CN113184821A - Method for preparing iron phosphate by using iron-containing slag - Google Patents
Method for preparing iron phosphate by using iron-containing slag Download PDFInfo
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- CN113184821A CN113184821A CN202110513422.9A CN202110513422A CN113184821A CN 113184821 A CN113184821 A CN 113184821A CN 202110513422 A CN202110513422 A CN 202110513422A CN 113184821 A CN113184821 A CN 113184821A
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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Abstract
The invention provides a method for preparing iron phosphate by using iron-containing slag. The method comprises the following steps: step S1, carrying out acid washing on the iron-containing slag to obtain acid-washed iron slag and acid washing liquid; step S2, mixing and granulating the iron slag after acid washing, acid and phosphate to obtain mixed particles; step S3, roasting the mixed particles to obtain a roasted product; step S4, heating and slurrying the roasted product under the condition that the pH value is 0.8-1.8 to obtain iron phosphate slurry; and step S5, performing solid-liquid separation on the iron phosphate slurry to obtain an iron phosphate crude product and a valuable metal solution. The iron phosphate crude product obtained by the method can be used as a raw material of a iron phosphate battery, the metal recovery rate in valuable metal solution can be up to more than 98.5%, the iron slag waste is completely and effectively utilized, the process is simple and easy to implement, the additive is low in price, the cost for synthesizing the iron phosphate can be optimized and reduced, and the slag-free comprehensive recycling of the iron slag is realized.
Description
Technical Field
The invention relates to the technical field of waste residue treatment, in particular to a method for preparing iron phosphate by using iron-containing slag.
Background
At present, a common phenomenon in the hydrometallurgy industry is that hazardous waste solid slag is difficult to treat, wherein common iron slag comprises jarosite slag, goethite slag, hematite slag, iron phosphate waste slag, lithium iron phosphate slag and the like. The iron vanadium slag and the iron slag are generally recovered by processes of brick making, organized special landfill, roasting electrolysis and the like which are used as raw materials of building materials, the method treats the slag to a certain extent, but the recovery rate of valuable metals is not high enough, and the effective utilization of various components of all the slag is not realized.
Although the ferric phosphate has low conductivity, the ferric phosphate can also be used as an embedded electrode of a lithium ion battery. However, as materials engineers overcome the conductivity problem, their use as electrode materials has become more prevalent in recent years. Due to FePO4Is stable to heat and is generally easy to recycle, so the material is an ideal electrode material for batteries of electric vehicles. If the iron-containing material waste residues can be fully utilized to prepare the iron phosphate precursor battery material, the problem of environmental protection is solved, and the full closed-loop circulation of various materials is realized.
From the view point of the prior art, the existing iron slag treatment and recovery process can recover part of valuable metals, but the recovery rate of the valuable metals is not high enough, and the effective utilization of various components of various iron-containing slag materials cannot be realized.
Disclosure of Invention
The invention mainly aims to provide a method for preparing iron phosphate by using iron-containing slag, which aims to solve the problem that iron and valuable metals in the iron-containing slag cannot be effectively recovered in the prior art.
In order to accomplish the above object, according to one aspect of the present invention, there is provided a method for preparing iron phosphate using iron-containing slag, the method comprising: step S1, carrying out acid washing on the iron-containing slag to obtain acid-washed iron slag and acid washing liquid; step S2, mixing and granulating the iron slag after acid washing, acid and phosphate to obtain mixed particles; step S3, roasting the mixed particles to obtain a roasted product; step S4, heating and slurrying the roasted product under the condition that the pH value is 0.8-1.8 to obtain iron phosphate slurry; and step S5, performing solid-liquid separation on the iron phosphate slurry to obtain an iron phosphate crude product and a valuable metal solution.
Further, the above step S1 is performed by acid washing with sulfuric acid, preferably with H in sulfuric acid2SO4The molar amount of the iron-containing slag is 0.5-2% of the total molar amount of iron in the iron-containing slag, preferably 1.0-1.5%, the volume of the sulfuric acid is preferably 1-5 times, preferably 2-3 times of the volume of the iron-containing slag, preferably the iron-containing slag is selected from one or more of yellow sodium iron vitriol slag, goethite slag, hematite slag, iron phosphate waste slag and iron phosphate lithium slag, and the particle size of the iron-containing slag is preferably less than 50 μm.
Further, in the above step S2, H represents a number+The molar weight of the acid is 2.0 to 2.2 times of the molar weight of the iron in the iron slag after acid washing, the molar weight of phosphate is preferably 1.0 to 1.05 times of the molar weight of theoretical phosphate in terms of phosphorus, the acid is preferably sulfuric acid, and the phosphate is preferably one or more of sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate and potassium phosphate.
Further, the particle size of the mixed particles is 0.5-8 cm.
Further, the roasting temperature in the step S3 is 120-300 ℃, the roasting time is 1-10 h, preferably the roasting is carried out in air, and the flow rate of the air is 1-20L/min, preferably 10-15L/min.
Further, in the step S4, the temperature of the heated slurry is 70 to 95 ℃ and the time is 10 to 30 hours, and it is preferable that the roasted product is stirred during the heated slurry, and the rotation speed of the stirring is 1000 to 2000 rpm.
Further, the step S4 includes: mixing the roasted product with water and a surfactant to obtain mixed slurry, wherein the preferable surfactant is sodium dodecyl sulfate and sodium hexadecyl sulfate, the preferable volume ratio of the surfactant to the roasted product is 0.05-0.2: 1, and the preferable volume ratio of the roasted product to the water is 1: 5-7; and heating the mixed slurry, and maintaining the pH value of the mixed slurry to be 0.8-1.8 in the heating process to obtain the iron phosphate slurry.
Further, before the step S4, the baked material is pulverized to a particle size of 0.1 to 50 μm.
Further, the step S5 includes: filtering the iron phosphate slurry to obtain a filter cake and a filtrate; and carrying out acid leaching on the filter cake to obtain crude iron phosphate, and preferably carrying out acid leaching by using sulfuric acid with the mass concentration of 0.5-2%.
Further, the method further comprises wet recovery of valuable metals in the filtrate obtained in step S5 and the pickling solution obtained in step S1.
By applying the technical scheme of the invention, most of impurity metal ions such as nickel, cobalt, copper and lithium in the iron-containing slag are washed out by acid washing, most of soluble salts are washed away, and iron is remained in the iron slag after acid washing; then mixing and granulating the iron slag after acid cleaning, acid and phosphate, and then roasting, wherein iron oxide in the iron slag after acid cleaning reacts with the acid under the roasting condition to form iron salt; after roasting is finished, the ferric phosphate slurry is obtained by heating and slurrying, solid-liquid separation is subsequently carried out to obtain a ferric phosphate crude product and a valuable metal solution, the obtained ferric phosphate crude product can be used as a raw material of a ferric phosphate battery, the metal recovery rate in the valuable metal solution can reach more than 98.5%, the total effective utilization of iron slag waste is realized, the process is simple and easy to implement, the additive is low in cost, the cost for synthesizing ferric phosphate can be optimized and reduced, and the comprehensive recycling of iron slag without slag is realized.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed in the background art of the present application, the recovery of valuable metals in the iron slag in the prior art is not sufficient, resulting in a large loss of valuable metals. In order to solve the problem, the present application provides a method for preparing iron phosphate from iron-containing slag, comprising: step S1, carrying out acid washing on the iron-containing slag to obtain acid-washed iron slag and acid washing liquid; step S2, mixing and granulating the iron slag after acid washing, acid and phosphate to obtain mixed particles; step S3, roasting the mixed particles to obtain a roasted product; step S4, heating and slurrying the roasted product under the condition that the pH value is 0.8-1.8 to obtain iron phosphate slurry; and step S5, performing solid-liquid separation on the iron phosphate slurry to obtain an iron phosphate crude product and a valuable metal solution.
According to the method, firstly, most of impurity metal ions such as nickel, cobalt, copper and lithium in the iron-containing slag are washed out by acid washing, most of soluble salts are washed away, and iron is remained in the iron slag after the acid washing; then mixing and granulating the iron slag after acid cleaning, acid and phosphate, and then roasting, wherein iron oxide in the iron slag after acid cleaning reacts with the acid under the roasting condition to form iron salt; after roasting is finished, the ferric phosphate slurry is obtained by heating and slurrying, solid-liquid separation is subsequently carried out to obtain a ferric phosphate crude product and a valuable metal solution, the obtained ferric phosphate crude product can be used as a raw material of a ferric phosphate battery, the metal recovery rate in the valuable metal solution can reach more than 98.5%, the total effective utilization of iron slag waste is realized, the process is simple and easy to implement, the additive is low in cost, the cost for synthesizing ferric phosphate can be optimized and reduced, and the comprehensive recycling of iron slag without slag is realized.
The pickling process of step S1 can refer to the conventional pickling method for iron-containing slag in the prior art, and in order to avoid the volatilization of acidic substances during the pickling process, the pickling process of step S1 is preferably performed by using sulfuric acid. In order to achieve sufficient elution of valuable metals from the iron-containing slag, H in sulfuric acid is preferred2SO4The molar weight of the sulfuric acid is 0.5-2% of the total molar weight of iron in the iron-containing slag, and the volume of the sulfuric acid is preferably 1-5 times of that of the iron-containing slag. The method of the present application can be applied to various iron-containing slags, preferably a mixture of any one or more of iron-containing slags selected from the group consisting of jarosite slags, goethite slags, hematite slags, iron phosphate slags and lithium iron phosphate slags, wherein the iron-containing slags have different components and different physical properties, but have a commonality when acid pickling is used, i.e., dissolution of valuable metals therein is similar. Preferably, the grain size of the iron-containing slag is less than 50 μm. When the mixture of various slags is used as the iron-containing slag, the iron-containing slag is crushed to a particle size of less than 50 μm by a ball milling process, and because the hardness of various slags is different, the mutual mixing of materials during ball milling has a ball milling crushing gain effect. The ball milling process can be dry ball milling or wet ball milling.
To make it practicalNow, the iron oxide in the iron slag after acid washing is fully converted, preferably in step S2, with H+The molar weight of the acid is 2.0 to 2.2 times of the molar weight of the iron in the iron slag after acid washing, the molar weight of phosphate is preferably 1.0 to 1.05 times of the molar weight of theoretical phosphate in terms of phosphorus, the acid is preferably sulfuric acid, and the phosphate is preferably one or more of sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate and potassium phosphate.
In the roasting process, the reaction between the acid and the iron slag after acid washing is a solid-phase reaction, and in order to increase the diffusion contact speed of the reactant in the mixed particles and further increase the reaction efficiency, the particle size of the mixed particles is preferably controlled to be 0.5-8 cm.
In some embodiments, the calcination temperature in the step S3 is controlled to be 120 to 300 ℃, preferably 150 to 250 ℃, and the calcination time is 1 to 10 hours, within the temperature range, the reactivity of the reactant is improved. In order to convert ferrous ions in the iron slag after acid cleaning, roasting is preferably carried out in air, and the flow rate of the air is 1-20L/min, preferably 10-15L/min.
In the present application, the heating slurry can realize the conversion of the roasted product into the iron phosphate, and in order to improve the conversion effect of the iron phosphate, in the step S4, the temperature of the heating slurry is preferably 70 to 95 ℃ for 10 to 30 hours, and the temperature of the heating slurry is preferably 80 to 90 ℃ for 15 to 24 hours. In some embodiments, the roasted material is stirred during the heating and slurrying process, and the stirring speed is 1000-2000 rpm, so that the uniformity of the slurrying reaction is further improved.
In some embodiments, the step S4 includes: mixing the roasted product with water and a surfactant to obtain mixed slurry; and heating the mixed slurry, and maintaining the pH value of the mixed slurry to be 0.8-1.8 in the heating process to obtain the iron phosphate slurry. By adding the surfactant, the particle size of the obtained iron phosphate is effectively controlled. And in the slurrying process, the pH is controlled to be 0.8-1.8, so that the basic iron phosphate generated by iron salt and phosphate is converted into the iron phosphate, the purity of the iron phosphate is improved, and the phosphorus-iron ratio of the iron phosphate is closer to 1: 1. In some embodiments, the preferred surfactants are sodium dodecyl sulfate and sodium hexadecyl sulfate, the volume ratio of the surfactant to the roasted product is preferably 0.05-0.2: 1, and the volume ratio of the roasted product to water is preferably 1: 5-7.
Similarly, in order to increase the slurry efficiency, the calcined material is pulverized to a particle size of 0.1 to 50 μm before the step S4. The pulverization may be ball milling.
In some embodiments of the present application, the step S5 includes: filtering the iron phosphate slurry to obtain a filter cake and a filtrate; and carrying out acid leaching on the filter cake to obtain crude iron phosphate, and preferably carrying out acid leaching by using sulfuric acid with the mass concentration of 0.5-2%. The iron phosphate is further purified by filtration and acid leaching, and valuable metal impurities on the iron phosphate are recovered.
The filtrate and the pickling solution obtained in the present application both contain valuable metals, which can be recovered by a conventional method of valuable metals by those skilled in the art, and in some embodiments, the method further comprises wet recovering the valuable metals from the filtrate obtained in step S5 and the pickling solution obtained in step S1. For example, extraction, etc., the specific operations can refer to the prior art, and are not described herein.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
Ball milling and crushing: 4 random mixed materials of iron slag yellow sodium iron vitriol slag, goethite slag, hematite slag and iron phosphate waste slag are added with water to be dispersed and ball milled for 30min, the granularity of the system is reduced to micro-nano level, namely less than 50 mu m, and the system is used as the iron-containing slag of the acid washing object.
Acid washing and filtering: the weight contents of iron, phosphorus and valuable metals (nickel, cobalt, manganese, lithium and copper) in the ball-milled sample are analyzed by adopting sampling ICP (inductively coupled plasma) and cooperating with an iron ion titration method, the weight contents are recorded in table 1, and then sulfuric acid solution with twice volume is adopted, and H is added according to the molar weight of 1 percent of the total iron content2SO4The iron slag and the pickling solution were obtained after pickling, and the contents of the elements in the iron slag after pickling were analyzed and also reported in table 1.
TABLE 1
Adding acid and mixing materials: adding sulfuric acid with the total molar quantity of iron being 1.05 times into the iron slag after acid cleaning, then weighing sodium dihydrogen phosphate with the dosage of 1.01 of the theoretical dosage, and mixing for 30min to obtain a mixture.
And (3) granulation: and (3) forming the mixture into 0.5-3 cm particles, and air-drying for 0.5h to obtain the mixed particles.
Oxidizing and roasting: the mixed granules are put into a 50L box furnace, and air of 10L/min is introduced to bake for 2 hours at 200 ℃ to obtain a baked product.
Ball milling and crushing: and cooling the roasted product, taking out, putting into a ball mill, and carrying out ball milling for 30min, wherein the crushed particle size is 0.1-50 μm.
Slurrying and synthesizing: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 90 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for 24 hours to react to obtain the iron phosphate slurry.
Filtering and washing: the resulting iron phosphate slurry was filtered to dehydrate and rinsed with an appropriate amount of 2% aqueous sulfuric acid, and all the filtrate and rinse were collected to give D50 ═ 2 μm iron phosphate particles, and the yield of iron phosphate was calculated to be 96.5%, where the phosphorus to iron ratio was 1: 0.995.
Recovering valuable metals: the total yield of valuable metals is 98.5%, and the valuable metals in the pickling solution, the filtrate and the leacheate enter a wet recovery system to be separated and recovered.
Example 2
Ball milling and crushing: 4 random mixed materials of iron slag yellow sodium iron vitriol slag, goethite slag, hematite slag and lithium iron phosphate waste slag are added with water to be dispersed and ball milled for 45min, and the granularity of the system is reduced to micro-nano level, namely less than 50 mu m.
Acid washing and filtering: sampling ICP (inductively coupled plasma) and iron ion titration method are matched to analyze iron, phosphorus and organic matters in ball-milled samplesThe weight contents of the metal values (nickel, cobalt, manganese, copper, lithium) are recorded in Table 2, and then H is added in a molar amount of 2% of the total iron content using a three-fold volume of sulfuric acid solution2SO4And (4) carrying out acid pickling to obtain the iron slag and acid pickling solution after acid pickling.
TABLE 2
Adding acid and mixing materials: adding sulfuric acid with the total molar weight of iron being 1.03 times into the acid-washed filter residue, weighing sodium dihydrogen phosphate with the amount being 1.00 of the theoretical amount, and mixing for 60min to obtain a mixture.
And (3) granulation: and granulating the mixture obtained in the step to prepare small particles of 2-5 cm, and air-drying to obtain the mixed particles.
Oxidizing and roasting: putting the mixed particles into a 50L box furnace, introducing 15L/min air, and baking for 1 hour at 250 ℃ to obtain a baked substance;
ball milling and crushing: and cooling the roasted product, taking out, putting into a ball mill, and carrying out ball milling for 15min, wherein the crushed particle size is 0.1-50 μm.
Slurrying and synthesizing: adding 5 times of pure water and 0.08 times of sodium dodecyl sulfate into the roasted product after ball milling; stirring and heating to 80 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 1.0, and continuously stirring at a high speed of 2000rpm for reaction for 15 hours to obtain the iron phosphate slurry.
Filtering and washing: and filtering and dehydrating the generated iron phosphate slurry, and adding a proper amount of 5% sulfuric acid aqueous solution for leaching. The yield of iron phosphate was 97.8% calculated as D50 ═ 1.5 μm iron phosphate particles, with a 1:0.991 ferrophosphorus ratio.
Recovering valuable metals: the total yield of valuable metals is 98.9%, and the valuable metals in the pickling solution, the filtrate and the leacheate enter a wet recovery system to be separated and recovered.
Example 3
Ball milling and crushing: 4 random mixed materials of iron slag yellow sodium iron vitriol slag, goethite slag, ferric phosphate and lithium iron phosphate waste slag are added into water to be dispersed and ball milled for 60min, and the granularity of the system is reduced to micro-nano level, namely less than 50 mu m.
Acid washing and filtering: the ball-milled samples were sampled for analysis of the weight content of iron, phosphorus, valuable metals (nickel, cobalt, manganese, lithium, copper) and recorded in table 3, and then H was added in a molar amount of 1.5% of the total iron content using twice the volume of the sulfuric acid solution2SO4And (4) carrying out acid pickling to obtain the iron slag and acid pickling solution after acid pickling.
TABLE 3
Adding acid and mixing materials: adding sulfuric acid with the total molar weight of iron being 1.08 times into the acid-washed filter residue, weighing sodium dihydrogen phosphate with the amount being 1.02 of the theoretical amount, and mixing for 60min to obtain a mixture.
And (3) granulation: and granulating the mixture in the step to prepare small particles of 4-7 cm, and air-drying to obtain the mixed particles.
Oxidizing and roasting: the granules were placed in a 50L box furnace and dried at 150 ℃ for 3 hours by introducing 10L/min of air.
Ball milling and crushing: and cooling the dried material, taking out, putting into a ball mill, and carrying out ball milling for 60min, wherein the particle size after crushing is 0.1-50 μm.
Slurrying and synthesizing: adding pure water with the volume 7 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume 0.1 time that of the roasted product; stirring and heating to 85 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 1.2, and continuously stirring at a high speed of 1000rpm for reaction for 20 hours to obtain the iron phosphate slurry.
Filtering and washing: and filtering and dehydrating the generated iron phosphate slurry, and adding a proper amount of 2% sulfuric acid aqueous solution for leaching. D50 ═ 2 μm iron phosphate particles were obtained, the yield of iron phosphate was calculated to be 97.9%, with a phosphorus-to-iron ratio of 1: 0.987.
Recovering valuable metals: the total yield of valuable metals is 98.6%, and the valuable metals in the pickling solution, the filtrate and the leacheate enter a wet recovery system to be separated and recovered.
Example 4
Ball milling and crushing: 4 random mixed materials of iron slag yellow sodium iron vitriol slag, goethite slag, hematite slag and iron phosphate waste slag are added with water to be dispersed and ball milled for 30min, the granularity of the system is reduced to micro-nano level, namely less than 50 mu m, and the system is used as the iron-containing slag of the acid washing object.
Acid washing and filtering: the weight contents of iron, phosphorus and valuable metals (nickel, cobalt, manganese, copper and lithium) in the ball-milled sample are analyzed by adopting sampling ICP (inductively coupled plasma) and cooperating with an iron ion titration method, the weight contents are recorded in the table 4, and then sulfuric acid solution with five times of volume is adopted, and H is added according to the mole amount of 0.5 percent of the total iron content2SO4And (4) carrying out acid pickling to obtain the iron slag and acid pickling solution after acid pickling.
TABLE 4
Example 5
The difference from example 1 lies in the acid addition compounding process, specifically: adding sulfuric acid with the total molar quantity of iron being 1.1 times into the iron slag after acid cleaning, then weighing sodium dihydrogen phosphate, wherein the using quantity of the sodium dihydrogen phosphate is 1.01 of the theoretical using quantity, and mixing for 30min to obtain a mixture.
After filtration and washing, the iron phosphate particles with a D50-2.1 μm ratio of 1:0.99 were obtained, and the recovery of iron phosphate was calculated to be 96.8%.
Example 6
The difference from the embodiment 1 lies in the granulation step, and the particle diameter of the mixed particles after granulation is 9-12 cm.
After filtration and washing, the obtained D50 ═ 1.9 μm iron phosphate particles, where the phosphorus-iron ratio was 1:0.995, and the calculated recovery of iron phosphate was 97.2%.
Example 7
The difference from example 1 is in the slurry synthesis step, specifically: adding 5 times of pure water and 0.05 time of sodium dodecyl sulfate into the roasted product after ball milling; stirring and heating to 80 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 1.0, and continuously stirring at a high speed of 2000rpm for reaction for 15 hours to obtain the iron phosphate slurry.
After filtration and washing, D50 ═ 2.2 μm iron phosphate particles were obtained, the yield of iron phosphate was calculated to be 96.3%, with a phosphorus-iron ratio of 1: 0.995.
Example 8
The difference from example 1 is in the slurry synthesis step, specifically: adding 5 times of pure water and 0.1 time of sodium dodecyl sulfate into the roasted product after ball milling; stirring and heating to 80 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 1.0, and continuously stirring at a high speed of 2000rpm for reaction for 15 hours to obtain the iron phosphate slurry.
After filtration and washing, D50 ═ 1.4 μm iron phosphate particles were obtained, the yield of iron phosphate was calculated to be 96.6%, with a phosphorus-iron ratio of 1: 0.995.
Example 9
The difference from example 1 is in the slurry synthesis step, specifically: adding 5 times of pure water and 0.2 time of sodium dodecyl sulfate into the roasted product after ball milling; stirring and heating to 80 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 1.0, and continuously stirring at a high speed of 2000rpm for reaction for 15 hours to obtain the iron phosphate slurry.
After filtration and washing, D50 ═ 1.1 μm iron phosphate particles were obtained, the yield of iron phosphate was calculated to be 96.7%, with a phosphorus-iron ratio of 1: 0.996.
Example 10
The difference from example 1 lies in the step of oxidizing roasting, in particular: the mixed granules are put into a 50L box furnace, and air of 10L/min is introduced to bake for 10 hours at 120 ℃ to obtain a baked product.
After filtration and washing, the obtained D50 ═ 2 μm iron phosphate particles, the yield of iron phosphate was calculated to be 96.2%, wherein the ratio of phosphorus to iron was 1: 0.994.
Example 11
The difference from example 1 lies in the step of oxidizing roasting, in particular: the mixed granules were put into a 50L box furnace, and air was introduced at 10L/min to bake at 300 ℃ for 1 hour to obtain a baked product.
After filtration and washing, D50 ═ 2 μm iron phosphate particles were obtained, and the yield of iron phosphate was calculated to be 95.3%, where the ferrophosphorus ratio was 1: 0.991.
Example 12
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 70 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for 24 hours to react to obtain the iron phosphate slurry.
After filtration and washing, the obtained D50 ═ 2 μm iron phosphate particles, the yield of iron phosphate was calculated to be 92.1%, wherein the ratio of phosphorus to iron was 1: 0.988.
Example 13
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 95 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for 24 hours to react to obtain the iron phosphate slurry.
After filtration and washing, the yield of iron phosphate is calculated to be 98.5% by obtaining D50 ═ 2 μm iron phosphate particles, wherein the ratio of phosphorus to iron is 1: 0.990.
Example 14
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 90 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for reaction for 30 hours to obtain the iron phosphate slurry.
After filtration and washing, D50 ═ 1.9 μm iron phosphate particles were obtained, and the yield of iron phosphate was calculated to be 96.6%, where the ferrophosphorus ratio was 1: 0.995.
Example 15
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 90 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for reaction for 10 hours to obtain the iron phosphate slurry.
After filtration and washing, the obtained D50 ═ 2.3 μm iron phosphate particles, the yield of iron phosphate was calculated to be 94.7%, wherein the phosphorus-iron ratio was 1: 0.984.
Example 16
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 60 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.8, and continuously stirring at a high speed of 1500rpm for reaction for 36 hours to obtain the iron phosphate slurry.
After filtration and washing, the iron phosphate particles with D50 ═ 1.8 μm were obtained, and the yield of iron phosphate was calculated to be 90.8%, wherein the ratio of phosphorus to iron was 1: 0.992.
Comparative example 1
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 90 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 2.2, and continuously stirring at a high speed of 1500rpm for 24 hours to react to obtain the iron phosphate slurry. The iron phosphate obtained after the filtration washing treatment had a D50 value of 1.9 μm, and the calculated recovery rate of iron phosphate was 98.9%. But valuable metal copper enters into the iron phosphate product to influence the product quality
Comparative example 2
The difference from example 1 is the slurry synthesis step, specifically: adding pure water with the volume of 6 times that of the roasted product after ball milling, and adding sodium dodecyl sulfate with the volume of 0.05 time that of the roasted product; stirring and heating to 90 ℃; and adding a proper amount of ammonia water to adjust the pH value of the system to be about 0.5, and continuously stirring at a high speed of 1500rpm for 24 hours to react to obtain the iron phosphate slurry. After filtration and washing treatment, the obtained iron phosphate had D50 of 2.5 μm and the recovery rate of iron was 55%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the method, firstly, most of impurity metal ions such as nickel, cobalt, copper and lithium in the iron-containing slag are washed out by acid washing, most of soluble salts are washed away, and iron is remained in the iron slag after the acid washing; then mixing and granulating the iron slag after acid cleaning, acid and phosphate, and then roasting, wherein iron oxide in the iron slag after acid cleaning reacts with the acid under the roasting condition to form iron salt; after roasting is finished, the ferric phosphate slurry is obtained by heating and slurrying, solid-liquid separation is subsequently carried out to obtain a ferric phosphate crude product and a valuable metal solution, the obtained ferric phosphate crude product can be used as a raw material of a ferric phosphate battery, the metal recovery rate in the valuable metal solution can reach more than 98.5%, the total effective utilization of iron slag waste is realized, the process is simple and easy to implement, the additive is low in cost, the cost for synthesizing ferric phosphate can be optimized and reduced, and the comprehensive recycling of iron slag without slag is realized.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing iron phosphate by using iron-containing slag, which is characterized by comprising the following steps:
step S1, carrying out acid washing on the iron-containing slag to obtain acid-washed iron slag and acid washing liquid;
step S2, mixing and granulating the iron slag subjected to acid cleaning, acid and phosphate to obtain mixed particles;
step S3, roasting the mixed particles to obtain a roasted product;
step S4, heating and slurrying the roasted product under the condition that the pH value is 0.8-1.8 to obtain iron phosphate slurry;
and step S5, performing solid-liquid separation on the iron phosphate slurry to obtain an iron phosphate crude product and a valuable metal solution.
2. The method according to claim 1, characterized in that said step S1 is carried out by using sulfuric acid, preferably H in said sulfuric acid2SO4The molar amount of the iron-containing slag is 0.5-2%, preferably 1.0-1.5%, of the total molar amount of iron in the iron-containing slag, preferably the volume of the sulfuric acid is 1-5 times, preferably 2-3 times, of the volume of the iron-containing slag, preferably the iron-containing slag is selected from one or more of yellow sodium jarosite slag, goethite slag, hematite slag, iron phosphate waste slag and lithium iron phosphate slag, and preferably the particle size of the iron-containing slag is less than 50 μm.
3. The method according to claim 1, wherein in step S2, H is selected from+The molar weight of the acid is 2.0 to 2.2 times of the molar weight of the iron in the iron slag after acid cleaning, the molar weight of the phosphate is preferably 1.0 to 1.05 times of the molar weight of theoretical phosphate in terms of phosphorus element, the acid is preferably sulfuric acid, and the phosphate is preferably one or more of sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium phosphate and potassium phosphate.
4. The method according to claim 1, wherein the mixed particles have a particle size of 0.5 to 8 cm.
5. The method according to claim 1, wherein the roasting temperature in the step S3 is 120-300 ℃, the roasting time is 1-10 h, preferably the roasting is carried out in air, and the flow rate of the air is 1-20L/min, preferably 10-15L/min.
6. The method according to claim 1, wherein in step S4, the temperature of the heated slurry is 70 to 95 ℃ and the time is 10 to 30 hours, and preferably the roasted product is stirred during the heated slurry, and the rotation speed of the stirring is 1000 to 2000 rpm.
7. The method according to claim 1 or 6, wherein the step S4 includes:
mixing the roasted product with water and a surfactant to obtain a mixed slurry, wherein the surfactant is preferably sodium dodecyl sulfate and sodium hexadecyl sulfate, the volume ratio of the surfactant to the roasted product is preferably 0.05-0.2: 1, and the volume ratio of the roasted product to the water is preferably 1: 5-7;
and heating the mixed slurry, and maintaining the pH value of the mixed slurry to be 0.8-1.8 in the heating process to obtain the iron phosphate slurry.
8. The method of claim 1, wherein the baked material is pulverized to a particle size of 0.1-50 μm before the step S4.
9. The method according to claim 1, wherein the step S5 includes:
filtering the iron phosphate slurry to obtain a filter cake and a filtrate;
and carrying out acid leaching on the filter cake to obtain crude iron phosphate, and preferably carrying out acid leaching by using sulfuric acid with the mass concentration of 0.5-2%.
10. The method of claim 9 further comprising wet recovering valuable metals from said filtrate from step S5 and said pickle liquor from step S1.
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