阅读说明：本技术 稀土氧化物的提纯方法及制得的产品 (The method of purification of rare earth oxide and product obtained ) 是由 付国燕 王玮玮 刘召波 付云枫 姚心 于 2019-09-27 设计创作，主要内容包括：公开一种稀土氧化物的提纯方法,形成溶液步骤,配制含硫酸根离子和稀土离子的溶液；沉淀步骤,以草酸盐为沉淀剂添加到所述溶液中进行沉淀反应；干燥焙烧步骤,将制得的沉淀物经过洗涤干燥后,焙烧得到粗制稀土氧化物；及除去硫酸根步骤,用酸性溶液洗涤所述粗制稀土氧化物。本发明的稀土氧化物的提纯方法,利用草酸盐作为沉淀剂,对含稀土离子的溶液进行沉淀处理,过滤、干燥、焙烧后获得粗制稀土氧化物粉体,然后用酸性溶液洗涤处理该粗制稀土氧化物得到除去硫酸根的稀土氧化物粉体。本发明的提纯方法有效地提高了稀土氧化物的纯度；简化了稀土沉淀物纯化的工艺流程；降低了能耗；避免了废渣固体废弃物的产生。(A kind of method of purification of rare earth oxide is disclosed, solution step is formed, prepares the solution of sulphate-containing ion and rare earth ion；Settling step is added in the solution as precipitating reagent using oxalates and carries out precipitation reaction；Drying and roasting step, by sediment obtained after washing is dry, roasting obtains crude rare earth oxide；And sulfate radical step is removed, the crude rare earth oxide is washed with acid solution.The method of purification of rare earth oxide of the invention, using oxalates as precipitating reagent, precipitation process is carried out to the solution containing rare earth ion, crude RE oxide powder is obtained after filtering, dry, roasting, is then removed the RE oxide powder of sulfate radical with the acid solution carrying out washing treatment crude rare earth oxide.Method of purification of the invention effectively improves the purity of rare earth oxide；Simplify the process flow of rare-earth precipitation object purifying；Reduce energy consumption；Avoid the generation of waste residue solid waste.)

1. a kind of method of purification of rare earth oxide, it is characterised in that:

Solution step is formed, the solution of sulphate-containing ion and rare earth ion is prepared；

Settling step is added in the solution as precipitating reagent using oxalates and carries out precipitation reaction；

Drying and roasting step, by sediment obtained after washing is dry, roasting obtains crude rare earth oxide；And

Sulfate radical step is removed, washs the crude rare earth oxide with acid solution.

2. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the formation solution step, The concentration of sulfate radical is 0.50~1.5mol/l, preferably 0.75~1.5mol/l in the solution.

3. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the settling step, In It is added before the precipitating reagent further include:

The solution is heated to 70~100 DEG C, preferably 75~95 DEG C；With

Dispersing agent is added into the solution.

4. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the settling step, with The molar ratio of rare earth ion and oxalates is that 1:1~1:5 adds precipitating reagent into the solution, while adding pH adjuster and make PH value of reaction system maintains between 1.0~3.0, and preferably 1.5~3.

5. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the settling step, add Stirring while adding the precipitating reagent, the speed of the stirring are 100~300r/min, preferably 100~200r/min；Addition It is persistently stirred after the complete precipitating reagent, the speed of the stirring is 50~200r/min, preferably 100~150r/min, stirring Time is 15~90min, preferably 30~90min.

6. the method for purification of rare earth oxide according to claim 1, which is characterized in that after the settling step also Including aging step, 70~100 DEG C of the Aging Temperature, preferably 75~95 DEG C；The digestion time is 30~200min, excellent It is selected as 60~180min.

7. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the drying and roasting step In, the maturing temperature is 700~1100 DEG C, preferably 800~1000 DEG C；Calcining time is 100~400min, preferably 120~300min.

8. the method for purification of rare earth oxide according to claim 1, which is characterized in that in the removing sulfate radical step In, the acid solution concentration expressed in percentage by weight is 2%~10%.

9. the method for purification of rare earth oxide according to claim 8, which is characterized in that wash it in the acid solution Afterwards, hot pure water is recycled to be washed, the rare earth oxide that filtering, drying are purified；The acid solution is selected from hydrochloric acid, carbon One of acid, oxalic acid, hypochlorous acid, acetic acid are a variety of.

10. a kind of earth oxide product, which is characterized in that be made by method of purification described in claim 1-9.

Technical field

The present invention relates to field of hydrometallurgy, and in particular to the method for purification of rare earth oxide and product obtained.

Background technique

Precipitating is essential purification method in metallurgy industry production, actually almost all of hydrometallurgy stream Can all there be precipitation process in journey, it has the characteristics that easy to operate, at low cost, small investment.Precipitating be take appropriate measures make it is molten Solute supersaturation in liquid, the method separated after being precipitated with solid forms.With the continuous improvement required product quality, Requirement to the impurity content in sediment is also continuously improved.In Extraction of rare earth element, rare earth element and impurity element are realized Efficiently separate and have great importance.The separation of rare earth element and non-rare earth impurity can be divided into crude separation and purification two Point, purification is except trace impurity from Rare Earth Elements Determination, and high purity rare earth oxide is produced frequently with oxalate precipitation Method and extraction etc. refine rare earth oxide.And commonly use sulfuric acid in extracting rare-earth element technical process and carry out extraction reaction, A large amount of sulfate ion can be introduced into enter in reaction system, and after depositing technology, sulfate radical can be with corresponding rare earth Element and precipitating reagent form double salt, have seriously affected the degree of purity of rare earth oxide.

For the sulfate radical in removal rare earth object, each Rare Earth Factory can remove sulfate ion therein, meeting using barium chloride Cause certain problem.Poisonous and harmful substance barium chloride is introduced first in precipitating.Secondly, a large amount of secondary residue sulphur can be generated Sour barium.Meanwhile needing to improve calcination process temperature to improve rare-earth precipitation object purity, cause the energy consumption for preparing rare-earth substance to mention Height, to seriously constrain the effective use and exploitation of rare-earth substance.

Summary of the invention

In order to overcome drawbacks described above, the present invention provides the method for purification and production obtained by this method of a kind of rare earth oxide Product.

The present invention provides a kind of method of purification of rare earth oxide, comprising: forms solution step, prepares sulphate-containing ion With the solution of rare earth ion；Settling step is added in the solution as precipitating reagent using oxalates and carries out precipitation reaction；Dry roasting Step is burnt, by sediment obtained after washing is dry, roasting obtains crude rare earth oxide；And sulfate radical step is removed, The crude rare earth oxide is washed with acid solution.

According to an embodiment of the present invention, in the formation solution step, the concentration of sulfate radical is in the solution 0.50~1.5mol/l, preferably 0.75~1.5mol/l.

Another embodiment according to the present invention, in the settling step, before the precipitating reagent is added further include: The solution is heated to 70~100 DEG C, preferably 75~95 DEG C；Dispersing agent is added with into the solution.

Another embodiment according to the present invention, in the settling step, with the molar ratio of rare earth ion and oxalates Precipitating reagent is added into the solution for 1:1~1:5, at the same add pH adjuster make pH value of reaction system maintain 1.0~ Between 3.0, preferably 1.5~3.

Another embodiment according to the present invention, in the settling step, stirring while adding the precipitating reagent, institute The speed for stating stirring is 100~300r/min, preferably 100~200r/min；It is persistently stirred after having added the precipitating reagent, institute State stirring speed be 50~200r/min, preferably 100~150r/min, mixing time be 15~90min, preferably 30~ 90min。

Another embodiment according to the present invention further includes aging step after the settling step, the ageing temperature 70~100 DEG C, preferably 75~95 DEG C of degree；The digestion time is 30~200min, preferably 60~180min；

Another embodiment according to the present invention, in the drying and roasting step, the maturing temperature is 700~1100 DEG C, preferably 800~1000 DEG C；Calcining time is 100~400min, preferably 120~300min.

Another embodiment according to the present invention, in the removing sulfate radical step, the acid solution weight percent Concentration is 2%~10%.

Another embodiment according to the present invention is washed in the acid solution and then is washed using hot pure water, The rare earth oxide that filtering, drying are purified；The acid solution is in hydrochloric acid, carbonic acid, oxalic acid, hypochlorous acid, acetic acid One or more solution.

The present invention also provides a kind of earth oxide products as made from above-mentioned method of purification.

The method of purification of rare earth oxide of the invention, using oxalates as precipitating reagent, to the solution containing rare earth ion Precipitation process is carried out, obtains crude RE oxide powder after filtering, dry, roasting, it then should with acid solution carrying out washing treatment Crude rare earth oxide is removed the RE oxide powder of sulfate radical.Method of purification of the invention effectively improves rare earth The purity of oxide；Simplify the process flow of rare-earth precipitation object purifying；Reduce energy consumption；Avoid waste residue solid waste It generates.

Detailed description of the invention

Its example embodiment is described in detail by referring to accompanying drawing, above and other feature of the invention and advantage will become It is more obvious.

Fig. 1 is the flow diagram of method of purification of the invention.

Specific embodiment

It elaborates With reference to embodiment to the present invention.

As shown in Figure 1, the method for purification of rare earth oxide of the invention, comprising: S1 forms solution step, prepares sulfur acid The solution of radical ion and rare earth ion；S2 settling step is added in solution carry out precipitation reaction by precipitating reagent of oxalates；S3 Drying and roasting step, by sediment obtained after washing is dry, roasting obtains crude rare earth oxide；And S4 removes sulfuric acid Root step washs crude rare earth oxide with acid solution.

In S1 step, the concentration of sulfate radical is 0.50~1.5mol/l, preferably 0.75~1.5mol/l in solution.

In S2 step, in order to accelerate to react before precipitating reagent is added, solution can be heated and improve reaction temperature.It is molten Liquid temperature is preferably kept at 70~100 DEG C, more preferably 75~95 DEG C.It, can be in the solution in order to increase the dispersibility of sediment Dispersing agent, such as polyethylene glycol etc. is added.

In S2 step, precipitating reagent is added into solution for 1:1~1:5 with the molar ratio of rare earth ion and oxalates, together Shi Tianjia pH adjuster, such as ammonium hydroxide etc. maintain pH value of reaction system between 1.0~3.0, and preferably 1.5~3.Add Stirring while adding precipitating reagent, the speed of stirring are 100~300r/min, preferably 100~200r/min.Precipitating reagent is added It persistently stirring afterwards, the speed of stirring is 50~200r/min, and preferably 100~150r/min, mixing time is 15~90min, Preferably 30~90min.By the step, rare earth ion and oxalate in mother liquor, which are formed, to be precipitated, and sulfate radical can be with scandium ion And other ions form double salt in solution, meanwhile, sulfate ion will form complex compound and be adsorbed on the surface of sediment containing scandium.

It can also include aging step after S2 step, convenient for being separated by solid-liquid separation.It is preferred that 70~100 DEG C of Aging Temperature, more Preferably 75~95 DEG C.Digestion time is preferably 30~200min, more preferably 60~180min.After ageing, solid-liquid is carried out Isolated sediment.Such as be separated by solid-liquid separation by filtering, 3-5 is washed respectively using water and ethyl alcohol during the separation process It is secondary, remove the impurity of sediment.

In the S3 step, sediment obtained is roasted after drying.At 700~1100 DEG C of temperature, preferably 800~ At 1000 DEG C, 100~400min, preferably 120~300min are roasted.It is cooled to room temperature later, obtains crude rare-earth oxidation Powder.

In S4 step, further purification removes sulfate radical.With acid solution, such as hydrochloric acid, carbonic acid, oxalic acid, hypochlorous acid, vinegar One of acid is a variety of, washs crude rare earth oxide.The concentration expressed in percentage by weight of acid solution is preferably 2%~10%.It is logical The washing of peracidity solution, sulfuric acid double salt is reacted with acid solution generates soluble sulfate, recycles pure water and ethanol washing Sulfate radical is removed, the rare earth oxide of purification is obtained after drying.

It washs in acid solution and then is washed using hot pure water, the rare-earth oxidation that filtering, drying are purified Object.