CN120817630A - A method for preparing high-purity iron oxide red using jarosite slag - Google Patents
A method for preparing high-purity iron oxide red using jarosite slagInfo
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Abstract
本发明公开了一种利用黄钾铁矾渣制备高纯氧化铁红的方法，将黄钾铁矾渣与草酸溶液混合，将反应后的产物进行固液分离，获得富锌粉产品，对富铁络合离子Fe(C2O4)3 3‑浸出液中加入草酸、还原铁粉，使之转变为草酸亚铁结晶沉淀，经过真空干燥处理获得高纯电池级草酸亚铁粉末，在惰性气氛条件下进行焙烧，最终得到纯度≥98.5%、粒径符合电池级使用标准的高纯氧化铁红产品，最终实现黄钾铁矾渣资源化、高值化利用。本发明方法不仅克服了传统铁矾渣处理处置工艺流程长、能耗高、冶炼成本高的缺点，为企业解决棘手的危废处置难题的同时，产生了多种高附加值产品，具有显著的社会效益与经济效益。
The invention discloses a method for preparing high-purity iron oxide red using jarosite slag, wherein the jarosite slag is mixed with an oxalic acid solution, the product after the reaction is subjected to solid-liquid separation, a zinc-rich powder product is obtained, oxalic acid and reduced iron powder are added to the iron-rich complex ion Fe( C2O4 ) 33 - leachate to convert it into a ferrous oxalate crystal precipitate, a high-purity battery-grade ferrous oxalate powder is obtained through vacuum drying, and the powder is roasted under inert atmosphere conditions to finally obtain a high-purity iron oxide red product with a purity of ≥98.5% and a particle size that meets battery-grade use standards, thereby ultimately realizing resource utilization and high-value utilization of the jarosite slag. The method of the present invention not only overcomes the shortcomings of the traditional jarosite slag treatment and disposal process being long, energy consumption being high, and smelting cost being high, but also solves the difficult hazardous waste disposal problem for enterprises while producing a variety of high-value-added products, with significant social and economic benefits.
Description
Technical Field
The invention belongs to the field of bulk hazardous/solid waste resource utilization in the nonferrous industry, and particularly relates to a method for carrying out high-value utilization on bulk hazardous waste jarosite slag in the nonferrous industry and preparing high-purity iron oxide red, which is particularly suitable for the resource utilization of iron-containing dust mud with the impurity content of CaO, mgO, al 2O3、SiO2, cu, pb and the like of which is not higher than 15% and the S content of 5-20% in the form of Fe 3+ in hazardous/solid resources, and can be widely applied to the field of bulk solid waste resource utilization in industries such as nonferrous metal smelting, ferrous metallurgy and the like.
Background
Jarosite slag, i.e. jarosite slag (hereinafter referred to as jarosite slag), is tailings produced by iron removal by an jarosite method when valuable metals such as zinc, copper, nickel, cobalt, manganese, etc. are wet-smelted in the nonferrous industry. The chemical formula of the iron vitriol slag is AFe 3(SO4)2(OH)6 (A is K +、Na+、Pb2+、H3O+, etc.), generally contains 25-40% of Fe and 5-15% of S, and further contains a certain amount of valuable metals such as Zn, pb, cu, ni, etc., the total amount is generally 10-20%, and the iron vitriol slag mainly exists in the forms of sulfate and oxide. Taking an example of an electric zinc wet zinc-smelting plant with annual production of 20 ten thousand tons, approximately 6 ten thousand tons of iron vitriol slag are produced each year, and by 2024, the zinc output of China is accumulated to approximately 800 ten thousand tons, and the iron vitriol slag output is approximately 300 ten thousand tons, so that the electric zinc wet zinc-smelting plant has become a typical large amount of dangerous waste in the nonferrous metallurgy industry. The treatment of the iron vitriol slag at the present stage mainly comprises a fire treatment process, a wet treatment process and a fire-wet combined process. However, the treatment methods have the defects that when the iron vitriol slag is treated by a fire method, the S content of the iron vitriol slag is high, the concentration of SO 2 in flue gas generated after roasting is high, the environment is polluted, the environmental treatment cost is greatly increased, and in addition, metals such as Cu, ag and the like are difficult to volatilize and generally directly enter reduced iron, SO that the yield of valuable elements is low, and serious resource waste is generated. The wet process is to add reagents such as acid, alkali and the like, and assist in modes such as high temperature, high pressure, microorganisms and the like, and selectively enrich valuable elements in the leaching solution by means of extraction and ion precipitation. However, the complex process flow and a large amount of generated waste water and slag still need to be further treated, the cost is high, the fire-wet combined process can more comprehensively recover valuable elements in the iron vitriol slag, but the process has high process cost, and can generate pollution of flue gas SO 2 and pollution of tailings and tail liquid, and the popularization and the application in actual production practice are not performed at present. the patent 'a wet treatment process of iron vanadium slag in zinc hydrometallurgy' (CN 202110434643.7) proposes a method for reducing iron vanadium slag by using SO 2, oxidizing solution, separating and purifying solid and liquid to finally prepare hematite, which overcomes the defects of high energy consumption and large pollution in the pyrogenic process, but has a severe process flow, and serious environmental problems are caused by SO 2 pollution in the reduction stage, and the patent 'a preparation method of iron vanadium slag autoclaved brick' (CN 201810891593.3) proposes a method for preparing iron vanadium slag autoclaved brick by taking iron vanadium slag as a raw material and mixing the iron vanadium slag with other solid wastes (coarse aggregate, Fine aggregate, iron tailings, etc.), and finally preparing the iron alum slag autoclaved brick with certain compressive strength. However, the method does not fundamentally solve the problems of treatment and disposal of the iron vitriol slag, and the prepared autoclaved brick has the advantages of environmental pollution caused by leaching of S and other harmful components, high equipment investment cost, low added value of products and no good market popularization value.
In view of the above, the invention provides a method for preparing high-purity iron oxide red by the process flow of preparing high-purity iron oxide red through oxalic acid selective leaching and iron extraction-hydrothermal reduction precipitation-solid phase reaction aiming at the cost problem and the environmental problem faced by the prior recycling and high-value utilization of iron vitriol slag. The method not only overcomes the defects of long process flow, high energy consumption and high smelting cost of the traditional iron vitriol slag treatment and disposal, but also brings new economic growth points for enterprises while solving the difficult dangerous waste disposal problem for enterprises, and has remarkable social benefit, economic benefit and environmental benefit.
Disclosure of Invention
The invention aims to solve the problems of long process flow, high energy consumption, large unorganized emission, low added value of products and the like in the existing jarosite slag treatment technology, and provides a method for preparing high-purity iron oxide red by using jarosite slag.
In order to achieve the aim, the method for preparing the high-purity ferric oxide red by utilizing jarosite slag comprises the steps of taking jarosite slag actually produced by nonferrous smelting enterprises as a raw material, firstly, taking an organic acid solution (preferably oxalic acid) as a leaching agent, taking iron powder as a reducing agent, mixing the three materials according to a certain proportion to prepare slurry, utilizing complexation reaction between iron ions and organic acid radical ions (such as oxalate ions), converting rich iron resources in electric furnace dust into high-value-added iron oxalate under the experimental conditions of low temperature and normal pressure, carrying out solid-liquid separation on the reacted slurry, wherein the Zn content in the leaching slag can be greatly improved, taking the Zn content as a zinc extraction raw material, simultaneously, the obtained zinc product purity is higher, taking reaction tail liquid as a solvent to continuously leach the jarosite slag, realizing near zero emission overall, and finally converting the ferrous oxalate into the high-purity ferric oxide red under the inert roasting atmosphere for enriching the product types, thereby finally realizing the utilization of the high-value ferrous oxalate red.
The invention discloses a method for preparing high-purity iron oxide red by using jarosite slag, which is implemented according to the following process and steps:
S1 raw material pretreatment
Carrying out particle size analysis and water content analysis on large amount of iron-rich dangerous waste jarosite slag of a zinc hydrometallurgy enterprise as a raw material, carrying out dehydration and drying treatment on jarosite slag according to the water content analysis result to obtain jarosite slag dry materials with the water content less than or equal to 5.0 percent, carrying out ore grinding treatment on jarosite slag dry materials according to the particle size analysis result to obtain fine-fraction jarosite slag raw materials with the particle size of-0.074 mm and the content more than or equal to 85 percent;
S2 oxalic acid selective leaching
Mixing the fine-fraction jarosite slag raw material obtained in the step S1 with oxalic acid solution with the mass fraction of 8-25%, adding according to the liquid-solid ratio of the oxalic acid solution to the jarosite slag of 10/1 ml/g-30/1 ml/g, fully stirring, uniformly mixing, placing a reaction device in constant-temperature water bath equipment with the temperature of 50-90 ℃ to enable iron-containing components in the jarosite slag and oxalate to undergo hydrothermal complex reaction to generate soluble iron-containing complex ions Fe (C 2O4)3 3-; solid-liquid separation is carried out on the product after the reaction, and carrying out multi-time fractional filtration on supernatant to remove suspended impurities in the leachate to obtain iron-rich complex ions Fe (C 2O4)3 3- leachate A; the suspended impurities are filtered and dehydrated to obtain zinc-rich powder products with ZnO content of more than 33%;
S3, preparing battery-grade ferrous oxalate through hydrothermal reduction precipitation
Adding iron-rich complex ions Fe (C 2O4)3 3- lixivium A obtained in the step S2 as a raw material, oxalic acid and reduced iron powder as additives according to the mass ratio of oxalic acid to Fe (C 2O4)3 3- substances in the lixivium A controlled to be (0.6-2)/1, the mass ratio of reduced iron powder to Fe (C 2O4)3 3- substances in the lixivium A controlled to be (0.8-2.5)/1), regulating and controlling the stirring speed, controlling the reaction temperature to be 30-60 ℃, controlling the reaction time to be 4-10 h, and converting the iron-rich complex ions Fe (C 2O4)3 3-) with higher concentration in the solution into ferrous oxalate crystal precipitate by virtue of oxidation-reduction reaction between iron ions in different valence states, filtering and washing the ferrous oxalate crystal precipitate, dehydrating in a vacuum drying box at a certain temperature, controlling the vacuum drying temperature to be 60-90 ℃, controlling the vacuum degree to be-0.2-0 MPa, and controlling the drying time to be 5-20 h, so that obtaining high-purity ferrous oxalate powder can be leached, and the filtered tail solution B can be used as a solvent of a subsequent circulating jarosite slag can be recycled;
S4 solid phase reaction for preparing high purity iron oxide red
And (3) taking the high-purity battery grade ferrous oxalate powder obtained in the step (S3) as a raw material, roasting at the temperature of 400-600 ℃ in an inert atmosphere for 4-10 hours, and finally obtaining the high-purity iron oxide red product with the purity of more than or equal to 99.0% and the particle size meeting the battery grade use standard.
In the step S1, fe is required to be mainly in a state of Fe 2O3 in the jarosite slag raw material, the total iron content is more than or equal to 25%, wherein Fe 3+ accounts for more than 80% of the total iron content, the water content of the fine-fraction iron-rich material is preferably less than or equal to 1.0%, and the particle content of-0.074 mm in the fine-fraction raw material is preferably more than or equal to 95%.
In the step S2, the oxalic acid solution is preferably added according to the liquid-solid ratio of 15/1ml/g to 20/1ml/g of the iron vitriol slag, the mass fraction of the oxalic acid solution is preferably controlled to be 10-15%, the stirring speed is controlled to be 200-300 r/min, the reaction temperature of the hydrothermal complexing reaction is preferably controlled to be 70-80 ℃, and the reaction time is generally 2-6 h, preferably 3-4 h.
In the step S3, the addition is preferably carried out according to the mass ratio of oxalic acid to Fe (C 2O4)3 3-) in the leaching solution A being controlled to be (1.0-1.5)/1 and the mass ratio of reduced iron powder to Fe (C 2O4)3 3-) in the leaching solution A being controlled to be (1.25-1.75)/1, and the reaction temperature is controlled to be 40-50 ℃, the reaction time is controlled to be 6-8 h and the stirring speed is controlled to be 200-300 r/min.
Preferably, in the step S3, the vacuum drying temperature is controlled to be 70-80 ℃, the vacuum degree is controlled to be-0.2 to-0.1 MPa, and the drying time is 10-15 hours.
Preferably, in the step S4, roasting is performed under an argon or nitrogen atmosphere, the gas flow is controlled to be 200-400 sccm, the roasting temperature is 400-450 ℃, and the roasting time is controlled to be 6-7 hours.
Compared with the prior art, the method for preparing the high-purity iron oxide red by using jarosite slag has the following innovations and beneficial effects:
(1) The method for treating the iron vitriol slag and preparing the high-purity iron oxide red through the wet process provided by the invention finally realizes harmless treatment and high-value utilization of the hazardous waste of the iron vitriol slag, and belongs to the original innovation. Compared with the traditional high Wen Huofa roasting treatment process, the process overcomes the defects of high roasting temperature and large emission, effectively reduces the threat of hazardous waste to the environment, and simultaneously reduces the production cost of the high-purity iron oxide red from the raw material end, thereby having obvious economic advantages.
(2) The invention provides a process flow for preparing high-purity iron oxide red through a 'hydrothermal complexation selective leaching-hydrothermal reduction precipitation preparation high-purity ferrous oxalate-solid phase reaction', and a method for carrying out high-value utilization on bulk typical hazardous waste iron vitriol slag in the colored industry. The hazardous waste is used as a raw material, and the ferric oxide red powder with the average particle size of 4.056 mu m is finally prepared by regulating and controlling the reaction conditions, the particle size is finer and controllable, the product purity is more than 98.5%, the highest product purity can reach more than 99%, the quality requirements of high-performance material production enterprises such as downstream batteries and the like on the product are met, the added value is high, and the method has more competitive power in the market.
(3) The invention provides a method for preparing high-purity iron oxide red finally by taking iron vitriol slag as a raw material, carrying out step separation and extraction on abundant iron resources in the iron vitriol slag through wet leaching. Compared with the conventional technology, the method has the advantages that the final tail liquid is not discharged, the tail liquid is returned to the leaching process for recycling, the tail liquid is not required to be neutralized, the discharge is greatly reduced, and the environmental protection treatment cost is reduced by more than 60 percent.
(4) The invention provides a method for recycling and high-value utilization of large-scale typical hazardous waste iron vitriol slag in the nonferrous industry and preparing iron oxide red with high added value. Compared with the traditional iron oxide red processing and treating and iron oxide red preparation process, the method has the advantages of reducing the production cost by more than 50%, along with more industrialization prospect, mild reaction condition, greatly simplified part of the traditional production process, small investment cost and obvious direct economic benefit.
Drawings
FIG. 1 is a process flow diagram of a method for preparing high purity iron oxide red from jarosite slag according to the present invention;
FIG. 2 is an XRD diffraction pattern of jarosite slag powder used in the method of the present invention, using Cu-K alpha target radiation, with a diffraction angle 2 theta of 10-90 deg., and an X-ray wavelength lambda= 0.15416 nm;
FIG. 3 is a scanning electron microscope image of jarosite slag powder employed in the method of the present invention;
FIG. 4 is a graph showing the law of the effect of temperature on the leaching rate of iron components in jarosite slag when the jarosite slag is leached by hydrothermal complexation in the method of the present invention;
FIG. 5 is a graph showing the effect of oxalic acid concentration on the leaching rate of iron components in jarosite slag when the jarosite slag is leached by hydrothermal complexation Huang Jia in the method of the present invention;
FIG. 6 is a graph showing the effect of the liquid-solid ratio on the leaching rate of iron components in jarosite slag when the jarosite slag is leached by hydrothermal complexation in the method of the present invention;
FIG. 7 is a graph showing the law of the effect of reaction time on the leaching rate of iron components in jarosite slag when the jarosite slag is subjected to hydrothermal complexation leaching by the method of the present invention;
FIG. 8 is a graph showing the particle size analysis of the acid leaching product obtained by thermally complexing jarosite slag with oxalic acid;
FIG. 9 is an XRD spectrum of an acid leaching product obtained by thermally complexing jarosite slag with oxalic acid by the method of the invention, the diffraction angle 2 theta is 10-90 degrees, and the X-ray wavelength lambda= 0.15416 nm is adopted;
FIG. 10 is a scanning electron microscope image of an acid leaching product obtained by thermally complexing jarosite slag with oxalic acid in the method of the present invention;
FIG. 11 is a graph showing the law of temperature effects on the purity and particle size of ferrous oxalate when the ferrous oxalate is prepared by hydrothermal reduction precipitation;
FIG. 12 is a graph showing the influence rule of iron powder addition ratio on the purity and particle size of ferrous oxalate when the method of the invention is used for preparing ferrous oxalate by hydrothermal reduction and precipitation;
FIG. 13 is a graph showing the particle size distribution of a ferrous oxalate product prepared by hydrothermal reduction precipitation in accordance with the method of the present invention;
FIG. 14 is an XRD diffraction pattern of a hydrothermal reduction precipitation process for preparing a ferrous oxalate product, using Cu-K alpha target radiation, with a diffraction angle 2 theta of 10-90 deg., and an X-ray wavelength lambda= 0.15416 nm;
FIG. 15 is a scanning electron microscope image of the hydrothermal reduction precipitation process of the present invention for preparing ferrous oxalate;
FIG. 16 is a graph showing the particle size analysis of the solid phase reaction of the present invention to prepare high purity iron oxide red powder (specific surface area: 1597 m 2/kg).
Detailed Description
In order to further describe the present invention, a method for preparing high purity iron oxide red using jarosite slag according to the present invention will be described in further detail with reference to the accompanying drawings and examples.
The test raw material in the examples is jarosite slag which is a zinc smelting byproduct produced in the production activities of certain zinc hydrometallurgy enterprises.
To understand the chemical composition of jarosite slag, chemical multi-element analysis was performed on jarosite slag, and the results are shown in table 1. The detection results show that the contents of Fe, zn and Pb in jarosite slag are 27.80%, 6.34% and 1.69% respectively. The jarosite slag has a high S content of 13.48% and other factors such as CaO, mgO, al 2O3、SiO2 content of 1.02%, 0.48%, 2.42%, 7.68%, and basicity (cao+mgo)/(SiO 2+Al2O3) =0.15, respectively, and is typically an acidic slag.
TABLE 1 jarosite slag chemical multi-element analysis/wt%
As can be seen from FIG. 2, the jarosite slag phase is relatively simple and comprises mainly ammonium jarosite NH 4Fe3(SO4)2(OH)6, lead jarosite Pb (Fe 3(SO4)2(OH)6)2 and zinc ferrite ZnFe 2O4. Wherein the valuable element iron is mainly in the form of ammonium jarosite, lead jarosite and zinc ferrite compounds and zinc is mainly in the form of zinc ferrite and sulfur is mainly in the ammonium jarosite and lead jarosite.
FIG. 3 is a scanning electron microscope image of jarosite slag powder used in the method of the present invention. As can be seen from FIG. 3, jarosite slag has a relatively small granularity, and mainly presents the existence state of a fine particle agglomeration macromolecular structure, and leaching of iron components in jarosite slag needs to break bonding among molecules through chemical acting force, so that separation and recovery of valuable components are difficult to realize by adopting a conventional physical separation mode.
Experimental research shows that the zinc ferrite phase in jarosite slag is destroyed after acid leaching treatment, so that iron components are further released, zinc components are further enriched, and meanwhile, clean extraction and cascade separation recovery of valuable components can be realized according to complexation among Fe ions, zn ions and oxalate ions.
As shown in a process flow chart of a method for preparing high-purity iron oxide red by using jarosite slag in the invention shown in fig. 1, in the embodiment, the method is implemented by adopting the following process steps:
S1 raw material pretreatment
The method comprises the steps of taking large amount of iron-rich dangerous waste jarosite slag of zinc hydrometallurgy enterprises as a raw material, firstly carrying out dehydration and drying treatment on jarosite slag in a drying oven at 80 ℃ for 12 h hours to obtain jarosite slag dry materials with water content less than or equal to 0.5%, carrying out ball milling on jarosite slag dry materials in a planetary ball mill for 6 hours according to the particle size analysis result, wherein the initial particle size distribution of jarosite slag is 72% in the particle size of-0.074 mm, and obtaining fine jarosite slag raw materials with the particle size of-0.074 mm and the particle size of 97.0%.
S2 oxalic acid selective leaching
Mixing the fine-fraction jarosite slag raw material obtained in the step S1 with oxalic acid solution in a set proportion, fully stirring, uniformly mixing, placing a reaction device in constant-temperature water bath equipment, adjusting reaction temperature, reaction time and other condition parameters to enable iron-containing components in jarosite slag and oxalate to undergo hydrothermal complexing reaction to generate soluble iron-containing complexing ions Fe (C 2O4)3 3-), carrying out solid-liquid separation on the reacted product, carrying out multiple fractional filtration on supernatant fluid to remove suspended impurities in the leachate to obtain iron-rich complexing ions Fe (C 2O4)3 3- leachate A, and carrying out filtration and dehydration on the suspended impurities to obtain zinc-rich powder products with ZnO content of more than 33%.
FIG. 4 is a graph showing the influence of temperature on the leaching rate of iron components in jarosite slag when the method of the invention is used for carrying out hydrothermal complexation leaching of jarosite slag, FIG. 5 is a graph showing the influence of oxalic acid concentration on the leaching rate of iron components in jarosite slag when the method of the invention is used for carrying out hydrothermal complexation Huang Jia leaching of jarosite slag, FIG. 6 is a graph showing the influence of liquid-solid ratio on the leaching rate of iron components in jarosite slag when the method of the invention is used for carrying out hydrothermal complexation leaching of jarosite slag, and FIG. 7 is a graph showing the influence of reaction time on the leaching rate of iron components in jarosite slag when the method of the invention is used for carrying out hydrothermal complexation leaching of jarosite slag.
According to the results of figures 4-7, under the conditions that the liquid-solid ratio is 20:1, the concentration of oxalic acid solution is 15% and the reaction time is 2 h, the leaching rate of jarosite slag is increased along with the increase of the temperature, the leaching rate is greatly increased and changed at the temperature of 30-40 ℃ and gradually becomes stable at the temperature of 70-80 ℃, the leaching rate is higher at the concentration of 10-15% along with the increase of the concentration of oxalic acid, the concentration of oxalic acid is further optimized to be 12-15%, the oxalic acid content in the solution is increased along with the increase of the liquid-solid ratio on the premise that the concentration of oxalic acid is not changed, the equipment investment cost and the production cost are comprehensively considered, the optimal reaction condition is preferably 15:1-20:1, the leaching efficiency is continuously increased along with the increase of the time, and the reaction time is preferably controlled to be 3-4 h.
The experimental conditions show that the proper conditions for obtaining the jarosite slag hydrothermal leaching are that the reaction temperature is 80 ℃, the oxalic acid concentration is 15%, the liquid-solid ratio is 20:1, the reaction time is 180 min, and the stirring speed is 300 r/min. The leached product was characterized by XRF analysis as shown in table 2.
TABLE 2 chemical multi-element analysis of jarosite residue acid leaching products/wt%
As is clear from Table 2, the suspended impurities were dehydrated by filtration to obtain a zinc powder-rich product having a ZnO content of 34.15%.
Fig. 8 is a graph for analyzing the particle size of an acid leaching product obtained by thermally complexing jarosite slag by oxalic acid water, and fig. 9 is an XRD spectrum of the acid leaching product obtained by thermally complexing jarosite slag by oxalic acid water, wherein the diffraction angle 2 theta is 10-90 degrees by adopting Cu-K alpha target radiation, and the X-ray wavelength lambda= 0.15416 nm.
As can be seen from fig. 8 and 9, the acid leaching product obtained in this experiment had a particle size d10=1.92 μm, d50= 5.318 μm, d90=21.45 μm. The leached slag was characterized by using a D8 ADVANCE X-ray diffraction analyzer, and the result is shown in FIG. 9, wherein the leached slag mainly comprises zinc oxalate (ZnSO 4·2H2 O) and lead sulfate (PbSO 4), namely, the molecular structure inside jarosite slag is destroyed under the chemical action of acid, and the existing valuable elements are released. And further carrying out Scanning Electron Microscope (SEM) detection on the external appearance of the leached slag sample.
As can be seen from a scanning electron microscope image of an acid leaching product obtained by thermally complexing jarosite slag with oxalic acid by the method shown in fig. 10, the surface of the jarosite slag subjected to acid leaching has obvious erosion marks, the surface becomes loose and rough, the acid-soluble phase of jarosite slag is leached in the reaction process, and the particle structure is damaged to be changed into an irregular step shape.
S3, preparing battery-grade ferrous oxalate through hydrothermal reduction precipitation
The method comprises the steps of taking Fe (C 2O4)3 3- lixivium A obtained in the step S2 as a raw material, oxalic acid and reduced iron powder as additives, adding according to a set mass ratio of oxalic acid to Fe (C 2O4)3 3- substances) in the lixivium A and a set mass ratio of reduced iron powder to Fe (C 2O4)3 3- substances) in the lixivium A, regulating and controlling stirring speed, controlling reaction temperature and reaction time, converting Fe (C 2O4)3 3-) with higher concentration in solution into ferrous oxalate crystal precipitate by virtue of redox reaction among iron ions with different valence states, filtering and washing the ferrous oxalate crystal precipitate, dehydrating in a vacuum drying box at a certain temperature and vacuum degree, controlling drying time, and recycling filtered tail liquid B as a solvent for leaching jarosite slag in a subsequent cycle.
Fig. 11 is a graph showing the influence rule of temperature on the purity and the particle size of ferrous oxalate when the ferrous oxalate is prepared by hydrothermal reduction precipitation, and fig. 12 is a graph showing the influence rule of iron powder addition ratio on the purity and the particle size of ferrous oxalate when the ferrous oxalate is prepared by hydrothermal reduction precipitation. The test results show that under the conditions that the molar mass ratio of the iron powder to the oxalic acid is 1.25:1 and the reaction time is 2 h, the influence of the reaction temperature on the purity and the particle size of the product is examined, and the result is shown in figure 11. It is shown that the time for the formation of ferrous oxalate is 40-45 ℃. The effect of the iron powder addition ratio on the product purity and particle size was examined under the conditions of a reaction temperature of 40 ℃ and a reaction time of 8h, and the results are shown in fig. 12. From the graph, the addition ratio of the iron powder suitable for generating ferrous oxalate is 1.25-1.5.
Fig. 13 is a particle size distribution diagram of a ferrous oxalate product prepared by hydrothermal reduction precipitation, and fig. 14 is an XRD diffraction pattern of the ferrous oxalate product prepared by hydrothermal reduction precipitation, wherein the diffraction angle 2 theta is 10-90 degrees, and the X-ray wavelength lambda= 0.15416 nm is adopted by Cu-K alpha target radiation. The ferrous oxalate product was analyzed using a Bettersize 2000 laser particle size analyzer, the results of which are shown in fig. 13, and the product was characterized using a D8 ADVANCE type X-ray diffraction analyzer, the results of which are shown in fig. 14. The prepared ferrous oxalate is corresponding to ferrous oxalate standard card JCPDS No.23-0293, and the detected peak intensity is high, thus proving that the product has good crystallization and high crystallinity, no impurity peak appears, and further proving that the product has higher purity.
FIG. 15 is a scanning electron microscope image of the hydrothermal reduction precipitation process of the present invention for preparing ferrous oxalate. As can be seen from fig. 5, the ferrous oxalate product is in a regular cuboid shape, has small particle size, good reactivity and excellent physicochemical properties, and can be used as a raw material for preparing iron oxide red with high added value.
S4 solid phase reaction for preparing high purity iron oxide red
And (3) taking the high-purity battery grade ferrous oxalate powder obtained in the step (S3) as a raw material, and reacting for 6 h under the conditions of Ar atmosphere and roasting temperature of 450 ℃ to finally obtain the high-purity iron oxide red product with the purity of more than or equal to 99.6% and the grain size meeting the battery grade use standard.
FIG. 16 is a graph showing the particle size analysis of the solid phase reaction of the present invention to prepare high purity iron oxide red powder (specific surface area: 1597 m 2/kg). As can be seen from fig. 16, the iron oxide red powder prepared by the reaction had a relatively fine particle size d10=2.28 μm, d50=4.31 μm, d90=8.28 μm. Table 3 shows the results of mass analysis of experimentally prepared iron oxide red. As shown in Table 3, the purity of the iron oxide red prepared by the embodiment is high and can reach 99.60%, the contents of main impurity components such as K, na, cu, zn, ni, sulfate, chloride and the like are low, the product quality is good, the use requirement of the battery grade iron oxide red can be met, and the market prospect is good.
TABLE 3 iron oxide Red product quality analysis results
Claims (10)
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