CN105886764A

CN105886764A - Method for preparing Sm2O3 from SmCl3 solution containing ZnCl2 through oxalic acid precipitation

Info

Publication number: CN105886764A
Application number: CN201610233789.4A
Authority: CN
Inventors: 李慧琴; 郭瑞华; 刘全; 刘永珍; 韩强
Original assignee: Inner Mongolia University of Science and Technology
Current assignee: Inner Mongolia University of Science and Technology
Priority date: 2016-04-15
Filing date: 2016-04-15
Publication date: 2016-08-24
Anticipated expiration: 2036-04-15
Also published as: CN105886764B

Abstract

The invention relates to a method for preparing Sm2O3 from a SmCl3 solution containing ZnCl2 through oxalic acid precipitation and belongs to the field of rare earth hydrometallurgy. NH4Cl is added into ZnCl2 and SmCl3 solutions as a liquid material, NH4Cl is added into an oxalic acid solution as a precipitant, and the concentrations of the NH4Cl in the liquid material and the precipitant are both 4mol/L. At a reaction temperature of 80DEG C, the precipitant is added into the liquid material, and the pH value of precipitating mother liquid is regulated to 6.8 by using ammonium bicarbonate. Sm<3+> in the liquid material is fully converted to samarium oxalate and precipitated, and after the samarium oxalate is burnt, an Sm2O3 product with a ZnO content which is smaller than 0.003% is obtained; and Zn<2+> in the liquid material is not precipitated. The method realizes the precipitation and separation of the Sm<3+> and the Zn<2+> by using the oxalic acid, can reduce production cost and simplify production procedures and facilitates the realization of industrial production.

Description

From containing ZnCl2 's SmCl3 The precipitation preparation of solution mesoxalic acid Sm2O3 Method

Technical field

The present invention relates to a kind of from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation preparation Sm₂O₃Method, belong to field of rare earth hydrometallurgy.

Background technology

Eu during enterprise uses zinc powder reduction europium-enriched solution at present³⁺Prepare europium oxide technique, in europium-enriched solution, add zinc powder by Eu³⁺It is reduced into Eu²⁺, and zinc powder is changed into Zn²⁺Enter in earth solution, containing Zn²⁺Earth solution as the feed liquid of reduction extraction, at reduction extraction segregation section Zn²⁺As easily extraction component with Sm³⁺、Gd³⁺After back extraction, samarium europium segregation section is returned to, Zn Deng trivalent rare earth ions²⁺With Sm³⁺Flow out from samarium europium segregation section raffinate together, directly with oxalic acid as precipitant, Zn²⁺Also precipitate together with samaric oxalate, affect Disamarium trioxide product quality, in order to ensure Disamarium trioxide product quality, Sm need to be carried out³⁺And Zn²⁺Separate；CN1715430A patent and the written zinc of document Li Hui qin and Rare Earth Separation and the preparation of basic zinc carbonate, rare earth, 2006,27 (6): 62-64, it is provided that a kind of zinc and Rare Earth Separation method, utilize N₂₃₅Realize Zn²⁺And RE³⁺Separate；CN103924078A, CN103924079A, CN103924080A patent provides uses P₅₀₇Extract and separate Sm³⁺And Zn²⁺Technology；Japan Patent JP2001151743 reports in the mixed solution of rare earth and zinc, and after adding three (2-amino-ethyl) amine and salicylide reaction, only rare earth crystallizes out, it is achieved thereby that rare earth and the separation of zinc；Rare earth separates with zinc and can also use addition excess of ammonia water or sodium hydroxide, and rare earth forms hydroxide and precipitates, and Zn²⁺Form ZnO₂ ^2-Staying in the solution, this method shortcoming is that rare earth hydrate precipitation is easily formed colloid, is difficult to filter, easily carries Zn secretly simultaneously in precipitation²⁺, additionally operation sequence is loaded down with trivial details, the most uneconomical, is difficult to carry out in the industrial production.

Summary of the invention

Present invention aim at providing a kind of from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation preparation Sm₂O₃Method, the method can reduce production cost, simplify production process, prepare Sm₂O₃In product, ZnO content is less than 0.003%

Technical solution:

The present invention is containing ZnCl₂SmCl₃Solution adds NH₄Cl as feed liquid, SmCl in feed liquid₃Concentration is 0.45-0.75 mol/L, ZnCl₂Concentration 0.06-0.12 mol/L, NH₄Cl concentration 4 mol/L, when feed temperature reaches 80 DEG C, adds precipitant, precipitant mesoxalic acid concentration 1 mol/L and NH in feed liquid₄The mixed solution of Cl concentration 4 mol/L, SmCl₃It is 1:2.71 with oxalic acid mol ratio, after adding precipitant, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the ZnO content Sm less than 0.003%₂O₃Product.

Invention effect

Containing ZnCl₂SmCl₃Solution adds NH₄Cl concentration be 4 mol/L be key problem in technology；If adding NH₄Cl concentration is increased to 3 mol/L, Sm from 0₂O₃In product, ZnO content is reduced to 0.05% from 3.85%；Add NH₄When Cl concentration is 4 mol/L, Sm₂O₃In product, ZnO content is less than 0.003%；If adding NH₄When Cl concentration is more than 4 mol/L, Sm₂O₃In product, ZnO content continues to reduce, but the amplitude of reduction is little, adds the NH of excessive concentrations₄Cl, NH₄Cl dissolves relatively slow in the solution, even there are part NH₄Cl does not dissolves, and can increase production cost simultaneously yet；Containing ZnCl₂SmCl₃Solution most preferably adds NH₄Cl concentration is 4 mol/L, it is simple to realize industrialization.

Detailed description of the invention

Embodiment 1

2000 L SmCl are added in settling tank₃Concentration is 0.45 mol/L, ZnCl₂The solution of concentration 0.0614 mol/L, then add 428 kg solid NH₄Cl, solid NH₄After Cl dissolves, solution being heated to 80 DEG C, adding 2441 L concentration of oxalic acid is 1 mol/L and NH₄Cl concentration is the mixed solution of 4 mol/L, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the Sm that ZnO content is 0.0025%₂O₃Product.

Embodiment 2

2000 L SmCl are added in settling tank₃Concentration is 0.6 mol/L, ZnCl₂The solution of concentration 0.12 mol/L, then add 428 kg solid NH₄Cl, solid NH₄After Cl dissolves, solution being heated to 80 DEG C, adding 3255 L concentration of oxalic acid is 1 mol/L and NH₄Cl concentration is the mixed solution of 4 mol/L, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the Sm that ZnO content is 0.0025%₂O₃Product.

Embodiment 3

2000 L SmCl are added in settling tank₃Concentration is 0.6 mol/L, ZnCl₂The solution of concentration 0.0614 mol/L, then add 428 kg solid NH₄Cl, solid NH₄After Cl dissolves, solution being heated to 80 DEG C, adding 3255 L concentration of oxalic acid is 1 mol/L and NH₄Cl concentration is the mixed solution of 4 mol/L, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the Sm that ZnO content is 0.0025%₂O₃Product.

Embodiment 4

2000 L SmCl are added in settling tank₃Concentration is 0.75 mol/L, ZnCl₂The solution of concentration 0.074 mol/L, then add 428 kg solid NH₄Cl, solid NH₄After Cl dissolves, solution being heated to 80 DEG C, adding 4068 L concentration of oxalic acid is 1 mol/L and NH₄Cl concentration is the mixed solution of 4 mol/L, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the Sm that ZnO content is 0.0003%₂O₃Product.

Claims

1. from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation preparation Sm₂O₃Method, it is characterised in that containing ZnCl₂SmCl₃Solution adds NH₄Cl as feed liquid, SmCl in feed liquid₃Concentration is 0.45-0.75 mol/L, ZnCl₂Concentration 0.06-0.12 mol/L, NH₄Cl concentration 4 mol/L, when feed temperature reaches 80 DEG C, adds precipitant, precipitant mesoxalic acid concentration 1 mol/L and NH in feed liquid₄The mixed solution of Cl concentration 4 mol/L, SmCl₃It is 1:2.71 with oxalic acid mol ratio, after adding precipitant, then by solid ammonium bicarbonate, mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺Being fully converted to samaric oxalate precipitation, samaric oxalate precipitation, through filtration, washing, calcination, obtains the ZnO content Sm less than 0.003%₂O₃Product.