阅读说明：本技术 从氟钽酸钾结晶母液中回收钽资源的方法 (Method for recovering tantalum resource from potassium fluotantalate crystallization mother liquor ) 是由 胡松 黄水根 辛勇胜 樊红波 彭小婧 于 2020-07-01 设计创作，主要内容包括：本发明是提供一种从氟钽酸钾结晶母液中回收钽资源的方法,是以氟钽酸钾结晶母液为原料,包括先对氟钽酸钾结晶母液进行酸化处理,加入萃取剂后的萃取,分离,回收制备钽资源,有效解决钽铌湿法冶炼行业现有技术方法中采用氨中和回收钽资源,造成的处理成本高,产生的含氨氮废水处理困难的问题。具有方法简单有效,节能减排,环保、污染小及经济效益明显等的特点。(The invention provides a method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor, which takes the potassium fluotantalate crystallization mother liquor as a raw material, and comprises the steps of acidizing the potassium fluotantalate crystallization mother liquor, adding an extracting agent, extracting, separating and recovering the prepared tantalum resources, thereby effectively solving the problems of high treatment cost and difficult treatment of the generated wastewater containing ammonia nitrogen caused by adopting ammonia to neutralize and recover the tantalum resources in the prior art method in the tantalum-niobium hydrometallurgy industry. The method has the characteristics of simplicity, effectiveness, energy conservation, emission reduction, environmental protection, small pollution, obvious economic benefit and the like.)

1. A method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor takes the potassium fluotantalate crystallization mother liquor as a raw material, and comprises the following steps:

1) acidifying, namely adding an acid solution into the potassium fluotantalate crystallization mother liquor by taking the potassium fluotantalate crystallization mother liquor as a raw material to perform acidifying treatment to obtain a potassium fluotantalate acidifying treatment solution;

2) extracting, namely adding an extracting agent into the potassium fluotantalate acidizing solution obtained in the previous step, extracting and separating to obtain tantalum-containing extract and raffinate, and discharging the raffinate after the raffinate is subjected to neutralization treatment and qualified treatment;

3) separating, namely separating and purifying the tantalum-containing extract liquid in the step 2), namely repeatedly extracting the potassium fluotantalate acidizing fluid by the tantalum-containing extract liquid until the tantalum content is more than or equal to 0.75g/l, and returning to production for recycling; obtaining a separation liquid containing tantalum and a separation crystallization mother liquid;

4) recovering, namely treating the recovered raffinate of the separated crystallization mother liquor in the step 3) until the tantalum content is less than or equal to 0.032g/l, and discharging the residual crystallization mother liquor after the residual crystallization mother liquor is qualified through alkali neutralization treatment.

2. The method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor as claimed in claim 1, wherein the tantalum content in the potassium fluotantalate crystallization mother liquor in step 1) is controlled to be 0.1-2 g/l.

3. The method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor as claimed in claim 1, wherein said acid solution in step 1) is an acidic aqueous solution generated in a tantalum-niobium hydrometallurgy process, and the concentration of the acid solution in the acidic aqueous solution in the potassium fluotantalate acidification treatment liquor is controlled to be 3-6 mol/l; the acidification treatment time is controlled to be 28-35 hours.

4. The method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor according to claim 1, wherein the extractant in step 2) is a mixture of alcohols and/or methyl isobutyl ketone; controlling the volume ratio of the extracting agent to the potassium fluotantalate acidizing solution to be 25-100: 1.

5. the method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor in claim 1, wherein in the step 2), a surfactant is further added during the extraction separation; the surfactant is a nonionic surfactant.

6. The method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor as claimed in claim 5, wherein the nonionic surfactant is octylphenol polyoxyethylene ether or carbon fatty alcohol polyoxyethylene ether or polyethylene glycol type nonionic surfactant.

Technical Field

The invention relates to the field of recycling of rare resources of chemical raw materials, in particular to a method for recycling tantalum resources from potassium fluotantalate crystallization mother liquor.

Technical Field

Tantalum is a high-value rare metal and is widely used in the fields of electronics, military industry, aerospace and medical treatment. Although tantalum is abundant in China, the ore is low in taste, fine and dispersed in embedded particle size, and very difficult to collect, divide and select, so that how to utilize the tantalum resource to the maximum extent is a research subject in the tantalum-niobium industry, and the recovery of the tantalum resource becomes particularly important. The potassium fluotantalate crystallization mother liquor still contains a small amount of tantalum, and the potassium fluotantalate crystallization mother liquor is used as waste liquor containing tantalum resources, so that the environment is easily polluted without recovery treatment, and the tantalum resources are wasted. However, the common practice in the tantalum-niobium hydrometallurgy industry at present is to precipitate tantalum by neutralizing potassium fluotantalate crystallization mother liquor with ammonia, and then filter and recover tantalum resources.

For example, chinese patent publication No. CN 103898331 a specifically discloses a method for comprehensively recovering tantalum and niobium from red mud, which mixes red mud with a reducing agent to perform reduction roasting, and then performs magnetic separation to obtain magnetic iron concentrate and non-magnetic slag; melting the mixture of the non-magnetic slag, the sodium hydroxide and the sodium carbonate at the temperature of 500-800 ℃, and converting tantalum-niobium into sodium tantalate and sodium niobate; crushing the melted blocky melt, heating, stirring and leaching by using a certain amount of acid to dissolve oxides of main components of calcium, aluminum, silicon and a small amount of iron in the nonmagnetic slag, and decomposing the complex compounds of tantalum and niobium to convert into hydroxide, but still remaining in the slag for enrichment; heating and dissolving the acid leaching residue in mixed acid of HF and HNO3, cooling, adding water and H₂SO₄Diluting; and (4) carrying out niobium-tantalum separation and extraction on the diluted solution by adopting a liquid membrane method. However, the recovery treatment process for tantalum is complex, too much acid is added, hydrofluoric acid is treated, and sulfuric acid and nitric acid are treated, so that the subsequent treatment after separation and extraction is difficult, the environmental impact is large, and the treatment cost is high. Low product yield, pollution discharge and amplification of industrial wastes and the like.

Disclosure of Invention

The invention aims to provide a method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor, which takes the potassium fluotantalate crystallization mother liquor as a raw material and comprises the steps of acidizing the potassium fluotantalate crystallization mother liquor, adding an extracting agent, extracting, separating and recovering the prepared tantalum resources, thereby effectively solving the problems of high treatment cost and difficult treatment of the generated ammonia-nitrogen-containing wastewater caused by adopting ammonia to neutralize and recover the tantalum resources in the prior art method in the tantalum-niobium hydrometallurgy industry. The method has the characteristics of simplicity, effectiveness, energy conservation, emission reduction, environmental protection, small pollution, obvious economic benefit and the like.

The technical scheme provided by the invention discloses a method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor, which takes the potassium fluotantalate crystallization mother liquor as a raw material and comprises the following steps:

1) acidifying, namely adding an acid solution into the potassium fluotantalate crystallization mother liquor by taking the potassium fluotantalate crystallization mother liquor as a raw material to perform acidifying treatment to obtain a potassium fluotantalate acidifying treatment solution;

2) extracting, namely adding an extracting agent into the potassium fluotantalate acidizing solution obtained in the previous step, extracting and separating to obtain tantalum-containing extract and raffinate, and discharging the raffinate after the raffinate is subjected to neutralization treatment and qualified treatment;

3) separating, namely separating and purifying the tantalum-containing extract liquid in the step 2), namely repeatedly extracting the potassium fluotantalate acidizing fluid by the tantalum-containing extract liquid until the tantalum content is more than or equal to 0.75g/l, and returning to production for recycling; obtaining a separation liquid containing tantalum and a separation crystallization mother liquid;

4) and (3) recovering, namely treating the separated crystallization mother liquor and the recovered raffinate in the step 3) until the tantalum content is less than or equal to 0.032g/l, and discharging the residual crystallization mother liquor and the residual recovered raffinate after the alkali neutralization treatment is qualified.

The method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor comprises the step 1) of controlling the tantalum content in the potassium fluotantalate crystallization mother liquor to be 0.1-2 g/l.

The method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor comprises the following steps of 1) controlling the concentration of an acid solution in an acid aqueous solution in a potassium fluotantalate acidification treatment liquid to be 3-6mol/l, wherein the acid solution is an acid aqueous solution generated in a tantalum-niobium hydrometallurgy process; the acidification treatment time is controlled to be 28-35 hours.

The method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor comprises the following steps of 2) mixing an alcohol and/or methyl isobutyl ketone as an extracting agent; controlling the volume ratio of the extracting agent to the potassium fluotantalate acidizing solution to be 25-100: 1.

in the method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor, preferably, a surfactant is added during the extraction separation in the step 2); the surfactant is a nonionic surfactant.

Further, the method for recovering the tantalum resource from the potassium fluotantalate crystallization mother liquor comprises the step of using a polyoxyethylene octylphenol ether or polyoxyethylene fatty alcohol ether or polyethylene glycol type nonionic surfactant as the nonionic surfactant.

The invention relates to a method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor, wherein in the step 1), the acid solution subjected to acidification treatment is a sulfuric acid aqueous solution generated in a tantalum-niobium wet smelting process. The preferred acidification temperature is 40-60 ℃.

The extractant alcohol according to the invention is preferably a secondary octanol.

The invention relates to a method for recovering tantalum resources from potassium fluotantalate crystallization mother liquor, which comprises the following process flows of:

potassium fluotantalate crystallization mother liquor raw material → sulfuric acid generated in the tantalum-niobium hydrometallurgy process → adjustment of acid liquor concentration → mixed acidification → addition of extracting agent → separation → return of tantalum-containing extract liquid for continuous recycling → crystallization mother liquor after tantalum extraction → addition of alkaline raw material lime for neutralization treatment and discharge.

The sulfuric acid aqueous solution is added into the potassium fluotantalate crystallization mother liquor, the acidity of the sulfuric acid in the crystallization mother liquor is adjusted to a required value, and the tantalum element in the crystallization mother liquor under the acidity is easily extracted by an extracting agent. And extracting tantalum in the treated crystallization mother liquor by using an extracting agent, returning the extracting agent containing tantalum to production and use after extraction is finished, and discharging the residual crystallization mother liquor after the residual crystallization mother liquor is neutralized by lime and qualified. The method reasonably utilizes the waste acid liquor generated in tantalum-niobium wet smelting, adjusts the acidity of sulfuric acid in the crystallization mother liquor, can reuse the tantalum-containing extractant for production, recovers the tantalum resources, and has the tantalum recovery rate of more than 92 percent and the highest rate of 96 percent. The method effectively solves the problems of high treatment cost and difficult treatment of the generated ammonia nitrogen-containing wastewater caused by adopting ammonia for neutralizing and recovering tantalum resources in the prior art method in the tantalum-niobium hydrometallurgy industry. The method is simple and effective, and the tantalum recovery method has the characteristics of energy conservation, emission reduction and obvious economic benefit compared with the conventional treatment method.

Detailed Description

In order to enhance the understanding of the present invention, the present invention will be described in further detail with reference to the following examples, which are only for the purpose of illustrating the present invention and are not to be construed as limiting the scope of the present invention.