate gravimetric method, ICP-MS and the test method described in Q/520122K-002-2020.
  • This example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the color of the phosphogypsum is gray-black, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, and the total phosphorus It is 1.524%, and the pH of the leach solution is between 1 and 2;
  • step (6) The upper layer of scum scraped off in step (5) is sent to a filter press for filtering.
  • the filter cake is decolorized residue.
  • the filtrate is recovered and transported to step (2) for preparing slurry A;
  • step 10 Filter the slurry obtained in step (9).
  • the filtered filtrate can be recovered and transported to step (2) to prepare slurry A.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (10) the filtrate of the last level of washing during the 4-level countercurrent washing is used as the washing liquid in the previous level of washing.
  • the washing liquid of the last level of washing is process water.
  • the temperature and dosage of the process water are the same as those in the steps of this embodiment ((10)).
  • the process water in 2) is the same.
  • the final filtrate from countercurrent washing in step (10) can be recovered and transported to step (9) to slurry the filter cake.
  • the water-soluble phosphorus in the purified gypsum is 0.0136%
  • the total phosphorus is 0.1142%
  • the water-soluble fluorine is 0.0167%
  • the free water content is 23.14%, dried at 45°C
  • the resulting gypsum is white powder with a whiteness of 78.92.
  • This example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the color of the phosphogypsum is gray-black, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the gypsum is 0.4986%, and the total phosphorus is 1.524%, the pH of the leach solution is between 1 and 2;
  • step (6) Send the scum on the surface of the slurry scraped off in step (5) to a filter press for filtration.
  • the filtrate after the filtration is recovered and processed and sent to step (2) for preparing slurry A;
  • step (5) The slurry after defoaming in step (5) is moved into the formation tank, and the diluent prepared in step (3) is added to the formation tank again.
  • Sulfuric acid the amount of dilute sulfuric acid added is 150kg;
  • step 10 Filter the slurry obtained in step (9).
  • the filtered filtrate can be recovered and transported to step (2) to prepare slurry A.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (10) the filtrate produced by the last level of washing during countercurrent washing is used as the washing liquid of the previous level of washing.
  • the washing liquid of the last level of washing is process water.
  • the temperature, composition and dosage of the process water are the same as those in the steps of this embodiment ( The process water in 2) is the same.
  • the final filtrate from countercurrent washing in step (10) can be recovered and transported to step (9) to slurry the filter cake.
  • the water-soluble phosphorus in the purified gypsum is 0.0124%
  • the total phosphorus is 0.0912%
  • the water-soluble fluorine content is 0.0142%
  • the free water is 22.34%, dried at 45°C
  • the resulting gypsum is white powder with a whiteness of 78.31.
  • This example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the color of the phosphogypsum is gray-black, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the gypsum is 0.4986%, and the total phosphorus is 1.524%, the pH of the leach solution is between 1 and 2;
  • step (6) Send the scum on the surface of the slurry scraped off in step (5) to a filter press for filtration.
  • the filtrate after the filtration is recovered and processed and transported to step (2) for adjustment to slurry A;
  • step (7) Move the defoamed slurry in step (5) into the formation tank, and add the slurry prepared in step (3) to the formation tank again.
  • Dilute sulfuric acid the added amount of dilute sulfuric acid is 120kg;
  • step 10 Filter the slurry obtained in step (9).
  • the filtered filtrate can be recovered and transported to step (2) to prepare slurry A.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (10) the filtrate produced by the last level of washing during countercurrent washing is used as the washing liquid of the previous level of washing.
  • the washing liquid of the last level of washing is process water.
  • the temperature, composition and dosage of the process water are the same as those in the steps of this embodiment ( 2) Same.
  • the final filtrate from countercurrent washing in step (10) can be recovered and transported to step (9) to slurry the filter cake.
  • the water-soluble phosphorus in the purified gypsum is 0.01214%
  • the total phosphorus is 0.1045%
  • the water-soluble fluorine content is 0.0134%
  • the free water is 22.58%, dried at 45°C
  • the resulting gypsum is white powder with a whiteness of 78.12.
  • This example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the color of the phosphogypsum is gray-black, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the gypsum is 0.4986%, and the total phosphorus is 1.524%, the pH of the leach solution is between 1 and 2;
  • step (6) Send the scum on the surface of the slurry scraped off in step (5) to a filter press for filtration.
  • the filtrate after the filtration is recovered and processed and transported to step (2) for adjustment to slurry A;
  • step (5) The slurry after defoaming in step (5) is moved into the formation tank, and the diluent prepared in step (3) is added to the formation tank again.
  • Sulfuric acid the amount of dilute sulfuric acid added is 120kg;
  • step 10 Filter the slurry obtained in step (9).
  • the filtered filtrate can be recovered and transported to step (2) to prepare slurry A.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (10) the filtrate from the last stage of washing in the 4-stage countercurrent washing is used as the washing liquid of the previous stage of washing.
  • the washing liquid of the last stage of washing is process water.
  • the temperature, composition and dosage of the process water are the same as those in this embodiment. Same as step (2).
  • the final filtrate from countercurrent washing in step (10) can be recovered and transported to step (9) to slurry the filter cake.
  • the water-soluble phosphorus in the purified gypsum is 0.0114%
  • the total phosphorus is 0.1113%
  • the water-soluble fluorine content is 0.0127%
  • the free water is 21.64%, dried at 45°C
  • the resulting gypsum is white powder with a whiteness of 79.24.
  • This example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the color of the phosphogypsum is gray-black, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the gypsum is 0.4986%, and the total phosphorus is 1.524%, the pH of the leach solution is between 1 and 2;
  • process water is a mixture of clean water and steam condensate, and the temperature is controlled at 70°C;
  • Acid decolorization Move the slurry prepared in step (3) into the reaction vessel, and stir continuously at a rotation speed of 400r/min. Add the dilute sulfuric acid prepared in step (4) into the slurry from the bottom of the reaction vessel. , the adding amount of dilute sulfuric acid is 950kg, and the adding time is controlled at 35min;
  • the filtrate of the last stage of countercurrent washing in step (11) is used as the washing liquid of the previous stage of countercurrent washing.
  • the washing liquid of the last stage of countercurrent washing is process water.
  • the amount of process water is 5.5 tons. , the temperature is controlled at 70°C;
  • the fluorine and water in the 5 batches of phosphogypsum were The contents of dissolved P 2 O 5 , total P 2 O 5 , Mg, Na, Fe, K, Al and organic carbon were greatly reduced. Among them, the whiteness of phosphogypsum increased from 22.71 to about 78. The soluble phosphorus is reduced to less than 0.016%, the total phosphorus is reduced to about 0.1%, the pH of the gypsum leachate is increased from 1 to 2 to 6 to 7, and can be directly discharged. The degree of purification of gypsum is much higher than that of conventional water washing in the existing technology. And the acid hydrolysis process, the quality index of the treated phosphogypsum is better than the relevant requirements of the building gypsum powder standard, and can be directly used in building materials.
  • this embodiment provides a phosphogypsum recovery system.
  • the phosphogypsum recovery methods in Embodiments 1 to 5 of the present invention can all be recovered using the recovery system in this embodiment.
  • the phosphogypsum recovery system in this embodiment includes a pulp mixing machine, an acidolysis device, a square tank, a formation tank, a filter press device, a filter press, a pulp mixing device, a filtering device and a countercurrent washing device.
  • the pulp mixing machine is equipped with Solid raw material inlet and liquid inlet. Add phosphogypsum and carbonate through the solid raw material inlet of the pulp mixer.
  • the liquid inlet of the pulp mixer is connected to the water source, the drain port of the filter device, and the drain port of the filter press through pipelines respectively. connection, the slurry outlet of the pulp mixer is connected to the acidolysis device.
  • the bottom of the acidolysis device is provided with a first acid liquid inlet.
  • the first acid liquid inlet is connected to the sulfuric acid storage device through a pipeline.
  • the acidolysis device is connected to a square tank. On the square tank It is equipped with a scraper, the square trough is connected to the filter press, the liquid outlet of the filter press is connected to the pulp mixing machine, the square trough is connected to the forming tank, the forming tank is provided with a second acid liquid inlet, and the second acid
  • the liquid inlet is connected to the sulfuric acid storage device, the formation tank is connected to the filter press device, the liquid outlet of the filter press device is connected to the phosphoric acid production system, the solid outlet of the filter press device is connected to the slurry mixing device, and the slurry mixing device is connected to the water source and water source through pipelines.
  • the countercurrent washing device is connected, the pulp mixing device is connected with the belt filter device, the liquid outlet of the belt filter device is connected with the pulp mixing machine, and the solid outlet of the belt filter device is connected with the countercurrent washing device.
  • the number of washing levels of the countercurrent washing device in this embodiment is 4.
  • the countercurrent washing device includes a first-level countercurrent washing area, a second-level countercurrent washing area, a third-level countercurrent washing area and a fourth-level countercurrent washing area.
  • the first-level countercurrent washing area The washing liquid inlet is connected to the water source and the drain port of the secondary countercurrent washing area.
  • the drain port of the first-level countercurrent washing area is connected to the pulp mixing device.
  • the washing liquid inlet of the second-level counter-current washing zone is connected to the water source and the drain port of the third-level counter-current washing zone respectively; the washing liquid inlet of the third-level counter-current washing zone is connected to the water source and the drain port of the fourth-level counter-current washing zone respectively.
  • the washing liquid inlet of the four-stage counter-current washing zone is connected to the water source, and the washed solids in the four-stage counter-current washing zone are recovered phosphogypsum.
  • the slurry mixer When in use, first add phosphogypsum and carbonate and the sizing liquid into the slurry mixer for slurry mixing. After the slurry is mixed, the slurry is transported to the acidolysis device. Dilute sulfuric acid is introduced from the bottom of the acidolysis device and carried out once. After acidolysis reaction, the acidolysis product is then transported to a square tank and allowed to stand for stratification. The scraper on the square tank scrapes the scum layer into a filter press for filtering. The solid after filtering is decolorized residue. The liquid after filtering can be used in the pulp mixer to prepare phosphogypsum and carbonate slurry liquids.
  • the remaining slurry in the square tank is transported to the formation tank, and then sulfuric acid is added to the formation tank for a secondary acidolysis reaction.
  • the slurry is transported to the filter press device for filter press, and the liquid produced by the filter press is transported to Phosphoric acid production system is used to produce phosphoric acid, and the solids produced by filter press
  • the pulp is mixed through the pulp mixing device and then transported to the belt filter device for filtration.
  • the liquid used in the pulp mixing device comes from process water or the liquid discharged from the countercurrent washing device.
  • the liquid produced by the belt filter device is transported to the slurry mixer for use as liquid for slurry mixing.
  • the solid produced by the belt filter device is transported to the countercurrent washing device. After being washed by the countercurrent washing device, purified phosphogypsum is obtained.
  • the recovery method of phosphogypsum in this comparative example specifically includes the following steps:
  • This comparative example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the phosphogypsum is gray-black in color, has a whiteness of 22.71, a free water content of 25.71%, a water-soluble phosphorus content of gypsum of 0.4986%, and a total phosphorus of 1.524%, the pH of the leach solution is between 1 and 2;
  • step (3) Place the material weighed in step (2) into a container, add 5.5 tons of process water and stir to form a uniform slurry.
  • the process water is a mixture of clean water and steam condensate, and the temperature is controlled at 70°C;
  • Acid decolorization Move the slurry prepared in step (3) into the reaction vessel, and stir continuously at a rotation speed of 400r/min. Add the dilute sulfuric acid prepared in step (4) into the slurry from the bottom of the reaction vessel. , the adding amount of dilute sulfuric acid is 1310kg, and the adding time is controlled at 35min;
  • step (7) The foamy liquid scraped out by the scraper in step (7) is sent to the filter press for filtration processing.
  • the filter cake is decolorized residue.
  • the filtrate after filtration is recovered and processed and sent to step (3) for use in seasoning slurry. ;
  • step 10 Filter the slurry A obtained in step (10).
  • the filtered filtrate can be recovered and transported to step (3) to prepare the slurry.
  • the filtered cake is subjected to 4-stage countercurrent washing to obtain purified phosphogypsum. ;
  • step (11) during the 4-stage countercurrent washing, the filtrate from the last stage of washing is used as the washing liquid of the previous stage of washing.
  • the washing liquid in the first-level washing is process water, and the temperature, composition and dosage of the process water are the same as in step (3) of this comparative example.
  • the final filtrate from countercurrent washing in step (11) can be recovered and transported to step (10) to slurry the filter cake.
  • the components of the purified phosphogypsum obtained in this comparative example were analyzed.
  • the analysis results are shown in Table 2 below.
  • the analysis methods used were quinoline phosphomolybdate gravimetric method (for analyzing phosphorus components) and ICP-MS (for analyzing metals). Composition) and the test method recorded in Q/520122K-002-2020 (for analyzing organic carbon composition), the data in Table 2 are based on the dry mass of purified phosphogypsum after removing free water.
  • Comparative Example 1 only performed one acidolysis step on phosphogypsum.
  • the content of water-soluble F, water-soluble P 2 O 5 , Mg, Na and other impurities in the recovered phosphogypsum are higher, it can be seen that the purity of the recovered phosphogypsum can be improved by using two acidolysis steps.
  • the recovery method of phosphogypsum in this comparative example specifically includes the following steps:
  • This comparative example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the phosphogypsum is gray-black in color, has a whiteness of 22.71, a free water content of 25.71%, a water-soluble phosphorus content of gypsum of 0.4986%, and a total phosphorus of 1.524%, the pH of the leach solution is between 1 and 2;
  • step (6) Use a scraper to scrape off the upper black oily liquid in step (5) to separate the floating organic matter. Recover the oily liquid scraped off by the scraper and put activated carbon into it to absorb the organic matter. After the adsorption is completed, press the liquid Filter, and the obtained filter cake is decolorized residue. The filtrate after pressure filtration is recovered and processed and then transported to step (2) for use in seasoning slurry;
  • step (7) Perform pressure filtration on the complete slurry formed in step (7).
  • the filtrate recovered by the filtration pressure will be recycled and processed and sent to the phosphoric acid workshop as raw material for phosphoric acid production.
  • the filter cake after filtration is added with process water to make slurry.
  • the process water The temperature, composition and dosage are the same as step (2) of this comparative example to obtain slurry A;
  • step (8) Filter the slurry obtained in step (8).
  • the filtered filtrate can be recovered and transported to step (2) to prepare slurry A.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (9) during the 4-stage countercurrent washing, the filtrate from the last stage of washing is used as the washing liquid of the previous stage of washing.
  • the washing liquid of the last stage of washing is process water.
  • the temperature, composition and dosage of the process water are the same as those in this comparative example. Same as step (2).
  • the final filtrate from countercurrent washing in step (9) can be recovered and transported to step (8) to slurry the filter cake.
  • the components of the purified phosphogypsum obtained in this comparative example were analyzed.
  • the analysis results are shown in Table 3 below.
  • the analysis methods used were quinoline phosphomolybdate gravimetric method (for analyzing phosphorus components) and ICP-MS (for analyzing metals). Composition) and the test method recorded in Q/520122K-002-2020 (for analyzing organic carbon composition), the data in Table 3 are based on the dry mass of purified phosphogypsum after removing free water.
  • the recovery method of phosphogypsum in this comparative example specifically includes the following steps:
  • This comparative example uses phosphogypsum from a phosphate compound fertilizer factory in Hubei province.
  • the phosphogypsum is gray-black in color, has a whiteness of 22.71, a free water content of 25.71%, a water-soluble phosphorus content of gypsum of 0.4986%, and a total phosphorus of 1.524%, the pH of the leach solution is between 1 and 2;
  • step (3) Place the material weighed in step (2) into a container, add 5.5 tons of process water and stir to form a uniform slurry.
  • the process water is a mixture of clean water and steam condensate, and the temperature is controlled at 70°C;
  • Acid decolorization Move the slurry prepared in step (3) into the reaction vessel, and stir continuously at a rotation speed of 400r/min. Add the dilute sulfuric acid prepared in step (4) into the slurry from the bottom of the reaction vessel. , the adding amount of dilute sulfuric acid is 950kg, and the adding time is controlled at 35min;
  • step (10) Filter the slurry obtained in step (10).
  • the filtered filtrate can be recovered and transported to step (3) to prepare the slurry.
  • the filter cake is washed with four levels of countercurrent to obtain purified phosphogypsum;
  • step (11) during the 4-stage countercurrent washing, the filtrate from the last stage of washing is used as the washing liquid of the previous stage of washing.
  • the washing liquid of the last stage of washing is process water.
  • the temperature, composition and dosage of the process water are the same as those in this comparative example.
  • Step (3) is the same.
  • the final filtrate from countercurrent washing in step (11) can be recovered and transported to step (10) to slurry the filter cake.
  • the components of the purified phosphogypsum obtained in this comparative example were analyzed.
  • the analysis results are shown in Table 4 below.
  • the analysis methods used were quinoline phosphomolybdate gravimetric method (for analyzing phosphorus components) and ICP-MS (for analyzing metals). Composition) and the test method recorded in Q/520122K-002-2020 (for analyzing organic carbon composition), the data in Table 4 are based on the dry mass of purified phosphogypsum after removing free water.
  • Comparative Example 3 reduced the amount of soluble carbonate in carbonate when recovering phosphogypsum.
  • the water-soluble F, water-soluble P 2 O 5 , and water-soluble carbonate in the recovered phosphogypsum were The contents of impurities such as Mg and Na increased relatively, especially the total P 2 O 5 content increased significantly. It can be seen that when recovering phosphogypsum, adding carbonate in the first acidolysis step can significantly increase the recovered phosphorus.
  • the purity of gypsum reduces the impurity content of organic carbon, and when the content of soluble carbonate is greater than 40%, it is beneficial to release various impurities wrapped in phosphogypsum, making the recovered phosphogypsum higher in purity.

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Abstract

La présente invention divulgue un procédé de récupération de phosphogypse. Le procédé de récupération comprend les étapes suivantes, consistant à : mélanger du phosphogypse avec du carbonate pour une acidolyse primaire, éliminer la mousse flottante, effectuer une acidolyse secondaire, puis effectuer un pressage sur filtre et un lavage pour obtenir du phosphogypse purifié. Selon le procédé de récupération de phosphogypse de la présente invention, après la récupération du phosphogypse, les indices de performance du phosphogypse sont remarquablement améliorés par rapport à ceux du phosphogypse avant traitement, le phosphore soluble du phosphogypse étant réduit à 0,016 % ou moins, le phosphore total étant diminué à environ 0,1 %, la valeur de pH d'une solution de lixiviation de gypse étant augmentée de 1-2 à 6-7, la solution de lixiviation de gypse pouvant être directement évacuée sans traitement, la teneur en Mg, Na, Fe, K, Al et en carbone organique étant fortement réduite, la blancheur du gypse étant augmentée de 22,71 à environ 78, le degré de purification du gypse étant beaucoup plus élevé que celui des procédés classiques de lavage à l'eau et d'acidolyse et le phosphogypse traité présente un indice de qualité supérieur aux exigences associées de normes de poudre de gypse de construction et peut être directement utilisé en tant que gypse de construction.
PCT/CN2023/077685 2022-09-06 2023-02-22 Procédé de récupération de phosphogypse WO2024051103A1 (fr)

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