CN114275756A - Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum - Google Patents
Method for recovering phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum Download PDFInfo
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Abstract
The invention relates to the technical field of environmental protection, in particular to a method for recovering a phosphorus resource byproduct magnesium ammonium phosphate in phosphogypsum. Placing phosphogypsum in an acid solution, shaking and filtering to obtain leachate; placing the zirconia beads in the leachate, and performing vibration adsorption to obtain zirconia beads adsorbed with the phosphorus element; placing the zirconium oxide beads adsorbed with the phosphorus element in an alkaline eluent to shake and elute to obtain an eluent containing the phosphorus element; adding magnesium salt and ammonium salt into the eluent containing phosphorus element, mixing uniformly to obtain reaction liquid, stirring for reaction, and filtering to obtain precipitate, wherein the precipitate is magnesium ammonium phosphate. The invention relates to a phosphogypsum phosphorus resource recovery technology based on the principles of rapid extraction, selective adsorption, efficient elution and induced crystallization. The soluble phosphorus in the phosphogypsum is efficiently recovered, the selective adsorption material can be recycled after elution, and the crystallized final product has higher economic value, simple process and low cost.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for recovering a phosphorus resource byproduct magnesium ammonium phosphate in phosphogypsum.
Background
Phosphogypsum is a by-product of phosphoric acid (wet-process phosphoric acid) prepared by extracting phosphorite with sulfuric acid, and theoretically, 4.8-5.0 tons of phosphogypsum can be discharged every 1 ton of phosphoric acid produced. Phosphogypsum contains a large amount of soluble phosphorus, and the open-air stockpiling quantity of the phosphogypsum is huge, so that a large amount of land is occupied, and leachate formed by leaching a phosphogypsum yard by rainwater can seriously pollute the land and the water environment.
At present, the recycling of phosphogypsum is carried out in many ways, including preparing sulfuric acid, preparing calcium sulfate whisker, preparing ammonium sulfate/potassium sulfate, preparing paper making filler/coating pigment, preparing building raw materials and products, preparing soil conditioner, preparing fertilizer, preparing road building filling material, preparing nano hydroxyapatite and the like. The phosphorus resource in the phosphogypsum is recovered through a scientific and reasonable process, so that the requirements of agriculture, industry and the like on phosphorus can be supplemented, and the environmental pollution caused by stacking the phosphogypsum can be greatly reduced.
The current technical process for recovering phosphorus resources in phosphogypsum comprises the following steps: chemical precipitation, biological methods, ion exchange methods, and the like. The technical processes have the following defects: (1) the precipitated sludge generated by the chemical precipitation method has complex components, and the iron phosphate, the aluminum phosphate and the calcium phosphate cannot be directly utilized in the form of fertilizer, so the precipitated sludge needs further post-treatment process and has higher cost; when the phosphorus content in the wastewater is low, the precipitation effect is not obvious; (2) the phosphorus-rich activated sludge produced by the biological method has large amount, contains heavy metals and the like, can not be directly used as a fertilizer, and is still very difficult to separate and identify PAO at present, so that the deep research on the EBPR process is greatly limited; (3) the ion exchange method has high cost and complex resin treatment process. In addition to the above phosphorus recovery method, the method of using an adsorbing material to specifically adsorb and then elute phosphorus is also a commonly used phosphorus recovery method, the existing adsorbing material of phosphorus is mainly a metal salt adsorbing material or a metal oxide, however, the metal salt adsorbing material is suitable for weak acidic, neutral and alkaline solutions, and the phosphogypsum leaching liquor has the characteristics of strong acidity, high phosphate concentration and many impurities; the traditional metal oxide adsorbing material is only suitable for adsorbing medium-low concentration phosphate and cannot meet the adsorption requirement of the phosphogypsum leaching liquor with higher phosphate concentration; more importantly, sulfate ions and calcium ions in the phosphogypsum leaching liquor influence the adsorption of metal salts and metal oxides on phosphate, so that the phosphorus adsorption efficiency is not ideal.
Disclosure of Invention
Based on the above, the invention aims to provide a method for recovering magnesium ammonium phosphate as a byproduct of phosphorus resources in phosphogypsum. The invention relates to a phosphogypsum phosphorus resource recovery technology based on the principles of rapid extraction, selective adsorption, efficient elution and induced crystallization. The soluble phosphorus in the phosphogypsum is efficiently recovered, the selective adsorption material can be recycled after elution, and the crystallized final product has higher economic value, simple process and low cost.
The technical scheme provided by the invention is as follows:
a method for recovering phosphorus resources and byproduct magnesium ammonium phosphate in phosphogypsum comprises the following steps:
(1) placing the phosphogypsum in an acid solution, shaking and filtering to obtain leachate;
(2) placing the zirconia beads in the leachate, and performing vibration adsorption to obtain zirconia beads adsorbed with the phosphorus element;
(3) placing the zirconium oxide beads adsorbed with the phosphorus element in an alkaline eluent to shake and elute to obtain an eluent containing the phosphorus element;
(4) adding magnesium salt and ammonium salt into the eluent containing phosphorus element, mixing uniformly to obtain reaction liquid, stirring for reaction, and filtering to obtain precipitate, wherein the precipitate is magnesium ammonium phosphate.
Further, in the step (1), the acid solution is a hydrochloric acid solution with a pH value of 1-2, and the material-to-liquid ratio of the phosphogypsum to the hydrochloric acid solution with a pH value of 1 is 1g:10mL, shaking time 6h, and filtering with 0.45 μm filter.
Further, in the step (2), before placing the zirconia beads in the leachate for oscillation and adsorption, adjusting the pH value of the leachate to 2, and oscillating for 12 hours; the particle size of the zirconia beads is 0.1-0.2mm, and the material-liquid ratio of the zirconia beads to the leaching solution is 1g: 15 ml.
Further, in the step (3), the alkaline eluent is 1M sodium hydroxide solution, and the shaking time is 12 h; the material-liquid ratio of the zirconium oxide beads adsorbed with the phosphorus element to the alkaline eluent is 1g: 15 ml.
Optimal reaction conditions can be obtained by controlling the pH value. Experiments prove that HCl with the pH value of 1 is beneficial to leaching out phosphorus in phosphogypsum, because the phosphogypsum is insoluble in ethanol, slightly soluble in water and soluble in acid, ammonium salt and glycerol; acidic conditions (pH 2) favor the adsorption of phosphorus from the leachate by the zirconia beads because the efficient adsorption characteristics of zirconium oxide to phosphorus are due to the hydrated form of zirconium which can provide hydroxide ions and water molecules, favoring phosphate exchange by producing tetranuclear and octanuclear species, as follows:
while the elution of the phosphorus on the zirconia beads is 1M NaOH, because a large amount of OH-can push the reaction to reversely proceed, the adsorbent loaded with Zr desorbs the adsorbed phosphate radical, and the reaction formula is the same as the above. Further, in the step (4), the magnesium salt is magnesium chloride, the ammonium salt is ammonium chloride, a molar ratio of Mg to N to P in the reaction solution is 2:2:1, and a pH of the reaction solution is 9.5.
As the molar ratio of N/P increases, the phosphorus removal rate increases; and the Mg/P ratio of 1-2 can increase the supersaturation degree of struvite, thus being beneficial to the removal of phosphorus and the generation of precipitates.
Further, in the step (4), the stirring reaction conditions are as follows: the rotating speed is 450r/min, the temperature is 25 ℃, and the time is 3 h.
Further, the zirconia balls after shaking and elution in the step (3) are recycled.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes zirconia bead material as the adsorption material, and the zirconia has higher selective adsorption capacity (the high-efficiency adsorption characteristic of the zirconium oxide to phosphorus is because of the hydration shape of the zirconiumFormula (iii) can provide hydroxide ions and water molecules, facilitating phosphate exchange by producing tetranuclear and octanuclear species. ) The method has the advantages of excellent phosphorus adsorption effect, no toxicity, environmental friendliness, stable chemical property and the like, and is favorable for recycling the zirconium oxide after phosphorus resources are recovered. According to experimental studies, zirconia beads adsorb PO4The capacity of (A) is up to 4948.905132 ug/g. Through detection, the concentration of fluorine ions in the phosphogypsum leaching liquor is up to 4890mg/L, and because of the characteristic of efficient selective phosphate adsorption of zirconia beads, the concentration of the fluorine ions in the eluent is only 54mg/L, and the removal rate is up to 98.89%. In addition, main impurities of sulfate radicals, calcium, magnesium, aluminum, manganese and iron in the phosphogypsum and the leachate can be removed by the method, and the removal rate is over 95 percent.
Drawings
FIG. 1 is a flow chart of a process for recovering phosphorus resources and byproduct magnesium ammonium phosphate from phosphogypsum in an embodiment of the invention;
FIG. 2 is a schematic representation of zirconia beads used in accordance with an embodiment of the present invention;
FIG. 3 is the phosphorus content in phosphogypsum leachate under different pH conditions according to example 2 of the present invention;
FIG. 4 shows the phosphorus content in the supernatant after the zirconium oxide beads are adsorbed in example 2 under different pH conditions;
FIG. 5 shows the phosphorus content of the supernatant after elution of zirconia beads under different pH conditions in example 2 of the present invention;
FIG. 6 is a comparison of the leach liquor of example 2 of the present invention with other ion concentrations in the eluent;
FIG. 7 is a SEM photograph of magnesium ammonium phosphate entities prepared in example 2 of the present invention;
FIG. 8 is an XRD pattern of magnesium ammonium phosphate prepared in example 2 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
FIG. 1 is a flow chart of a process for recovering phosphorus resources and byproduct magnesium ammonium phosphate from phosphogypsum in an embodiment of the invention;
FIG. 2 is a schematic representation of zirconia beads used in accordance with an embodiment of the present invention;
example 1 testing of zirconia beads adsorbing PO4Capacity of
Weighing 3.9545gKH2PO4Dissolved in 800ml of ultrapure water and transferred to a beaker, shaken evenly and transferred to a 1000ml volumetric flask, and the volume is determined to the marked line to obtain PO4 solution with the concentration of 900 ug/ml. Taking 35ml preparedPO4Putting the solution into a 50ml centrifuge tube, weighing 3.1458g of zirconia beads with the particle size of 0.1-0.2mm, putting the zirconia beads into the solution, setting three groups (with the pH of 2,7 and 13 respectively), sealing the centrifuge tube, and oscillating for 24 h; three blank control groups were set simultaneously and the conditions were the same except that no zirconia beads were added. And after the oscillation time is finished, taking out the centrifuge tube, standing for 3 hours, taking supernatant, and testing the phosphorus content. The results show that at pH 2, the zirconia beads possessed a maximum adsorption capacity of 4948.905132 ug/g.
Example 2
(1) Solutions with pH 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 were prepared using ultrapure water, 1MHCl, 1MNaOH and were ready for use. Crushing and grinding the blocky phosphogypsum to be uniform for later use. A leaching experiment is carried out according to the proportion of 1g of phosphogypsum to 10ml of solution, 1g of phosphogypsum and 10ml of prepared solution with different pH values are put into a 50ml centrifugal tube, and the solution is fully oscillated for 6 hours. The mixed solution is filtered by a filter membrane with the aperture of 0.45 mu m, and the content of phosphorus in the filtrate is determined according to GB 11893-1989-ammonium molybdate spectrophotometry for determining total phosphorus in water. As shown in figure 3, the results show that acidic conditions favour the transfer of phosphorus from the phosphogypsum solids into solution, with the highest content of phosphorus being transferred by HCl solution at pH 1.
(2) Leaching the solution with the pH value of 1 obtained in the step (1) to obtain a phosphorus-containing solution, filtering the phosphorus-containing solution through a filter membrane with the pore diameter of 0.45 mu m (detecting that the pH value is 1.15), then putting 15ml of filtrate into a 50ml centrifuge tube, and dripping 1MHCl and 1MNaOH to adjust the pH value of the filtrate to be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12; zirconia beads (the particle diameter is between 0.1 and 0.2 mm) in the shape of a ball are respectively filled into centrifuge tubes filled with solutions with different pH values (the ratio of material to liquid is 1g: 15 ml). Slightly vibrate the centrifugal tube for 12h to prevent the zirconia beads with overlarge vibration amplitude from being adhered to the wall of the centrifugal tube, so that the zirconia beads can effectively adsorb PO in the solution4. And filtering the adsorbed solution through a filter membrane with the aperture of 0.45 mu m, and determining the content of phosphorus in the filtrate according to GB 11893-1989-ammonium molybdate spectrophotometry for determining total phosphorus in water. The results are shown in FIG. 4, where the solution after adsorption was low in phosphorus under acidic and alkaline conditions, indicating that the zirconia beads were effective in adsorbing PO at these pH conditions4Since the leachate has a pH of 1.15, it is economically feasible to useIn other words, the pH 2 solution environment is the optimal adsorption condition.
(3) 15ml of the prepared solution having pH of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 1m naoh was put into a centrifuge tube, and zirconia beads having particle diameters of 0.1 to 0.2mm were put into the centrifuge tube by leaching at pH of 1 and adsorbing at pH of 2 (feed-to-solution ratio 1g: 15 ml). Slightly vibrate the centrifugal tube for 12h to prevent the zirconia beads with overlarge vibration amplitude from adhering to the wall of the centrifugal tube, so that the PO adsorbed by the zirconia beads4The elution was transferred to solution. Filtering the eluted solution through a filter membrane with the aperture of 0.45 mu m, and determining the content of phosphorus in the filtrate according to GB 11893-1989-ammonium molybdate spectrophotometry for determining total phosphorus in water. As shown in FIG. 5, the alkaline condition favors the elution of PO by the zirconia beads41M NaOH solution elution of PO4The efficiency is highest. The results of the recovery rate of the phosphogypsum resource recovery process by the eluents with different pH values are summarized in table 1.
TABLE 1
(4) The concentration of the main cations and anions (fluoride ion, sulfate ion, calcium ion, magnesium ion, aluminum ion, potassium ion, manganese ion, and iron ion) in the phosphogypsum leaching solution (the phosphorus-containing solution eluted by the solution with the pH value of 1 in the step (1)) and the eluent (the eluent eluted by the 1M NaOH solution) was measured (the atomic fluorescence spectrometer is used for cation test, and the anion chromatograph is used for anion test), and the results are shown in FIG. 6. The concentration of fluorine ions in the phosphogypsum leaching liquor is as high as 4890mg/L, because of the characteristic of efficient selective adsorption of phosphate by zirconia beads, the concentration of the fluorine ions in the eluent is only 54mg/L, and the removal rate is as high as 98.89%. In addition, main impurities of sulfate radicals, calcium, magnesium, aluminum, manganese and iron in the phosphogypsum and the leachate can be removed, and the removal rate is over 95 percent.
(5) Eluting the eluent (namely PO) obtained by the elution of the 1M NaOH solution in the step (4)4Solution) 15mL were transferred to a 200mL beaker, and 0.2415g of MgCl were weighed2And 0.135gNH4Cl reagents, each dissolved in 50ml of ultrapure water to give MgCl2Solution and NH4Cl solution, and MgCl2Solution and NH4The Cl solutions were transferred to the containers respectively4In a 200ml beaker of the eluent, the mixture is stirred slightly and kept stand until the pH value is stable, and the pH value of the mixed solution is adjusted to 9.5 by NaOH and HCl. Then at nMg: nN: and (3) placing the beaker of the mixed solution on an electromagnetic stirrer under the conditions of nP (2: 2: 1), pH (9.5) and temperature of 25 ℃, controlling the stirring speed to be 450r/min, and reacting for 3 h. After the precipitate was formed, the beaker containing the mixed solution was allowed to stand, the supernatant was decanted, the precipitate was dried, analyzed by SEM (fig. 7) and XRD (fig. 8), and the purity of magnesium ammonium phosphate was calculated to be 99.351677% according to the following formula.
The figures and the tables referred to in all the examples of the invention indicate that the phosphorus content is 10ml of liquid sample and n-6 indicates 6 samples.
And (4) conclusion: phosphogypsum and hydrochloric acid with pH value of 1 are mixed evenly and oscillated for 6h according to the proportion of 1g to 10 ml. After shaking, the mixed solution was filtered through a 0.45 μm filter membrane, and the supernatant was collected. To the supernatant was added 1M sodium hydroxide solution to make the solution pH 2, zirconia beads were added, and the solution and the beads were gently shaken for 12 h. The zirconia beads were taken out and put into a 1M sodium hydroxide solution, and the solution and the zirconia beads were gently shaken for 12 hours. The zirconia beads are taken out for repeated recycling, and the eluent is high-concentration sodium phosphate solution. Reformulating MgCl2And NH4Cl solution, which is added to the eluent to make nMg: nN: the magnesium ammonium phosphate (MgNH) with the purity of 99.351677 percent is obtained after the reaction of 3 hours and the temperature of 25 ℃ and the stirring speed of 450r/min under the condition that the pH value is controlled to be 9.5 and the nP is 2:2:14PO4·6H2O struvite).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for recovering phosphorus resources and byproduct magnesium ammonium phosphate in phosphogypsum is characterized by comprising the following steps:
(1) placing the phosphogypsum in an acid solution, shaking and filtering to obtain leachate;
(2) placing the zirconia beads in the leachate, and performing vibration adsorption to obtain zirconia beads adsorbed with the phosphorus element;
(3) placing the zirconium oxide beads adsorbed with the phosphorus element in an alkaline eluent to shake and elute to obtain an eluent containing the phosphorus element;
(4) adding magnesium salt and ammonium salt into the eluent containing phosphorus element, mixing uniformly to obtain reaction liquid, stirring for reaction, and filtering to obtain precipitate, wherein the precipitate is magnesium ammonium phosphate.
2. The method for recovering the phosphorus resource byproduct magnesium ammonium phosphate in the phosphogypsum as claimed in claim 1, wherein in the step (1), the acidic solution is hydrochloric acid solution with pH value of 1-2, and the material-to-liquid ratio of the phosphogypsum to the hydrochloric acid solution with pH value of 1 is 1g:10mL, shaking time 6h, and filtering with 0.45 μm filter.
3. The method for recycling phosphorus resource and byproduct magnesium ammonium phosphate in phosphogypsum according to claim 1, wherein in the step (2), before putting zirconia beads in the leachate for oscillation and adsorption, the pH value of the leachate is adjusted to be below 3, and the oscillation time is 12 hours; the particle size of the zirconia beads is 0.1-0.2mm, and the material-liquid ratio of the zirconia beads to the leaching solution is 1g: 15 ml.
4. The method for recycling phosphorus resource byproduct magnesium ammonium phosphate in phosphogypsum according to claim 1, wherein in the step (3), the alkaline eluent is 1M sodium hydroxide solution, and the oscillation time is 12 h; the material-liquid ratio of the zirconium oxide beads adsorbed with the phosphorus element to the alkaline eluent is 1g: 15 ml.
5. The method for recovering phosphorus resource and byproduct magnesium ammonium phosphate from phosphogypsum according to claim 1, wherein in the step (4), the magnesium salt is magnesium chloride, the ammonium salt is ammonium chloride, the molar ratio of Mg to N to P in the reaction solution is 2:2:1, and the pH value of the reaction solution is 9.5.
6. The method for recovering the phosphorus resource byproduct magnesium ammonium phosphate in the phosphogypsum as claimed in claim 1, wherein in the step (4), the stirring reaction conditions are as follows: the rotating speed is 450r/min, the temperature is 25 ℃, and the time is 3 h.
7. The method for recovering the phosphorus resource and byproduct magnesium ammonium phosphate from phosphogypsum according to claim 1, wherein the zirconia balls after shaking elution in the step (3) are recycled.
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