Device for removing soluble fluorine and phosphorus in phosphogypsum

Abstract

The utility model provides a device for removing soluble fluorine and phosphorus in ardealite. An ardealite raw ore storage tank is connected with a precipitation tank I; the precipitation tank is connected with the purification tank; the precipitation tank is connected with the aeration tank; the purification tank is connected with the purification generator; the purification generator is connected with the filter tank; the filter tank is connected with the water purifying device; the water purifying device is connected with the reservoir; the filter tank is connected with the sedimentation tank; the sedimentation tank is connected with the aeration tank; and the aeration tank is connected with the pressure filter. The flow device for purifying and utilizing the soluble components of the phosphogypsum has the advantages that impurities and recyclable substances in the phosphogypsum are effectively extracted and separated, purified water generated in the flow can circularly enter the flotation process of the phosphogypsum, various components in the soluble components of the phosphogypsum are fully utilized, and the flotation efficiency of the phosphogypsum is improved. And the recyclability of the ardealite treatment process is improved.

Description

TECHNICAL FIELD

[0001] The utility model discloses the phosphogypsum resource utilization field, and specifically relates to phosphogypsum soluble component and soluble fluorine phosphorus solidification device. BACKGROUND

[0002] Phosphogypsum is the main by-product in the production process of industrial wet-process phosphoric acid, which contains residual phosphoric acid, sulfuric acid, fluoride and heavy metals (such as arsenic, cadmium, lead, etc.) and other soluble salts and other insoluble impurities. When phosphogypsum is stored, the soluble harmful components in the phosphogypsum will dissolve in water to form a mixed solution under the influence of rainwater erosion and other factors. If these solutions are directly discharged without treatment, the acidic components in them will cause soil acidification, affecting the soil microbial environment and vegetation growth. High concentrations of fluoride and heavy metals will pollute surface water and groundwater, and after entering the water body, they may be enriched through the food chain, endangering the ecological system and human health. With the improvement of environmental protection requirements, the treatment and application of the soluble components in phosphogypsum that are harmful to the environment are becoming increasingly important in order to avoid serious pollution to the environment.

[0003] As a recyclable resource with great potential, phosphogypsum can be applied in the fields of agriculture, chemical industry, cement, and building materials industry. Currently, phosphogypsum is mainly used in the building materials industry. After proper treatment, phosphogypsum can be used as an important building material. By treating phosphogypsum, the soluble components and elements such as fluorine and phosphorus that affect building materials can be extracted, which can improve the quality of phosphogypsum and make it more suitable for application in the building materials industry. A large number of studies have found that after treatment, soluble fluorine, soluble phosphorus, eutectic fluorine, and eutectic phosphorus in phosphogypsum can strengthen building materials and prolong their service life. Fluorine element impurities in phosphogypsum can be treated to make fluorocarbon paint, which can resist ultraviolet rays, acid rain, and other erosion to prolong the service life of building materials; phosphorus elements can be used to make phosphorus-based flame retardants, which can effectively organize flame spread and improve the fireproof performance of building materials, making them more environmentally friendly than traditional halogen-based flame retardants and in line with China's green development concept. Other soluble components in phosphogypsum can also be used in certain environmental remediation projects. For example, certain pollutants (such as heavy metals and difficult-to-degrade substances) can be fixed by reacting with soil, sediment, etc., thereby reducing the migration and diffusion of these harmful substances and helping to restore the polluted ecological environment. However, if the solution containing the soluble components of phosphogypsum is directly discharged into the water body without effective treatment, it may cause water quality deterioration and water body eutrophication. The phosphorus element in the solution may promote the excessive growth of algae, leading to water body anoxia, which in turn affects the survival environment of aquatic organisms and may cause large-scale water bloom, endangering water availability.

[0004] In the prior art, the main technical means for treating soluble impurities in phosphogypsum are adsorption, precipitation, membrane separation technology, electrocoagulation, and biological treatment. These technical means can effectively treat and utilize elements such as fluorine and phosphorus in phosphogypsum and other organic substances, and can reduce impurities that are difficult to remove from phosphogypsum. However, in the process of treating soluble impurities, a large amount of resources are consumed, and the by-products produced are difficult to handle and can pollute the environment. Patent 202211147498.5 discloses a method for synergistically harmless treatment of phosphogypsum leachate. The invention adjusts the pH of the mixed system with alkaline materials, performs solid-liquid separation after sufficient reaction, then adds phosphate to the filtrate in a certain proportion, performs solid-liquid separation after sufficient reaction, and can effectively treat phosphogypsum leachate, but the by-products are more and the yield is lower. Patent 202310220713.8 discloses a method for resourceful treatment of phosphogypsum leachate. The invention uses a multi-stage precipitation-filtration device to precipitate and purify the phosphogypsum leachate, and finally separates the products, which can effectively separate the products at each stage, but the process is too long and there is a risk of introducing external impurities and contaminating the products. Patent 201410418263.4 discloses a method for closed cycle utilization of phosphogypsum leachate. The invention can effectively mix the leachate from the phosphogypsum yard with the production system wastewater through the leachate collection pool to produce slurry and obtain new phosphogypsum, completing the cycle, but a large amount of high-concentration concentrated sulfuric acid is used in the cycle. Patent 202110501702.8 discloses a method for resourceful treatment and utilization of phosphogypsum leachate. The invention removes metal impurities and precipitates in the leachate by adjusting the pH value, and then treats the obtained filtrate to meet the discharge standard, but the impurities produced during the treatment process need to consume additional resources for treatment.

[0005] In existing literature, membrane separation technology, evaporation concentration method, electrolysis method, and biological treatment method have been reported for removing soluble impurities and separating organic impurities, heavy metal salts, and silicates from phosphogypsum to purify and resourcefully utilize the soluble components in phosphogypsum. However, there is no reported industrial method for purifying soluble components in phosphogypsum, separating heavy metal salts, organic impurities, and resourcefully utilizable products such as fluorite, apatite, and hydroxyapatite from phosphogypsum. SUMMARY

[0006] The utility model discloses a main purpose provides a kind of removal phosphogypsum soluble component and the device of soluble fluorine phosphorus solidification, utilize the element of soluble component in phosphogypsum mainly fluorine, phosphorus and other recyclable elements, with this multistage separation and purification method, soluble component in phosphogypsum is separated into fluorine, phosphorus mineral, organic impurity, pure water and other products, on the basis of completing the purification and separation of phosphogypsum, fluorine, phosphorus element in it is effectively utilized, process water is recycled by separation formula dehydration, process partial realizes process water self-circulation.

[0007] The utility model discloses the following technical scheme can be realized.

[0008] Phosphogypsum soluble component purification and utilization flow device, phosphogypsum raw ore storage tank is connected with sedimentation tank I;

[0009] Sedimentation tank is connected with purification tank;

[0010] Sedimentation tank is connected with aeration tank;

[0011] Purification tank is connected with purification generator;

[0012] Purification generator is connected with filter groove;

[0013] Filter groove is connected with water purification device;

[0014] Water purification device is connected with water storage pool;

[0015] Filter groove is connected with sedimentation tank;

[0016] Sedimentation tank is connected with aeration tank;

[0017] Aeration tank is connected with pressure filter.

[0018] Compared with prior art, the utility model has the advantages that provide a kind of phosphor stone soluble component's purification and utilization flow device, effectively extract and separate the impurity and recyclable material in phosphogypsum, and the clean water generated in flow can be recycled into the flotation process of phosphogypsum, fully utilizes each component in phosphogypsum soluble component, and perfects the recyclability of phosphogypsum treatment process. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 For phosphogypsum soluble component and the device of soluble fluorine phosphorus solidification;I. Sedimentation tank, II. Purification tank, III. Purification generator, IV. Filter groove, V water purification device, VI. Sedimentation tank, VII. Aeration tank, VIII. Pressure filter.

[0020] Figure 2 For the specific flow of purification and utilization of soluble component in phosphogypsum.

[0021] Figure 3 Elemental components in the leachate before and after purification of phosphogypsum and the content of elemental components before and after purification.

[0022] Figure 4 Fluorine and phosphorus content in the leachate before purification.

[0023] Figure 5 Fluorine and phosphorus content in the leachate after preliminary purification in the purification tank II.

[0024] Figure 6 Fluorine and phosphorus content in the solution after completion of purification. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the present application more clear, the technical scheme in the embodiment of the present application will be described clearly and completely below in combination with the drawings in the embodiment of the present application. It should be understood that the specific embodiments described herein are only used to explain the present application and not to limit the present application.

[0026] Embodiment 1

[0027] Phosphogypsum soluble component purification and utilization device, the phosphogypsum accumulation mine is connected with the sedimentation tank I through the feeding machine, and the preliminary purification liquid of the phosphogypsum and the insoluble impurities are obtained

[0028] The sedimentation tank I is connected with the purification tank II and mixed with the water purification material.

[0029] The sediment produced by the sedimentation tank I is discharged into the aeration tank VII.

[0030] The reaction occurs in the purification generator III.

[0031] The filter tank IV separates the impurities and the solution.

[0032] The secondary water purification is completed in the water purification device V.

[0033] The filter tank IV is connected with the sedimentation tank VI.

[0034] The impurities in the sedimentation tank VI pass through the aeration tank VII.

[0035] The mixed solution is separated in the pressure filter VIII.

[0036] The sedimentation tank I is a inclined plate primary sedimentation tank, which performs primary sedimentation after the phosphogypsum accumulation mine is put in, and separates the easily separated substances such as mud and sand.

[0037] The purification tank II is a glass steel water treatment tank, which is purchased from Sichuan Jieming Morning Environmental Protection Equipment Co., Ltd. Its function is to preliminarily remove impurities from the mixed solution of the phosphogypsum accumulation mine, and to preliminarily purify it by adding alum and other substances.

[0038] The purifier III is a SNT glass steel integrated pressure tank, purchased from Luohe Zehai Water Tank in Henan. Its function is to preliminarily treat the mixed solution of the phosphogypsum accumulation mine, remove the easily separated minerals such as SiO2 in it, and achieve preliminary purification.

[0039] The filter tank IV is a vane type filter tank, purchased from Lida Purification Equipment Co., Ltd. Its function is to filter the phosphogypsum accumulation mine solution after the completion of purification, and remove the solid impurities attached in the treatment of the phosphogypsum accumulation mine.

[0040] The water purifying device V is a RO reverse osmosis pure water machine, purchased from Chengdu Infiltration Technology Co., Ltd. Its function is to remove the dissolved salts such as Na + , Mg 2+ , K + in the solution, and reduce the conductivity of the water, so that it can be recycled for industrial production.

[0041] The sedimentation tank VI is a radial flow sedimentation tank, purchased from Shandong Shengguangyuan Environmental Protection Technology Co., Ltd. Its function is to remove the heavy metals and colloidal pollutants in the phosphogypsum accumulation mine solution by adding chemical coagulants in the tank.

[0042] The aeration tank VII is a plug flow aeration tank, purchased from Bohai Environment Company. Its function is to dissolve oxygen in the air into the solution, and exhaust the unnecessary gas and volatile substances in the phosphogypsum accumulation mine solution into the air, so as to achieve the purpose of separating impurities.

[0043] The pressure filter VIII is a full-automatic high-pressure diaphragm filter. Its function is to input the phosphogypsum accumulation mine slurry into the filter chamber under the pressure action of the feed pump, separate the solid and liquid in the filter material through the filter medium (filter cloth), and then input air into the diaphragm to fully squeeze the solid in the filter chamber after the solid in the slurry forms a cake, so as to reduce the water content and obtain high-purity fluorite, apatite and other minerals.

[0044] Example 2

[0045] The device of Example 1 is used, and the phosphogypsum used is the phosphogypsum accumulated in the phosphogypsum mine field of a phosphorus chemical enterprise in Hubei, and its chemical composition is shown in the table:

[0046] Table 1 Analysis data table of phosphogypsum

[0047]

[0048] Table 2 Main chemical components of the original phosphogypsum

[0049]

[0050] The phosphogypsum raw material also contains iron oxide, aluminum oxide, magnesium oxide, iron sulfide, acid insoluble organic matter, etc.

[0051] Figure 1 The process of phosphogypsum soluble components and soluble fluorine phosphorus curing is implemented, including the following steps:

[0052] (1) The phosphogypsum stockpile is added to the precipitation tank I, and is fully stirred and mixed with pure water to make the phosphogypsum effectively dissolved in water. At this time, the fluorine and phosphorus element content in the solution is measured, as shown in Figure 4 .

[0053] (2) The mixed phosphogypsum slurry is transported and separated, wherein the precipitation is introduced into the aeration tank VII through the pipeline, and the solution is introduced into the purification tank II

[0054] (3) The once-filtered solution in the purification tank II is mixed with alum, activated carbon, zeolite and other substances according to a solid-liquid ratio of 1:3, and is stirred and reacted at a pH of 6-7.

[0055] (4) The slurry after reaction in step (2) is introduced into the purification generator III, and calcium chloride and quicklime are added to the purification generator III to configure a solid-liquid ratio of 1:3, and the pH value is adjusted to 7-11. Finally, a solid-liquid mixture of fluorite, apatite and calcium sulfate is obtained.

[0056] (5) The mixed solution after reaction in the purification generator III is introduced into the filter tank IV to separate the mineral components of the solution.

[0057] (6) The solution after separation in step (5) is introduced into the water purification device V to complete the purification of water and is introduced into the water storage tank for storage as recyclable pure water, and the fluorine and phosphorus elements therein are detected, as shown in Figure 5 .

[0058] (7) The precipitation in step (5) is added to the precipitation tank VI

[0059] (8) The precipitation in the precipitation tank VI is introduced into the aeration tank VII together with the precipitation in step (2) for washing.

[0060] (9) The precipitation obtained in step (8) is added to the pressure filter VIII to obtain high-purity fluorite, apatite, silica sand, organic carbon and other substances.

[0061] (10) The solution obtained in step (9) is measured for fluorine and phosphorus content to determine the fluorine and phosphorus curing rate, and the results are shown in Figure 6 .

[0062] The test results are shown in Figures 3-6 . The data is analyzed by liquid chromatography and XRF

[0063] Table 3 Mineralogical analysis of the product after cleaning

[0064]

[0065] Major elements were measured by an ore microscope and trace elements were measured by XRF.

Claims

1. A device for removing soluble fluorine phosphorus in phosphogypsum, characterized in that, a phosphogypsum raw ore storage tank is connected with a precipitation tank I, the precipitation tank I is connected with a purification tank II, the purification tank II is connected with a purification generator III; the purification generator III is connected with a filter tank IV; the filter tank IV is connected with a water purification device V; the water purification device V is connected with a water storage pool.

2. The device for removing soluble fluorine phosphorus in phosphogypsum according to claim 1, characterized in that, the filter tank IV is connected with a precipitation pool VI, the precipitation pool VI is connected with an aeration tank VII; the aeration tank VII is connected with a pressure filter VIII.

3. The device for removing soluble fluorine phosphorus in phosphogypsum according to claim 1, characterized in that, the precipitation tank I is connected with the aeration tank VII, and the aeration tank VII is connected with the pressure filter VIII.

4. The apparatus for removing soluble fluorine phosphorus in ardealite according to claim 1, characterized in that, The purification tank II is a glass steel water treatment tank.

5. The apparatus for removing soluble fluorine phosphorus in ardealite according to claim 1, characterized in that, The purification generator III is an SNT glass steel integrated pressure tank.

6. The apparatus for removing soluble fluorine phosphorus in ardealite according to claim 1, characterized in that, The filter tank IV is a vane type filter tank.

7. The apparatus for removing soluble fluorine phosphorus in ardealite according to claim 1, characterized in that, The water purification device V is an RO reverse osmosis pure water machine.

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