阅读说明：本技术 一种用锶渣制备锶钡铁氧体的方法 (Method for preparing strontium barium ferrite from strontium slag ) 是由 陶长元 何宇 刘作华 崔志伟 张�雄 刘仁龙 杜军 谢昭明 范兴 孔令峰 吴丙山 于 2020-04-24 设计创作，主要内容包括：本发明公开了一种用锶渣制备锶钡铁氧体的方法,包括步骤(1)酸洗研磨预处理：将锶渣通过多次盐酸洗涤脱除锶渣中的可溶性杂质,过滤烘干后再进行研磨；步骤(2)BaCl<Sub>2</Sub>、SrCl<Sub>2</Sub>混合溶液的制备：在搅拌槽中加入一定量步骤(1)所得的粉状锶渣与过量的氯化钡溶液,混合均匀后,在一定反应条件下反应一定时间,过滤后,得含BaCl<Sub>2</Sub>、SrCl<Sub>2</Sub>滤液；步骤(3)铁氧体前驱体的制备：在步骤(2)的滤液中加入一定量的氯化铁溶液,以NaOH为沉淀剂,调节pH到11.5,搅拌反应15min,过滤,得滤渣,在100℃下烘干研磨；步骤(4)铁氧体的制备：将步骤(3)得到的固体放在瓷坩埚里,在马弗炉中以一定的升温速率到特定温度后,在该温度下保持一定时间,取出,冷却后将产物研磨成粉末。(The invention discloses a method for preparing strontium barium ferrite by strontium slag, which comprises the following steps of (1) acid-washing grinding pretreatment: washing strontium slag with hydrochloric acid for multiple times to remove soluble impurities in the strontium slag, filtering, drying and grinding; step (2) BaCl 2 、SrCl 2 Preparation of mixed solution: adding a certain amount of the powdery strontium slag obtained in the step (1) and an excessive barium chloride solution into a stirring tank, uniformly mixing, reacting for a certain time under certain reaction conditions, and filtering to obtain BaCl-containing material 2 、SrCl 2 Filtering the solution; step (3) preparation of ferrite precursor: adding a certain amount of ferric chloride solution into the filtrate obtained in the step (2), taking NaOH as a precipitator, adjusting the pH value to 11.5, stirring for reaction for 15min, filtering to obtain filter residue, and drying and grinding at 100 ℃; step (4) preparation of ferrite: putting the solid obtained in the step (3) in porcelainAfter the crucible is heated to a specific temperature in a muffle furnace at a certain heating rate, the crucible is kept at the temperature for a certain time, and the crucible is taken out, cooled and ground into powder.)

1. A method for preparing strontium barium ferrite by using strontium slag is characterized by comprising the following steps:

(1) acid washing and grinding pretreatment: washing strontium slag with the hydrochloric acid, and grinding into powder;

(2) preparation of mixed solution: adding the powdery strontium slag into a barium chloride solution, mixing, and filtering to obtain a mixed solution;

(3) preparing a ferrite precursor: adding ferric chloride into the filtrate; adding an alkaline precipitator and filtering to obtain filter residue; drying and grinding the filter residue to obtain a ferrite precursor;

(4) preparing ferrite: and roasting the ferrite and grinding to obtain the strontium barium ferrite.

2. The method for preparing strontium barium ferrite from strontium slag according to claim 1, wherein the method comprises the following steps:

in the step (1), the strontium slag contains impurities of calcium hydroxide and magnesium carbonate;

adding hydrochloric acid in the hydrochloric acid pickling process for several times, and fully washing under the stirring condition;

and (3) feeding the washed, filtered and dried strontium slag into a grinding or ball mill, and screening to obtain powdery strontium slag with the granularity of less than 200 meshes.

3. The method for preparing strontium barium ferrite from strontium slag according to claim 1 or 2, wherein the method comprises the following steps: in step (2), the barium chloride is in excess.

4. The method for preparing strontium barium ferrite from strontium slag according to claim 1 or 3, wherein the method comprises the following steps: in the step (3), the precipitator is NaOH, and the pH value is adjusted to 11.5.

5. The method for preparing strontium barium ferrite from strontium slag according to claim 1 or 3, wherein the method comprises the following steps:

and (4) putting the solid obtained in the step (3) into a ceramic crucible, heating the solid to 1000 ℃ from 20 ℃ in a muffle furnace at a heating rate of 8 ℃/min, keeping the temperature at 1000 ℃ for 2h, taking out the solid after the temperature is reduced to room temperature, cooling, and grinding the product into powder to obtain the strontium barium ferrite.

Technical Field

The invention belongs to the technical field of solid waste recycling treatment, and particularly relates to a method for preparing strontium barium ferrite from strontium slag.

Background

At present, the method for producing strontium carbonate in China is mainly a carbon reduction method, and a large amount of solid waste, namely strontium waste residue or strontium slag, can be generated by the process. The strontium salt enterprises can generate eight ten thousand tons of strontium slag every time one thousand tons of strontium salt is produced, which is always a serious problem for the enterprises. The strontium waste slag is alkaline water-quenched slag, and long-term stacking not only occupies a large amount of land, but also causes serious environmental problems. At present, the strontium waste residue is mainly applied to paving, cement preparation and the like. Although the problem of long-term stockpiling of strontium slag is solved, the strontium slag has high content, about 20 percent of strontium remains, and the waste of strontium resources can be caused during paving and the like. In recent years. With the increasing demand of strontium carbonate, strontium ferrite and the like, especially high-purity strontium carbonate and strontium ferrite. Therefore, the strontium ferrite is extracted and prepared from the waste residue, so that the resource is reasonably utilized, the environmental pollution is reduced, the purpose of emission reduction is finally achieved, and another way for effectively utilizing the strontium waste residue is provided for enterprises.

At present, researchers at home and abroad have more researches on the resource utilization of strontium in strontium slag and the like, wherein the researches mainly surround the wet leaching of strontium in the strontium slag and the preparation of strontium magnetic materials. The wet process leaching research of strontium in strontium slag includes converting strontium sulfate in the strontium slag into strontium carbonate with sodium carbonate and ammonium carbonate and preparing soluble strontium chloride with hydrochloric acid. The preparation research of the strontium magnetic material is to prepare strontium ferrite by a coprecipitation method under the condition of wet leaching and then prepare various types of ferrite by metal doping. In a word, the prior domestic and foreign resource utilization technology for strontium slag mainly has the following problems: (1) the process flow is complex; (2) low conversion rate of high added value and insignificant economic benefit.

Disclosure of Invention

The invention aims to provide a method for preparing strontium barium ferrite by using strontium slag, which is characterized by comprising the following steps of:

(1) acid washing and grinding pretreatment: washing strontium slag with hydrochloric acid, and grinding into powder;

(2) preparation of mixed solution: adding the powdery strontium slag into a barium chloride solution, mixing, and filtering to obtain a mixed solution; wherein, the barium ions are excessive (slightly excessive) relative to the strontium in the strontium slag;

(3) preparing a ferrite precursor: adding ferric chloride to the filtrate, wherein the ratio of ferric ions to strontium ions is about 12; adding an alkaline precipitator and filtering to obtain filter residue; drying and grinding the filter residue to obtain a ferrite precursor;

(4) preparing ferrite: and roasting the ferrite and grinding to obtain the strontium barium ferrite.

Further, in the step (1), the strontium slag contains impurities of calcium hydroxide and magnesium carbonate;

further, adding hydrochloric acid in the hydrochloric acid pickling process for several times, and fully washing under the stirring condition;

further, feeding the washed, filtered and dried strontium slag into a grinding or ball mill, and screening to obtain powdery strontium slag with the granularity less than 200 meshes;

further, in the step (2)Excess barium chloride, filtering to obtain BaCl₂、SrCl₂Mixing the solution;

further, in the step (3), the precipitant is NaOH, and the pH is adjusted to 11.5.

Further, in the step (4), the solid obtained in the step (3) is placed in a ceramic crucible, heated from 20 ℃ to 1000 ℃ in a muffle furnace at a heating rate of 8 ℃/min, kept at 1000 ℃ for 2h, taken out when the temperature is reduced to room temperature, cooled, and ground into powder to obtain the barium strontium ferrite.

The technical effect of the invention is needless to say that in the method, substances such as calcium hydroxide, magnesium carbonate and the like in the strontium slag are removed by acid washing, strontium-containing compounds in the strontium slag mainly exist in the form of strontium sulfate, the strontium sulfate reacts with barium chloride to generate barium sulfate and strontium chloride, and the strontium barium ferrite is prepared by a coprecipitation method.

Compared with the prior art, the invention has the beneficial effects that:

1) the method adopts pretreatment to remove impurities firstly, so that the main body of a substance capable of reacting with barium chloride in the strontium slag is strontium sulfate, the consumption of barium chloride can be reduced, and the influence of subsequent impurity removal on the strontium content can be avoided.

2) The invention adopts the strontium slag as the raw material for preparing the strontium ferrite, not only can reduce the stock quantity of the strontium slag, but also can bring good economic benefit and realize the high-value resource recycling of the strontium slag.

3) The technical scheme of the invention has the advantages of simple operation, low cost and high added value.

Drawings

Fig. 1 is an XRD analysis of the prepared intermediate and ferrite.

Detailed Description

The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.

Obtaining strontium slag, wherein the main components of the strontium slag are as follows:

element(s)	O	Sr	Ca	Si	S	Mg	Fe	Al	K	Ba	Ti
												Content%	38.05	19.04	13.56	9.38	6.61	4.29	3.83	3.43	0.71	0.49	0.38

(1) Acid washing and grinding pretreatment: 10.00g of strontium slag is put into a stirring tank, 50mL of hydrochloric acid with the concentration of 6mol/L is added for 5 times, and the strontium slag is fully washed under the stirring condition to remove impurities such as calcium hydroxide, magnesium carbonate and the like in the strontium slag; feeding the washed, filtered and dried strontium slag into a grinding or ball mill, and screening (sieving by a 200-mesh sieve) after grinding to obtain powdery strontium slag with the granularity of-200 meshes;

(2)BaCl₂、SrCl₂preparation of mixed solution: adding 1.00g of the powdery strontium slag obtained in the step (1) and an excessive barium chloride solution (the added volume is 60mL and the concentration is 0.05 mol/L) into a stirring tank, uniformly mixing, finishing the reaction, and filtering to obtain BaCl₂、SrCl₂Mixing the solution;

(3) preparing a ferrite precursor: adding ferric chloride solution (4.50 g of anhydrous ferric chloride is dissolved in 50mL of ultrapure water) into the filtrate obtained in the step (2), adjusting the pH to 11.5 by using 1.00mol/L NaOH solution as a precipitator, stirring for reaction for 15min, filtering to obtain filter residue, drying and grinding at 100 ℃ to obtain a ferrite precursor;

(4) preparing ferrite: and (4) putting the solid obtained in the step (3) into a ceramic crucible, heating the solid to 1000 ℃ from 20 ℃ in a muffle furnace at a heating rate of 8 ℃/min, keeping the temperature for 2h, cooling to room temperature, taking out, cooling, and grinding the product into powder to obtain the strontium barium ferrite. The powder was found to be adsorbed by the magnet close to the powder, and XRD detected that the solid was Sr_0.5Ba_0.5Fe₁₂O₁₉. The procedure of the test on the product and the results are shown in FIG. 1.