CN111252750A - Method for preparing iron phosphate and aluminum oxide from phosphorus aluminum slag - Google Patents
Method for preparing iron phosphate and aluminum oxide from phosphorus aluminum slag Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
- C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust
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- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
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Abstract
The invention belongs to the technical field of compound preparation, and particularly relates to a method for preparing iron phosphate and aluminum oxide from phosphorus-aluminum slag. The method comprises the following steps: dissolving the phosphorus-aluminum slag by using an alkaline solution, and performing solid-liquid separation and crystallization to obtain phosphate crystals and an aluminate solution; dissolving phosphate crystals, adding a calcium-containing solution to react to generate a calcium phosphate precipitate, then adding concentrated sulfuric acid into the calcium phosphate precipitate, performing solid-liquid separation to obtain a phosphoric acid solution, and adding an iron source and an oxidant to react to obtain iron phosphate; and carrying out seed separation and calcination on the aluminate solution to obtain the alumina. The method takes the phosphorus-aluminum slag as a raw material, dissolves and separates phosphorus salt and aluminum salt through alkaline solution, then extracts phosphorus from the phosphorus salt to prepare iron phosphate, and extracts aluminum from the aluminum salt to prepare aluminum oxide, wherein the recovery rates of phosphorus and aluminum are both higher than 96 percent, the phosphorus and aluminum in the phosphorus-aluminum slag are fully utilized, and the processed slag can be directly buried, so that the method has the advantages of environmental protection and no pollution.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to a method for preparing iron phosphate and aluminum oxide from phosphorus-aluminum slag.
Background
As the phosphorus use amount in China is far more than the phosphorus yield which can be provided in China at present, urgent needs are provided for phosphorus. China has rich phosphorite resources and is the third place in the world, but mostly takes poor ores as the main part, and the problem of difficult development exists. If the phosphorite is reasonably developed and utilized, the shortage of phosphorus resources can be made up. Although the use and research and development directions of the phosphorite are various at present, and a plurality of reports are provided for the method for extracting the phosphorite, the extraction and use of the phosphorite in the current industry are not sufficient, the research on the further extraction and use of the residual slag in the industry is not sufficient, and the waste of mineral resources is caused.
In the current extraction method of phosphorus-aluminum-containing ore materials, after the purpose of extracting a target object is achieved, the obtained ore residues are generally processed through two ways, namely cement manufacturing and direct landfill. However, the situation that phosphorus is not completely extracted exists in the extraction process, so that not only is the resource waste caused, but also the phosphorus content of the landfill environment is too high due to direct landfill, and the environment pollution is caused.
Disclosure of Invention
The invention aims to provide a method for preparing iron phosphate from phosphorus aluminum slag, and aims to solve the technical problems of insufficient extraction and use of the existing phosphorus ore, overhigh phosphorus content in slag and the like.
It is another object of the present invention to provide a method for producing alumina from a phosphoaluminous slag.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing iron phosphate from phosphorus aluminum slag comprises the following steps:
dissolving the phosphorus-aluminum slag by using an alkaline solution, and performing solid-liquid separation and crystallization to obtain phosphate crystals and an aluminate solution;
dissolving the phosphate crystal, adding a calcium-containing solution to react to generate a calcium phosphate precipitate, then adding concentrated sulfuric acid into the calcium phosphate precipitate, performing solid-liquid separation to obtain a phosphoric acid solution, and adding an iron source and an oxidant to react to obtain the iron phosphate.
As a preferable technical scheme of the invention, in the step of dissolving the phosphorus-aluminum slag by using an alkaline solution, the dissolving temperature is 40-100 ℃.
In a preferred embodiment of the present invention, in the step of dissolving the aluminophosphate slag with an alkaline solution, the alkaline solution is sodium hydroxide and/or potassium hydroxide.
As a preferable technical scheme of the invention, the mass concentration of the alkaline solution is 20-30%.
As a preferred technical scheme of the invention, in the step of adding calcium-containing solution to react to generate calcium phosphate precipitate, the reaction temperature is 80-90 ℃.
As a preferable technical scheme of the invention, in the step of adding calcium-containing solution to react to generate calcium phosphate precipitate, the reaction time is 2-4 h.
In a preferred embodiment of the present invention, the calcium-containing solution is at least one selected from a calcium hydroxide solution and a calcium oxide solution.
As a preferable technical scheme of the invention, the mass concentration of the calcium-containing solution is 60-90%.
In a preferred embodiment of the present invention, the iron source is at least one selected from the group consisting of ferrous sulfate, ferric nitrate, red iron oxide, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate, and ferrous carbonate.
As a preferred embodiment of the present invention, the iron source is added by spraying.
As a preferable technical scheme of the invention, the oxidant is at least one selected from hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium superphosphate, sodium peroxide and potassium permanganate.
In a preferred embodiment of the present invention, the oxidizing agent is added by spraying.
As a preferable technical scheme of the invention, before the step of adding the iron source and the oxidant to carry out the reaction, the pH value of the phosphoric acid solution is adjusted to 4-5.
In order to achieve the above object, the present invention also provides a method for producing alumina from a phosphoaluminate slag, comprising the steps of:
dissolving the phosphorus-aluminum slag by using an alkaline solution, performing solid-liquid separation and crystallization to obtain a phosphate crystal and an aluminate solution, and performing seed separation and calcination on the aluminate solution to obtain the aluminum oxide.
As a preferable technical scheme of the invention, the seed separation is to add aluminum hydroxide seed crystals into the aluminate solution, and obtain the aluminum hydroxide through decomposition, sedimentation and separation.
The invention takes the phosphorus-aluminum slag with the main component of aluminum phosphate as the raw material, and the mixed solution of phosphate and aluminate is obtained by adding alkaline solution to dissolve the phosphorus-aluminum slag, so that 99 percent of phosphorus and aluminum elements in the phosphorus-aluminum slag can be dissolved out, and the invention has the advantages of high dissolution rate of phosphorus and aluminum and high recovery rate; secondly, the calcium-containing solution is added in the process of extracting phosphorus from phosphate crystals to prepare the iron phosphate, so that impurity components introduced by adding an alkaline solution can be removed, and the recovery rate of phosphorus is improved; thirdly, as the aluminate solution is generated in the process of preparing the iron phosphate, the metallurgical-grade aluminum oxide can be prepared by separating aluminum from the aluminate solution, so that the phosphorus aluminum slag resource is fully utilized; finally, after the phosphorus and the aluminum are extracted from the phosphorus-aluminum slag, the obtained slag hardly contains phosphorus and aluminum, can be directly buried and cannot cause environmental pollution.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as encompassing the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a method for preparing iron phosphate from phosphorus aluminum slag, which comprises the following steps:
s1, dissolving the phosphorus-aluminum slag by using an alkaline solution, and performing solid-liquid separation and crystallization to obtain phosphate crystals and an aluminate solution;
s2, dissolving the phosphate crystal, adding a calcium-containing solution to react to generate a calcium phosphate precipitate, then adding concentrated sulfuric acid into the calcium phosphate precipitate, performing solid-liquid separation to obtain a phosphoric acid solution, and adding an iron source and an oxidant to react to obtain the iron phosphate.
The invention takes the phosphorus-aluminum slag with the main component of aluminum phosphate as the raw material, and the mixed solution of phosphate and aluminate is obtained by adding alkaline solution to dissolve the phosphorus-aluminum slag, so that 99 percent of phosphorus and aluminum elements in the phosphorus-aluminum slag can be dissolved out, and the invention has the advantages of high dissolution rate of phosphorus and aluminum and high recovery rate; meanwhile, the calcium-containing solution is added in the process of extracting phosphorus from phosphate crystals to prepare the iron phosphate, so that impurity components introduced by adding the alkaline solution can be removed, and the recovery rate of phosphorus is improved. In addition, after the phosphorus and the aluminum are extracted from the phosphorus-aluminum slag, the obtained slag hardly contains phosphorus and aluminum, can be directly buried and cannot cause environmental pollution.
Since the main component of the aluminophosphate slag is aluminophosphate, in S1, the aluminophosphate slag can be dissolved and reacted to generate aluminate and phosphate by adding an alkaline solution into the aluminophosphate slag, and the solid obtained by solid-liquid separation is red mud slag, and the liquid is a mixed solution of the aluminate and the phosphate; the mixed solution of aluminate and phosphate is concentrated, cooled and crystallized to precipitate phosphate crystal, and the rest liquid is aluminate solution. The relevant chemical reaction formula is as follows:
AlPO4+4OH-→AlO2 -+PO4 3-+2H2O。
in some embodiments, the temperature at which the alkaline solution dissolves the aluminophosphate slag is set to 40 ℃ to 100 ℃. By optimizing the dissolving temperature, the dissolving rate of phosphorus and aluminum can be improved, the formation of subsequent phosphate crystals is promoted, and the separation of phosphate and aluminate and the recovery of phosphorus and aluminum are facilitated. Specifically, the typical, but not limiting, temperature at which the alkaline solution dissolves the aluminophosphate slag may be 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃.
In some embodiments, in order to reduce the production cost, a highly alkaline sodium hydroxide solution, a potassium hydroxide solution, or a mixed solution of sodium hydroxide and potassium hydroxide is selected as the alkaline solution for dissolving the aluminophosphate slag.
In some embodiments, the alkaline solution has a mass concentration of 20% to 30%. If the concentration of the alkaline solution is too low, more alkaline solution needs to be consumed for reaction, and the volume requirement of the required reaction container is also larger, so that the production cost is increased; the concentration of the alkaline solution is too high, and although the reaction itself is not greatly influenced, the high-concentration alkaline solution releases a large amount of heat in the preparation process, so that the equipment is damaged, and the danger of production operation and the production cost are increased. Specifically, the alkaline solution is typically, but not limited to, at a concentration of 20%, 22%, 24%, 26%, 28%, 30%.
In S2, after dissolving phosphate crystals, adding a calcium-containing solution to perform a displacement reaction to generate a calcium phosphate precipitate, wherein phosphorus exists in the form of the calcium phosphate precipitate, then adding concentrated sulfuric acid to perform a reaction to generate calcium sulfate and phosphoric acid, and removing the calcium sulfate precipitate through solid-liquid separation to obtain a high-purity phosphoric acid solution.
In some embodiments, the phosphate crystals are dissolved by adding hot water. The dissolution with hot water can not only accelerate the dissolution rate of phosphate crystals, but also provide certain heat for the subsequent reaction of phosphate solution and calcium-containing solution.
In some embodiments, the calcium-containing solution is added to react with the phosphate solution at a temperature of 80 ℃ to 90 ℃ for a time of 2h to 4 h. By optimizing the reaction temperature and the reaction time of the calcium-containing solution and the phosphate solution, the reaction efficiency can be improved and the production time can be shortened on the premise of ensuring the full reaction of the calcium-containing solution and the phosphate solution. Specifically, typical but not limiting reaction temperatures are 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃; typical but not limiting reaction times are 2h, 2.5h, 3h, 3.5h, 4 h.
Preferably, the calcium-containing solution is slowly added to the phosphate solution to react under stirring at 8000-10000 rpm. Through stirring, the calcium-containing solution and the phosphate solution can be fully mixed, the reaction is facilitated to be complete, and the reaction rate can be increased. Specifically, typical, but not limiting, stirring speeds are 8000rpm, 8500rpm, 9000rpm, 9500rpm, 10000 rpm.
The calcium-containing solution is specifically selected to react with phosphate to form calcium phosphate. Thus, in some embodiments, the calcium-containing solution may be a calcium hydroxide solution and/or a calcium oxide solution.
In some embodiments, the calcium-containing solution has a mass concentration of 60% to 90%. If the concentration of the calcium-containing solution is too low, the calcium-containing solution and phosphate do not completely react, and a part of phosphate is not converted into calcium phosphate precipitate and remains in the solution, so that the recovery rate of phosphorus is influenced; the concentration of the calcium-containing solution is too high, which not only increases the cost, but also is beneficial to removing the subsequent calcium element. In particular, typical, but not limiting, concentrations of calcium-containing solutions are 60%, 65%, 70%, 75%, 80%, 85%, 90%.
In some embodiments, the concentrated sulfuric acid reacts with the calcium phosphate precipitate to form a calcium sulfate precipitate and a phosphoric acid solution, and since the obtained phosphoric acid solution may contain a portion of aluminum impurities, in order to remove the aluminum impurities and improve the quality of the obtained iron phosphate, the pH of the phosphoric acid solution may be adjusted to 4-5, so that the aluminum impurities in the phosphoric acid solution are converted into aluminum hydroxide precipitate to remove the aluminum impurities.
Preferably, the pH of the phosphoric acid solution may be adjusted by adding ammonia or ammonium carbonate.
More preferably, ammonia is used to adjust the pH of the phosphoric acid solution to avoid the introduction of impurities.
In S2, an iron source and an oxidizing agent are added to a phosphoric acid solution to react with each other, thereby obtaining iron phosphate. In some embodiments, the iron source is at least one selected from ferrous sulfate, ferric nitrate, ferric oxide red, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate, and ferrous carbonate, and has the advantages of low cost and abundant sources.
Preferably, ferrous sulfate with low cost and rich sources is selected as the iron source.
In some embodiments, the oxidizing agent is selected from at least one of hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium superphosphate, sodium peroxide, potassium permanganate. Preferably, the hydrogen peroxide with strong oxidizability is selected as the oxidant, so that the method has the advantages of small using amount, low cost and no introduction of impurity ions.
In some embodiments, the iron source and/or the oxidizing agent are added in a spray. The iron source and/or the oxidant are added by spraying, so that the loss of phosphorus can be minimized, and the impurity content of the obtained finished iron phosphate product is lower.
The method for preparing the iron phosphate from the phosphorus-aluminum slag can ensure that the dissolution rate of phosphorus reaches more than 99 percent, the dissolution rate of fluorine reaches 0 percent, the dissolution rate of silicon reaches 0.1 percent, and the recovery rate of phosphorus reaches 96 percent, so that the method can accurately extract phosphorus and avoid introducing other impurities; the finished product of the iron phosphate prepared by the method is faint yellow powder, the main content of the powder is 60-70%, and the standard of a battery grade is achieved.
The embodiment of the invention also provides a method for preparing alumina from the phosphorus-aluminum slag, which comprises the following steps:
dissolving the phosphorus-aluminum slag by using an alkaline solution, performing solid-liquid separation and crystallization to obtain a phosphate crystal and an aluminate solution, and performing seed separation and calcination on the aluminate solution to obtain the aluminum oxide.
The method takes the phosphorus-aluminum slag with the main component of aluminum phosphate as a raw material, the phosphorus-aluminum slag is dissolved by adding an alkaline solution to obtain a phosphate crystal and an aluminate solution, aluminum is separated from the aluminate solution to obtain aluminum hydroxide, and the aluminum hydroxide is calcined to obtain aluminum oxide, so that the phosphorus-aluminum slag resource is fully utilized.
The optimization of the temperature, the selection of the alkaline solution and the selection of the concentration of the alkaline solution when the phosphorus-aluminum slag is dissolved by the alkaline solution in the embodiment of the invention has been explained in detail in the foregoing, and thus, the details are not repeated herein. In some embodiments, the seed separation is to add aluminum hydroxide seed crystals to the aluminate solution, and obtain aluminum hydroxide through decomposition, sedimentation and separation, wherein the related chemical reaction formula is as follows:
NaAlO2+2H2O→Al(OH)3+NaOH。
in the present invention, the calcination temperature at which aluminum hydroxide is calcined to produce alumina is not particularly limited, and may be a calcination temperature required for producing alumina in accordance with a conventional method.
The method for preparing the iron phosphate from the phosphorus-aluminum slag can ensure that the dissolution rate of aluminum reaches over 99 percent and the recovery rate of the aluminum reaches 96 percent, so the method can accurately extract the aluminum and avoid introducing other impurities; the alumina prepared by the method has the cost of white powder, the main content of 98.5 percent and reaches the metallurgical grade qualified product.
In conclusion, the invention takes the phosphorus-aluminum slag with the main component of aluminum phosphate as the raw material, and the phosphate crystal and the aluminate solution are obtained by adding the alkaline solution to dissolve the phosphorus-aluminum slag, so that the phosphate crystal and the aluminate solution have the advantages of high dissolution rate of phosphorus and aluminum and high recovery rate, can be used for preparing the iron phosphate and the alumina, and the prepared iron phosphate and the prepared alumina have higher quality.
In order to clearly understand the details of the above-described implementation and operation of the present invention for those skilled in the art and to significantly embody the advanced performance of the embodiments of the present invention, the above-described technical solution is illustrated by a plurality of embodiments below.
The components of the phosphorus-aluminum slag of the present invention were measured, and the results are shown in Table 1.
TABLE 1 measurement results of the composition of the phosphorous aluminum slag of the present invention
| Burn out reduction (1025 ℃ C.) | 3.71(％) | PbO | 5.65(mg/kg) |
| Al2O3 | 35.19(％) | ZnO | 70.50(mg/kg) |
| SiO2 | 11.04(％) | CdO | 6.05(mg/kg) |
| Fe2O3 | 0.12(％) | SrO | 157.48(mg/kg) |
| P2O5 | 48.82(％) | MnO | 20.07(mg/kg) |
| S | 0.78(％) | Cr2O3 | 58.40(mg/kg) |
| F | ＜0.10(％) | NiO | 4.55mg/kg) |
| Li2O | 0.40(％) | CoO | 5.60(mg/kg) |
| TiO2 | 0.12(％) | CuO | 45.38(mg/kg) |
| CaO | 703.09(mg/kg) | MgO | 112.43(mg/kg) |
| K2O | 734.80(mg/kg) | Rb2O | 23.24(mg/kg) |
| Na2O | 608.68(mg/kg) | Cs2O | 5.05(mg/kg) |
| BaO | 172.21(mg/kg) | BeO | 344.71(mg/kg) |
Example 1
Adding 240g of phosphorus-aluminum slag into 600mL of 24% sodium hydroxide solution, heating and reacting for 2.5h at 40 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.05% and 99.01% respectively; adding 140mL of 90% calcium hydroxide solution into the phosphate crystal, heating and reacting at 85 ℃ for 2.5h, adding 70mL of concentrated sulfuric acid, filtering to obtain a phosphoric acid solution, adding ammonia water to adjust the pH value of the phosphoric acid solution to 4.6, adding 70g of ferrous oxide and 45mL of hydrogen peroxide solution, and reacting to obtain the iron phosphate, wherein the phosphorus recovery rate is 96.78%. 6g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain aluminum oxide, and the aluminum recovery rate is 96.58%.
Example 2
Adding 200g of phosphorus-aluminum slag into 550mL of 30% sodium hydroxide solution, heating and reacting for 2h at 80 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.14% and 99.08% respectively; adding 100mL of 65% calcium hydroxide solution into the phosphate crystal, heating and reacting for 4h at 83 ℃, adding 76mL of concentrated sulfuric acid, filtering to obtain a phosphoric acid solution, adding ammonia water to adjust the pH value of the phosphoric acid solution to 4.8, adding 65g of ferrous oxide and 35mL of hydrogen peroxide solution, and reacting to obtain the iron phosphate, wherein the phosphorus recovery rate is 96.93%. 9g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain aluminum oxide, and the aluminum recovery rate is 96.35%.
Example 3
Adding 280g of phosphorus-aluminum slag into 500mL of 28% sodium hydroxide solution, heating and reacting for 1.5h at 70 ℃, filtering, crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.06% and 99.11% respectively; adding 200mL of 60% calcium hydroxide solution into the phosphate crystal, heating and reacting for 3.5h at 87 ℃, adding 80mL of concentrated sulfuric acid, filtering to obtain a phosphoric acid solution, adding ammonia water to adjust the pH value of the phosphoric acid solution to 5, adding 75g of ferrous oxide and 30mL of hydrogen peroxide solution, and reacting to obtain the iron phosphate, wherein the phosphorus recovery rate is 97.05%. 8g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain aluminum oxide, and the aluminum recovery rate is 96.42%.
Example 4
Adding 300g of phosphorus-aluminum slag into 800mL of 20% potassium hydroxide solution, heating and reacting for 1h at 100 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are respectively 99.15% and 99.07%; adding 160mL of 80% calcium hydroxide solution into the phosphate crystal, heating and reacting at 90 ℃ for 3h, adding 60mL of concentrated sulfuric acid, filtering to obtain a phosphoric acid solution, adding ammonia water to adjust the pH value of the phosphoric acid solution to 4.3, adding 80g of iron oxide red and 40mL of hydrogen peroxide solution, and reacting to obtain the iron phosphate, wherein the phosphorus recovery rate is 97.12%. 5g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain the alumina, and the aluminum recovery rate is 96.46%.
Example 5
Adding 270g of phosphorus-aluminum slag into 650mL of 26% potassium hydroxide solution, heating and reacting for 3h at 90 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.23% and 99.14% respectively; adding 150mL of 70% calcium hydroxide solution into the phosphate crystal, heating and reacting for 2h at 80 ℃, adding 69mL of concentrated sulfuric acid, filtering to obtain a phosphoric acid solution, adding ammonia water to adjust the pH value of the phosphoric acid solution to 4, adding 72g of iron oxide red and 50mL of hydrogen peroxide solution, and reacting to obtain the iron phosphate, wherein the phosphorus recovery rate is 97.06%. And adding 10g of aluminum hydroxide seed crystal into the aluminate solution, and carrying out seed separation and calcination on the obtained solution to obtain aluminum oxide, wherein the aluminum recovery rate is 96.37%.
Comparative example 1
Adding 240g of phosphorus-aluminum slag into 600mL of 24% sodium hydroxide solution, heating and reacting for 2.5h at 40 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.05% and 99.01% respectively; 70g of ferrous oxide and 45mL of hydrogen peroxide solution are added into the phosphate crystal to react to obtain the iron phosphate, and the phosphorus recovery rate is 85.12%. 6g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain aluminum oxide, and the aluminum recovery rate is 96.59%.
Comparative example 2
Adding 200g of phosphorus-aluminum slag into 550mL of 30% sodium hydroxide solution, heating and reacting for 2h at 80 ℃, filtering, and crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.14% and 99.08% respectively; adding 65g of ferrous oxide and 35mL of hydrogen peroxide solution into the phosphate crystal to react to obtain the iron phosphate, wherein the phosphorus recovery rate is 83.87%. 9g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain aluminum oxide, and the aluminum recovery rate is 96.41%.
Comparative example 3
Adding 280g of phosphorus-aluminum slag into 500mL of 28% sodium hydroxide solution, heating and reacting for 1.5h at 70 ℃, filtering, crystallizing to obtain phosphate crystals and aluminate solution, wherein the leaching rates of phosphorus and aluminum in the slag are 99.06% and 99.11% respectively; and adding 75g of ferrous oxide and 30mL of hydrogen peroxide solution into the phosphate crystal to react to obtain the iron phosphate, wherein the phosphorus recovery rate is 84.51%. 8g of aluminum hydroxide seed crystal is added into the aluminate solution, the obtained solution is subjected to seed precipitation and calcination to obtain the alumina, and the aluminum recovery rate is 96.24%.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing iron phosphate from phosphorus aluminum slag is characterized by comprising the following steps:
dissolving the phosphorus-aluminum slag by using an alkaline solution, and performing solid-liquid separation and crystallization to obtain phosphate crystals and an aluminate solution;
dissolving the phosphate crystal, adding a calcium-containing solution to react to generate a calcium phosphate precipitate, then adding concentrated sulfuric acid into the calcium phosphate precipitate, performing solid-liquid separation to obtain a phosphoric acid solution, and adding an iron source and an oxidant to react to obtain the iron phosphate.
2. The method of producing iron phosphate from aluminophosphate slag according to claim 1, wherein in the step of dissolving the aluminophosphate slag in an alkaline solution, the temperature of the dissolution is 40 ℃ to 100 ℃.
3. The method of producing iron phosphate from aluminophosphate slag according to claim 1, wherein in the step of dissolving the aluminophosphate slag with an alkaline solution, the alkaline solution is sodium hydroxide and/or potassium hydroxide; and/or the mass concentration of the alkaline solution is 20-30%.
4. The method for producing iron phosphate from aluminophosphate slag according to claim 1, wherein in the step of adding a calcium-containing solution to react to form calcium phosphate precipitate, the reaction temperature is 80 ℃ to 90 ℃; and/or the presence of a gas in the gas,
the reaction time is 2h-4 h.
5. The method for producing iron phosphate from phosphoaluminate slag according to claim 1, wherein the calcium-containing solution is at least one selected from the group consisting of a calcium hydroxide solution and a calcium oxide solution; and/or the presence of a gas in the gas,
the mass concentration of the calcium-containing solution is 60-90%.
6. The method for producing iron phosphate from the phosphoaluminate slag according to any one of claims 1 to 5, characterized in that the iron source is selected from at least one of ferrous sulfate, ferric nitrate, red iron oxide, ferrous oxide, ferric chloride, ferrous chloride, ferric sulfate, ferrous nitrate, ferric carbonate, ferrous carbonate; and/or the presence of a gas in the gas,
the iron source is added by spraying.
7. The method for producing iron phosphate from the phosphoaluminate slag according to any one of claims 1 to 5, wherein the oxidizing agent is at least one selected from hydrogen peroxide, oxygen, ozone, sodium hypochlorite, ferric persulfate, ammonium persulfate, sodium peroxide, potassium permanganate; and/or the presence of a gas in the gas,
the oxidant is added by spraying.
8. The method for producing iron phosphate from phosphoaluminous slag according to any one of claims 1 to 5, wherein the pH of the phosphoric acid solution is adjusted to 4 to 5 before the step of adding the iron source and the oxidizing agent for reaction.
9. A method for preparing alumina from phosphorus-aluminum slag is characterized by comprising the following steps:
dissolving the phosphorus-aluminum slag by using an alkaline solution, performing solid-liquid separation and crystallization to obtain a phosphate crystal and an aluminate solution, and performing seed separation and calcination on the aluminate solution to obtain the aluminum oxide.
10. The method for preparing the aluminum oxide according to claim 9, wherein the seed separation is to add aluminum hydroxide seed crystals into the aluminate solution, and obtain the aluminum hydroxide through decomposition, sedimentation and separation.
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