CN113277885A - Resource utilization method of phosphoric acid residues - Google Patents
Resource utilization method of phosphoric acid residues Download PDFInfo
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- CN113277885A CN113277885A CN202110644098.4A CN202110644098A CN113277885A CN 113277885 A CN113277885 A CN 113277885A CN 202110644098 A CN202110644098 A CN 202110644098A CN 113277885 A CN113277885 A CN 113277885A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
- C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
Abstract
The invention relates to a resource utilization method of phosphoric acid residues, belonging to the technical field of clean processing and utilization of phosphorus resources. The invention aims to provide a resource utilization method of phosphoric acid residues. The method comprises the following steps: 1) acid hydrolysis: mixing phosphoric acid residues, metal element-containing substances and water, and carrying out acidolysis reaction to obtain mixed slurry A; 2) roasting: and roasting the mixed slurry A at the roasting temperature of 180-750 ℃ for 0.2-5.0 h to obtain the polyphosphate slow-release fertilizer. The method for preparing the medium trace element polyphosphate slow-release fertilizer by taking the phosphoric acid residues as the main raw material is simple, the cost of the raw material is low, and the metal element substances comprise phosphorus tailings, magnesite, dolomite, calcite, metal oxides, metal hydroxides, sulfates and the like. Not only widens the resource utilization direction of the phosphoric acid slag, reduces the burden of stacking waste resources for phosphorus chemical enterprises at the present stage, but also increases the diversity of phosphate fertilizers, and has important economic and environmental protection significance.
Description
Technical Field
The invention relates to a resource utilization method of phosphoric acid residues, belonging to the technical field of clean processing and utilization of phosphorus resources.
Background
The phosphoric acid residue is a byproduct of extraction, concentration, dearsenification and defluorination processes or storage processes based on a wet-process phosphoric acid process, and the annual yield of the phosphoric acid residue is huge. With the consumption of phosphorus resources and the requirements on environmental protection and green development concepts, the integrated utilization of low-value phosphorus resources such as phosphoric acid residues is urgently needed.
At present, the domestic utilization of the phosphoric acid residues is mainly embodied in four aspects: using the phosphoric acid residues for preparing fertilizer-grade monoammonium phosphate; returning the phosphoric acid residue to the phosphoric acid extraction tank for reuse; the phosphoric acid slag is used for preparing the triple superphosphate; returning the phosphoric acid residue to a phosphorite flotation tank to be used as a pH regulator; the phosphoric acid residue is made into feed grade calcium hydrophosphate after defluorination and dearsenification. Although the research applications can consume a part of the phosphoric acid residues, the phosphoric acid residues are still not fully utilized, the utilization has many defects, and many useful elements in the phosphoric acid residues are not reasonably utilized.
Chinese patent publication No. CN 105439646 a discloses a method for producing phosphorus-magnesium fertilizer by using wet-process phosphoric acid slag, which comprises pressure filtering the slag acid, using the filtrate to prepare diammonium phosphate, and mixing the filter cake with bitter soil to prepare phosphorus-magnesium compound fertilizer. The defects are that the prepared phosphorus-magnesium fertilizer has high fluorine content, low nutrient content and selectivity to slag acid.
Chinese patent publication No. CN 111689875A discloses a method for producing feed-grade urea phosphate from wet-process phosphoric acid residues, which comprises mixing phosphoric acid residues with a urea solution, filtering, adding sodium sulfate into the liquid phase for defluorination, and concentrating to obtain urea phosphate. And (3) introducing sulfuric acid into the solid phase to obtain a fluorosilicic acid solution. The disadvantages are that the whole process needs to introduce sulfuric acid and phosphogypsum by-product is generated.
Chinese patent publication No. CN 106278390A discloses a method for comprehensively recycling wet-process phosphoric acid residues, which comprises mixing phosphoric acid residues with a nitric acid solution, filtering, neutralizing the filtrate with ammonia water, potassium hydroxide and other substances to prepare a ternary fertilizer containing nitrogen, phosphorus and potassium, and preparing filter residues into a superphosphate or medium-low nutrient compound fertilizer. The disadvantage is that the utilization market of the filter residue is low.
The Chinese patent publication No. CN106380231A discloses a method for producing calcium superphosphate by using phosphate rock tailings and phosphoric acid slag acid, which comprises the steps of fully mixing the three raw materials of the phosphate rock tailings, the phosphoric acid slag acid and the phosphate rock powder, and adding concentrated H2SO4Reacting for 1 hour under the stirring state; adding quicklime to neutralize free acid, and then transferring into a compost storehouse for curing for 5-7 days to obtain a qualified common superphosphate fertilizer product. The process requires the introduction of sulphuric acid, with the production of phosphogypsum by-product. And the prepared calcium superphosphate has low nutrient content.
Disclosure of Invention
Aiming at the defects, the invention provides a resource utilization method of phosphoric acid residues, the method is simple and low in cost, and the prepared product can be used as a medium-trace element polyphosphate slow-release fertilizer.
The resource utilization method of the phosphoric acid residues comprises the following steps:
1) acid hydrolysis: mixing phosphoric acid residues, metal element-containing substances and water, and carrying out acidolysis reaction to obtain mixed slurry A; the metal element-containing material comprises at least one of magnesium-containing material, calcium-containing material, iron-containing material, zinc-containing material and manganese-containing material;
2) roasting: and roasting the mixed slurry A at the roasting temperature of 180-750 ℃ for 0.2-5.0 h to obtain the medium-trace element polyphosphate slow-release fertilizer.
In some embodiments of the invention, the phosphoric acid residue is a byproduct of an extraction, concentration, dearsenification and defluorination process or a storage process in a wet-process phosphoric acid process.
In some embodiments of the invention, the elemental metal-containing material is at least one of phosphate tailings, magnesite, dolomite, calcite, limestone, marble, travertine, calcium carbonate, magnesium carbonate, basic magnesium carbonate, metal oxides, metal hydroxides, and sulfates.
In some embodiments of the invention, in step 1), the molar ratio of phosphorus to the metal element in the mixed slurry a is 0.8 to 2.0: 1. In some embodiments of the invention, the molar ratio of phosphorus to metal elements in the mixed slurry a is 1.0-1.8: 1; in some embodiments of the invention, the molar ratio of phosphorus to metal elements in the mixed slurry a is 1.2 to 1.7: 1; in some embodiments of the present invention, the molar ratio of phosphorus to the metal element in the mixed slurry a is 1.4 to 1.6: 1.
In some embodiments of the present invention, in step 1), the temperature of the acidolysis reaction is 20 to 95 ℃, and the time of the acidolysis reaction is 1.0 to 5.0 hours.
In some embodiments of the present invention, the mixed slurry a is dried to obtain a material B, and then the material B is calcined.
In some embodiments of the invention, the drying temperature is less than 120 ℃. In one embodiment of the present invention, the drying temperature is 100 to 120 ℃.
In some embodiments of the invention, in step 2), the calcined material is granulated.
In one embodiment of the present invention, the firing temperature of mixed slurry a in step 2) is >400 ℃.
In another embodiment of the present invention, in step 2), the calcination temperature of the mixed slurry A is 400 ℃ or less.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention explores a medium-trace element polyphosphate slow-release fertilizer prepared from phosphoric acid residues, wherein the water-soluble components account for 3-20 wt%, the citrate-soluble components account for 75-98 wt%, and the low-percentage water-soluble nutrients enable the fertilizer to be applied to soil and not to be easily leached, and the citrate-soluble nutrients with high percentage can continuously provide sufficient nutrition for crops.
2. The metal element-containing substance added in the invention can be replaced by raw ore with less impurities and capable of being decomposed by phosphoric acid, and phosphorus tailings, magnesite, dolomite, calcite, limestone, marble and travertine are typical. Meanwhile, the effective elements such as P, Ca, Mg, Fe, K, S, Mn and the like in the phosphate slag are reserved and utilized by plants, and the fluosilicate in the phosphate slag is treated with HF and SiF in the acidolysis and roasting processes4Overflow of the form(s) gives a high value of additional product. All the used raw materials have a wide selection range, and can be properly replaced by a plurality of industrial wastes, so that the raw material cost is greatly reduced.
3. The preparation method disclosed by the invention is simple in preparation process, convenient and feasible in operation, free of waste slag, green and environment-friendly, and capable of realizing industrial production, reducing the burden of stacking waste resources for phosphorus chemical enterprises at the present stage, and increasing the diversity of phosphate fertilizers.
Detailed Description
The resource utilization method of the phosphoric acid residues comprises the following steps:
1) acid hydrolysis: mixing phosphoric acid residues, metal element-containing substances and water, and carrying out acidolysis reaction to obtain mixed slurry A; the metal element-containing material comprises at least one of magnesium-containing material, calcium-containing material, iron-containing material, zinc-containing material and manganese-containing material;
2) roasting: and roasting the mixed slurry A at the roasting temperature of 180-750 ℃ for 0.2-5.0 h to obtain the polyphosphate slow-release fertilizer.
The method takes the phosphoric acid residues as the main raw material to prepare the medium-trace element polyphosphate slow-release fertilizer, has simple method and low cost of the raw material, not only expands the application direction of the phosphoric acid residues, but also has important economic and environmental protection significance.
Phosphoric acid residues commonly used in the art are suitable for use in the present invention, and in some embodiments of the present invention, the phosphoric acid residues are the residue acids generated in wet-process phosphoric acid processes, including but not limited to, the residue acids generated during concentration, defluorination, dearsenification, storage, etc. of phosphoric acid. In some embodiments of the invention, the phosphoric acid sludge is an evaporation concentrate sludge acid, a phosphoric acid press residue, a defluorination press residue or a storage sediment residue in a wet phosphoric acid process.
The step 1) is acidolysis, wherein the phosphoric acid residue is mixed with substances containing Ca, Mg, Fe, Zn, Mn and the like, and a proper amount of water is added for acidolysis.
The acidolysis of the invention only needs to add water, and other acids do not need to be added, thus reducing the cost. In one embodiment of the invention, the water is added in an amount of 5 to 30 wt% based on the total weight of the whole system.
The acidolysis can obtain the hydrogen phosphate mixed slurry A, wherein the type of the hydrogen phosphate is related to the metal elements in the phosphoric acid residues and the metal elements in the metal element-containing substances.
The metal element-containing material mainly provides metal elements for the product, and materials commonly used in the art can be used, including but not limited to at least one of magnesium-containing materials, calcium-containing materials, iron-containing materials, zinc-containing materials and manganese-containing materials. In some embodiments of the present invention, the metal element substance includes carbonates (phosphate tailings, magnesite, dolomite, calcites, limestone, marble, travertine, calcium carbonate, magnesium carbonate, basic magnesium carbonate, etc.), metal oxides (calcium oxide, magnesium oxide, zinc oxide, etc.), metal hydroxides (calcium hydroxide, magnesium hydroxide, etc.), and sulfates (ferrous sulfate, ferric sulfate, manganese sulfate, zinc sulfate, etc.).
In some embodiments of the invention, in step 1), the molar ratio of phosphorus to the metal element in the mixed slurry a is 0.8 to 2.0: 1. The amount of the metal element is the total amount of the metal element in the metal element-containing substance, and for example, when the metal element-containing substance contains Ca, Mg, Fe, Zn and Mn, the molar ratio of P/(Ca + Mg + Fe + Zn + Mn) is controlled to be 0.8-2.0: 1.
In some embodiments of the invention, the molar ratio of phosphorus to metal elements in the mixed slurry a is 0.8 to 2.0: 1; in some embodiments of the invention, the molar ratio of phosphorus to metal elements in the mixed slurry a is 1.0-1.8: 1; in some embodiments of the invention, the molar ratio of phosphorus to metal elements in the mixed slurry a is 1.2 to 1.7: 1; in some embodiments of the present invention, the molar ratio of phosphorus to the metal element in the mixed slurry a is 1.4 to 1.6: 1.
In some embodiments of the present invention, in step 1), the temperature of the acidolysis reaction is 20 to 95 ℃, and the time of the acidolysis reaction is 1.0 to 5.0 hours. In some embodiments of the invention, proper stirring may be beneficial to shorten the reaction time.
The gas generated during acidolysis is mainly CO2And HF, which can be absorbed and utilized by a tail gas absorption system.
And step 2) is roasting. And roasting the mixed slurry A under a certain condition to obtain the multi-element short-chain polyphosphate slow-release fertilizer.
In one embodiment of the present invention, mixed slurry a is directly calcined.
In another embodiment of the present invention, the mixed slurry a is dried to obtain a material B, and then the material B is calcined.
Drying methods conventional in the art may be employed. In one embodiment of the invention, the drying temperature is below 120 ℃. In one embodiment of the present invention, the drying temperature is 100 to 120 ℃.
The gas generated during drying is mainly H2And O and HF can be absorbed and utilized by a tail gas absorption system.
In order to obtain a granular product, in one embodiment of the present invention, in step 2), the mixed slurry a or the material B is calcined, and then the calcined material is granulated.
The calcination temperature is closely related to the fluorine content in the calcined product and the product quality. In one embodiment of the invention, the firing temperature is >400 ℃. At the moment, the prepared medium trace element polyphosphate slow release fertilizer has low fluorine content, and the fluorine content can be reduced to be below 2.0 percent. However, the molecular chain of polyphosphate in the product has the risk of high-temperature cracking, which is not beneficial to the growth of polymer chain.
In another embodiment of the present invention, the firing temperature is 400 ℃ or less. At the moment, the obtained product has better quality, but the fluosilicate is remained in the fertilizer product, and the fluorine content of the obtained product is higher.
The gas generated during roasting is mainly HF and H2O and SiF4And the tail gas can be absorbed and utilized by a tail gas absorption system.
In addition, the method of the invention can also comprise the step of adding other nutrient components after roasting. In one embodiment of the present invention, ferrous ions (such as ferrous sulfate) are added to the roasted product to obtain a fertilizer containing both a fast-acting iron component and a slow-release component.
The molar ratio of Ca, Mg, Fe, Zn and Mn can also be adjusted by a conventional method, so that the Ca, Mg, Fe, Zn and Mn can be properly mixed with nutrient elements which are lacked by plants. In one embodiment of the invention, Ca and Mg elements account for 5-25 wt% of the polyphosphate slow release fertilizer, and Fe, Zn and Mn elements account for 0.2-4.0 wt% of the polyphosphate slow release fertilizer.
Research shows that the polymeric phosphate is more beneficial to the root growth of crops, and further promotes the absorption of the crops to nutrient elements in soil to achieve the effect of increasing yield. In addition, the polymeric phosphate needs to be hydrolyzed into orthophosphate to be directly absorbed and utilized by plants, and has in-situ slow release performance. Therefore, the polyphosphate obtained by the method not only can better promote the absorption of crops, but also can achieve the effect of slow release.
Wherein, the molar ratio of Ca, Mg, Fe, Zn and Mn can be properly adjusted according to nutrient elements which are deficient by plants. In one embodiment of the invention, Ca and Mg elements account for 5-25 wt% of the polyphosphate slow-release fertilizer, and ferrous iron, Zn and Mn elements account for 0.2-4.0 wt% of the polyphosphate slow-release fertilizer.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention. In the examples, the percentages by weight are percentages by weight unless otherwise specified.
Example 1
The used phosphoric acid residue 1 is concentrated residue, and the composition is shown in table 1; the metal element substance adopts typical dolomite phosphorus tailings 1 (as a calcium source and a magnesium source), the composition of which is shown in table 2, and the main components of the dolomite phosphorus tailings are calcium carbonate, magnesium carbonate and small amounts of fluorapatite and silicon dioxide.
TABLE 1 phosphoric acid residue 1 composition (unit wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 34.63 | 2.37 | 1.34 | 1.75 | 0.83 | 1.48 | 0.34 | 0.03 | 4.80 | 2.98 |
TABLE 2 phosphorus tailing 1 composition (in wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 7.62 | 32.99 | 15.35 | 6.36 | 0.70 | 0.57 | 0.21 | 0.12 | 1.52 | 1.01 |
720g of phosphoric acid residue 1 is accurately weighed and placed in a reactor, 400g of phosphate tailings is slowly added, namely P/(Ca + Mg + Fe + Zn + Mn) ═ 0.86, 150g of water is added into a mixed system and reacts for 5 hours under the normal temperature condition, and the reaction is accelerated by continuous stirring. After the reaction, the sample was calcined at 350 ℃ for 2.0 h. And granulating the roasted sample to obtain the granular polyphosphate slow-release fertilizer.
The results of elemental analysis of the obtained product are shown in Table 3, the polymerization parameters are shown in Table 4, and the analysis of citrate-soluble nutrients and water-soluble nutrients is shown in Table 5:
TABLE 3 polyphosphate elemental analysis Table (in wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 43.13 | 22.78 | 11.01 | 5.01 | 1.34 | 2.04 | 0.51 | 0.11 | 4.80 | 1.44 |
TABLE 4 polyphosphate polymerization degree, polymerization rate table
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 2.99 | 82.95％ |
TABLE 5 polyphosphate citrate soluble nutrient and water soluble nutrient analysis table
In table 5, "dissolved P/total P (%)" is the ratio of the phosphorus content dissolved with the solvent to the total phosphorus content in the polyphosphate, in units; similarly, "dissolved Ca/total Ca (%)" is the ratio of the amount of calcium dissolved by the solvent to the amount of total calcium in the polyphosphate, in units; "dissolved Mg/total Mg (%)" is the ratio of the amount of magnesium dissolved with solvent to the total amount of magnesium in polyphosphate, in%. The citric acid solution is a citric acid solution with the concentration of 20g/L as a solvent, and the water solution is water as a solvent. Wherein, the method for measuring citrate soluble nutrient and water soluble nutrient and the evaluation adopt GB/T8573-2017 for measurement.
Example 2
The phosphoric acid slag and the phosphate tailings used were the phosphoric acid slag 1 and the phosphate tailings 1 (as a calcium source and a magnesium source) in example 1, respectively. Weighing 440g of phosphoric acid slag in a reactor, slowly adding 200g of phosphorus tailings 1, namely P/(Ca + Mg + Fe + Zn + Mn) is 1.0, adding 150g of water into a mixed system, reacting for 5 hours at normal temperature, and continuously stirring to accelerate the reaction. After the reaction, the sample was calcined at 200 ℃ for 5.0 h. And granulating the roasted sample to obtain the granular polyphosphate fertilizer.
The results of the elemental analysis of the obtained product are shown in Table 6, the polymerization parameters are shown in Table 7, and the analysis of citrate-soluble nutrients and water-soluble nutrients is shown in Table 8:
TABLE 6 polyphosphate salts elementary analysis table (unit wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 46.49 | 20.40 | 9.89 | 4.80 | 1.33 | 2.10 | 0.50 | 0.10 | 4.81 | 1.55 |
TABLE 7 polymerization degree and polymerization rate table of polyphosphate
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 2.36 | 62.09％ |
TABLE 8 polyphosphate citrate soluble nutrient and water soluble nutrient analysis table
Example 3
The compositions of the phosphoric acid sludge 2 and the phosphoric acid sludge 3 used are shown in table 9; the metal element substance used was a typical dolomite phosphate tailing 2 (as a calcium source and a magnesium source) having the composition shown in table 10, and the main components thereof were calcium carbonate, magnesium carbonate, fluorapatite and a small amount of silica.
TABLE 9 phosphoric acid residue composition (unit wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F | |
| Phosphoric acid residue 2 | 29.55 | 6.34 | 6.06 | 1.87 | 0.12 | 3.06 | 1.58 | 0.02 | 12.02 | 4.16 |
| Phosphoric acid residue 3 | 21.29 | 1.90 | 2.42 | 18.02 | 0.19 | 0.88 | 0.60 | 0.01 | 0.98 | 17.38 |
TABLE 10 phosphorus tailings 2 composition (in wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 10.11 | 25.47 | 14.37 | 4.98 | 0.45 | 0.32 | 0.66 | 0.34 | 1.03 | 1.67 |
400g of phosphoric acid slag 2 and 200g of phosphoric acid slag 3 are respectively weighed and placed in a reactor, 150g of phosphorus tailings 2 are slowly added, namely P/(Ca + Mg + Fe + Zn + Mn) ═ 1.0, 200g of water is added into a mixed system, the mixed system is reacted for 5 hours at normal temperature, and the reaction is accelerated by continuous stirring. After the reaction, the containers were placed together in a forced air drying oven and dried at 105 ℃. The sample was weighed and calcined at 450 ℃ for 2.0 h. And granulating the roasted sample to obtain the granular polyphosphate fertilizer.
The results of the all-element analysis of the obtained product are shown in Table 11, the polymerization parameters are shown in Table 12, and the analysis of citrate-soluble nutrients and water-soluble nutrients is shown in Table 13:
TABLE 11 polyphosphate all element analysis table (unit wt%)
| P2O5 | CaO | MgO | SiO2 | Fe2O3 | Al2O3 | K2O | MnO | SO3 | F |
| 34.66 | 13.21 | 9.93 | 5.07 | 0.31 | 2.84 | 1.68 | 0.12 | 10.11 | 1.38 |
TABLE 12 polyphosphate polymerization degree, polymerization rate table
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 2.49 | 76.08％ |
TABLE 13 polyphosphate citrate soluble nutrient and water soluble nutrient analysis table
Example 4
The phosphoric acid sludge used was the concentrated sludge 1 of example 1. The metal element-containing substance adopts two types of mixture, i.e. the phosphorus-magnesium ore and the dolomite. The materials and compositions used are shown in table 14.
TABLE 14 composition of substances Table (unit wt%)
| P2O5 | CaO | MgO | ZnO | Fe2O3 | K2O | MnO | SO3 | F | |
| Phosphoric acid residue 1 | 34.63 | 2.37 | 1.34 | / | 0.83 | 0.34 | 0.03 | 4.80 | 2.98 |
| Phosphorus magnesium ore | 16.65 | 30.95 | 13.53 | / | / | / | / | 2.94 | 4.45 |
| Dolomite | 0.02 | 42.32 | 17.50 | / | / | / | / | 0.76 | / |
560g of phosphoric acid residue 1 was precisely weighed and placed in a reactor, and 100g of phosphorite and 50g of dolomite were slowly added so that P/(Ca + Mg + Fe + Zn + Mn) became 1.5. Adding 50g of water into the mixed system, reacting for 5 hours at normal temperature, and continuously stirring to accelerate the reaction. After the reaction, the sample was calcined at 650 ℃ for 0.5 h. And granulating the roasted sample to obtain the granular polyphosphate fertilizer.
The results of elemental analysis of the obtained product are shown in Table 15, the polymerization parameters are shown in Table 16, and the analysis of citrate-soluble nutrients and water-soluble nutrients is shown in Table 17:
TABLE 15 polyphosphate elemental analysis Table (in wt%)
| P2O5 | CaO | MgO | ZnO | Fe2O3 | K2O | MnO | SO3 | F |
| 51.12 | 15.93 | 7.22 | / | 1.24 | 0.50 | / | 7.63 | 0.99 |
TABLE 16 polymerization degree and polymerization rate table of polyphosphate
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 4.05 | 86％ |
TABLE 17 analysis of citrate-soluble and water-soluble nutrients
Example 5
The phosphoric acid sludge used was the concentrated sludge 1 of example 1. The metal-containing substances are mixed by two types, including metal oxides as calcium sources and magnesium sources (calcium oxide and magnesium oxide), metal sulfates supplement trace elements (ferrous sulfate, manganese sulfate and zinc sulfate) required by crops, and the used substances and the compositions are shown in Table 18.
TABLE 18 composition of substances Table (unit wt%)
480g of phosphoric acid residue 1 is accurately weighed and placed in a reactor, 30g of calcium oxide, 33g of magnesium oxide, 5.0g of manganese sulfate, 5.0g of zinc sulfate heptahydrate and 7.0g of ferrous sulfate heptahydrate are slowly added, so that P/(Ca + Mg + Fe + Zn + Mn) is 1.3. Adding 200g of water into the mixed system, reacting for 3 hours at normal temperature, and continuously stirring to accelerate the reaction. After the reaction, the sample was calcined at 250 ℃ for 4.0 h. And granulating the roasted sample to obtain the granular polyphosphate fertilizer.
The results of elemental analysis of the obtained product are shown in Table 19, the polymerization parameters are shown in Table 20, and the composition of citrate-soluble nutrients and water-soluble nutrients is shown in Table 21:
TABLE 19 polyphosphate elemental analysis Table (in wt%)
| P2O5 | CaO | MgO | ZnO | Fe2O3 | K2O | MnO | SO3 | F |
| 50.19 | 12.43 | 11.80 | 0.58 | 1.68 | 0.49 | 0.72 | 6.99 | 1.01 |
TABLE 20 polymerization degree and polymerization rate table of polyphosphate
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 2.861 | 67.36％ |
TABLE 21 polyphosphate citrate soluble nutrient and water soluble nutrient analysis table
Example 6
The phosphoric acid sludge used was the concentrated sludge of example 1. The metal element-containing substance adopts metal hydroxide as calcium source and magnesium source (calcium hydroxide and magnesium hydroxide), and metal sulfate supplements trace elements (ferrous sulfate, manganese sulfate and zinc sulfate) required by crops, and the substances and the compositions are shown in Table 22.
TABLE 22 composition of substances Table (unit wt%)
500g of phosphoric acid residue 1 is accurately weighed and placed in a reactor, and 38g of calcium hydroxide, 36g of magnesium hydroxide, 5.0g of manganese sulfate, 10.0g of zinc sulfate heptahydrate and 10.0g of ferrous sulfate heptahydrate are slowly added, so that P/(Ca + Mg + Fe + Zn + Mn) is 1.5. Adding 160g of water into the mixed system, reacting for 1 hour at normal temperature, and continuously stirring to accelerate the reaction. After the reaction, the sample was calcined at 500 ℃ for 0.5 h. And granulating the roasted sample to obtain the granular polyphosphate fertilizer.
The results of elemental analysis of the obtained product are shown in Table 23, the polymerization parameters are shown in Table 24, and the analyses of citrate-soluble nutrients and water-soluble nutrients are shown in Table 25:
TABLE 23 polyphosphate elemental analysis Table (in wt%)
| P2O5 | CaO | MgO | ZnO | Fe2O3 | K2O | MnO | SO3 | F |
| 52.47 | 12.31 | 9.55 | 0.85 | 2.14 | 0.52 | 1.46 | 9.79 | 0.19 |
TABLE 24 polyphosphate polymerization degree, polymerization rate pH Table
| Name (R) | Weight-average degree of polymerization | Rate of polymerization |
| Product(s) | 3.97 | 90.01％ |
TABLE 25 polyphosphate citrate soluble nutrient and water soluble nutrient analysis table
Therefore, by adopting the method, the phosphoric acid residues can be recycled to obtain the medium-trace element polyphosphate slow-release fertilizer, the content of citrate-soluble nutrients in the fertilizer is higher, the content of water-soluble nutrients in the fertilizer is lower, and the fertilizer is not easy to leach and can continuously provide sufficient multi-element nutrients for crops after being applied to soil.
Claims (9)
1. The resource utilization method of the phosphoric acid residues is characterized by comprising the following steps:
1) acid hydrolysis: mixing phosphoric acid residues, metal element-containing substances and water, and carrying out acidolysis reaction to obtain mixed slurry A; the metal element-containing material comprises at least one of magnesium-containing material, calcium-containing material, iron-containing material, zinc-containing material and manganese-containing material;
2) roasting: and roasting the mixed slurry A at the roasting temperature of 180-750 ℃ for 0.2-5.0 h to obtain the polyphosphate slow-release fertilizer.
2. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: the phosphoric acid residue is a byproduct of extraction, concentration, dearsenification and defluorination processes or storage processes in a wet-process phosphoric acid process.
3. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 1), the metal-element-containing substance is at least one of phosphate tailings, magnesite, calcium carbonate, dolomite, calcite, limestone, marble, travertine, magnesium carbonate, basic magnesium carbonate, metal oxide, metal hydroxide and sulfate.
4. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 1), the molar ratio of phosphorus to metal elements in the mixed slurry A is 0.8-2.0: 1; preferably, the molar ratio of phosphorus to metal elements is 1.0-1.8: 1; further preferably, the molar ratio of phosphorus to metal elements is 1.2-1.7: 1; more preferably, the molar ratio of phosphorus to the metal element is 1.4 to 1.6: 1.
5. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 1), the temperature of the acidolysis reaction is 20-95 ℃, and the time of the acidolysis reaction is 1.0-5.0 h.
6. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 2), drying the mixed slurry A to obtain a material B, and roasting the material B; preferably the drying temperature is below 120 ℃; further preferably, the drying temperature is 100 to 120 ℃.
7. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: and 2), granulating the roasted material.
8. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 2), the roasting temperature of the mixed slurry A is more than 400 ℃.
9. The resource utilization method of phosphoric acid residues according to claim 1, characterized in that: in the step 2), the roasting temperature of the mixed slurry A is less than or equal to 400 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683070A (en) * | 2021-09-07 | 2021-11-23 | 中化云龙有限公司 | Method for producing composite multi-element polyphosphate and co-producing fluosilicic acid by wet-process phosphoric acid residues |
| CN114106837A (en) * | 2021-11-25 | 2022-03-01 | 中化农业（临沂）研发中心有限公司 | Saline-alkali soil conditioner containing polyphosphate, preparation method and application thereof |
| CN114956904A (en) * | 2022-06-20 | 2022-08-30 | 四川大学 | Humic acid/ammonium polyphosphate/nano ZnO compound fertilizer and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161602A (en) * | 2010-12-28 | 2011-08-24 | 瓮福（集团）有限责任公司 | Method for preparing phosphorus-magnesium compound fertilizer by utilizing raffinate and phosphate tailings with high magnesium content |
| CN103113139A (en) * | 2013-03-05 | 2013-05-22 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Method for producing multivariate nitro compound fertilizer from wet-process phosphoric acid purification sludge |
| CN104016307A (en) * | 2014-06-13 | 2014-09-03 | 云南三环中化化肥有限公司 | Comprehensive utilization method for wet phosphoric acid dregs |
| CN105130508A (en) * | 2015-09-18 | 2015-12-09 | 云南三环中化化肥有限公司 | Production method for double phosphate fertilizer |
| KR20150142967A (en) * | 2014-06-13 | 2015-12-23 | (주)세기 | The waste phosphoric acid sludge recycling methode |
| CN105439646A (en) * | 2015-08-26 | 2016-03-30 | 云南三环中化化肥有限公司 | Method for producing phosphorus magnesia fertilizer by using wet phosphoric acid residues |
| CN108456007A (en) * | 2018-04-02 | 2018-08-28 | 金正大生态工程集团股份有限公司 | A kind of calcium polyphosphate magnesium fertilizer and preparation method thereof prepared as raw material using phosphoric acid and phosphorus tailing |
| CN111018571A (en) * | 2019-11-22 | 2020-04-17 | 中国农业大学 | Method for activating and utilizing low-grade phosphate ore |
-
2021
- 2021-06-09 CN CN202110644098.4A patent/CN113277885A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161602A (en) * | 2010-12-28 | 2011-08-24 | 瓮福（集团）有限责任公司 | Method for preparing phosphorus-magnesium compound fertilizer by utilizing raffinate and phosphate tailings with high magnesium content |
| CN103113139A (en) * | 2013-03-05 | 2013-05-22 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Method for producing multivariate nitro compound fertilizer from wet-process phosphoric acid purification sludge |
| CN104016307A (en) * | 2014-06-13 | 2014-09-03 | 云南三环中化化肥有限公司 | Comprehensive utilization method for wet phosphoric acid dregs |
| KR20150142967A (en) * | 2014-06-13 | 2015-12-23 | (주)세기 | The waste phosphoric acid sludge recycling methode |
| CN105439646A (en) * | 2015-08-26 | 2016-03-30 | 云南三环中化化肥有限公司 | Method for producing phosphorus magnesia fertilizer by using wet phosphoric acid residues |
| CN105130508A (en) * | 2015-09-18 | 2015-12-09 | 云南三环中化化肥有限公司 | Production method for double phosphate fertilizer |
| CN108456007A (en) * | 2018-04-02 | 2018-08-28 | 金正大生态工程集团股份有限公司 | A kind of calcium polyphosphate magnesium fertilizer and preparation method thereof prepared as raw material using phosphoric acid and phosphorus tailing |
| CN111018571A (en) * | 2019-11-22 | 2020-04-17 | 中国农业大学 | Method for activating and utilizing low-grade phosphate ore |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683070A (en) * | 2021-09-07 | 2021-11-23 | 中化云龙有限公司 | Method for producing composite multi-element polyphosphate and co-producing fluosilicic acid by wet-process phosphoric acid residues |
| CN114106837A (en) * | 2021-11-25 | 2022-03-01 | 中化农业（临沂）研发中心有限公司 | Saline-alkali soil conditioner containing polyphosphate, preparation method and application thereof |
| CN114106837B (en) * | 2021-11-25 | 2023-11-21 | 中化农业（临沂）研发中心有限公司 | Saline-alkali soil conditioner containing polyphosphate and preparation method and application thereof |
| CN114956904A (en) * | 2022-06-20 | 2022-08-30 | 四川大学 | Humic acid/ammonium polyphosphate/nano ZnO compound fertilizer and preparation method thereof |
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