CN105886764B

CN105886764B - From containing ZnCl2SmCl3Solution mesoxalic acid precipitation prepares Sm2O3Method

Info

Publication number: CN105886764B
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: 2018-02-06
Anticipated expiration: 2036-04-15
Also published as: CN105886764A

Abstract

The present invention relates to one kind from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation prepares Sm₂O₃Method, belong to field of rare earth hydrometallurgy.The present invention is in ZnCl₂And SmCl₃NH is added in solution₄Cl adds NH as feed liquid in oxalic acid solution₄Cl is as precipitating reagent, NH in feed liquid and precipitating reagent₄Cl concentration is 4 mol/L, and at 80 DEG C of reaction temperature, precipitating reagent is added in feed liquid, mother liquor of precipitation of ammonium pH value is formulated into 6.8 with ammonium hydrogen carbonate, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate passes through calcination, obtains the Sm that ZnO content is less than 0.003%₂O₃Product, and Zn in feed liquid²⁺Do not precipitate, the method achieve and separate Sm with oxalic acid precipitation³⁺And Zn²⁺, production cost can be reduced, simplify production process, be easy to implement industrialized production.

Description

From containing ZnCl2SmCl3Solution mesoxalic acid precipitation prepares Sm2O3Method

Technical field

The present invention relates to one kind from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation prepares Sm₂O₃Method, it is wet to belong to rare earth Method field of metallurgy.

Background technology

Enterprise uses Eu in zinc powder reduction europium-enriched solution at present³⁺Europium oxide technique is prepared, zinc powder is added into europium-enriched solution By Eu³⁺It is reduced into Eu²⁺, and zinc powder is changed into Zn²⁺Enter in earth solution, contain Zn²⁺Earth solution as reduction extraction Feed liquid, in reduction extraction segregation section Zn²⁺As easy extraction component with Sm³⁺、Gd³⁺Returned Deng trivalent rare earth ionses after back extraction To samarium europium segregation section, Zn²⁺With Sm³⁺Flowed out together from samarium europium segregation section raffinate, be directly used as precipitating reagent, Zn by the use of oxalic acid²⁺Also can Precipitated with samaric oxalate, influence samarium oxide product quality, in order to ensure samarium oxide product quality, Sm need to be carried out³⁺And Zn²⁺Separation； The preparation of CN1715430A patents and the written zinc of document Li Hui qins and Rare Earth Separation and basic zinc carbonate, rare earth, 2006,27 (6):62-64, there is provided a kind of zinc and Rare Earth Separation method, utilize N₂₃₅Realize Zn²⁺And RE³⁺Separation；CN103924078A、 CN103924079A, CN103924080A patent, which provide, uses P₅₀₇Extract and separate Sm³⁺And Zn²⁺Technology；Japan Patent JP2001151743 is reported in the mixed solution of rare earth and zinc, after adding three (2- amino-ethyls) amine and bigcatkin willow aldehyde reaction, Only rare earth crystallizes out, it is achieved thereby that the separation of rare earth and zinc；Rare earth separates to use with zinc adds excess of ammonia Water or sodium hydroxide, rare earth forms hydroxide and precipitated, and Zn²⁺Form ZnO₂ ^2-Stay in the solution, this method shortcoming is hydrogen-oxygen Change rare-earth precipitation and easily form colloid, it is difficult to filter, while Zn is easily carried secretly in precipitating²⁺, operational sequence is cumbersome in addition, and without Ji, is difficult to carry out in the industrial production.

The content of the invention

Present invention aims at provide one kind from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation prepares Sm₂O₃Method, should Method can reduce production cost, simplify production process, prepare Sm₂O₃ZnO content is less than 0.003% in product

Technical solution：

The present invention is containing ZnCl₂SmCl₃NH is added in solution₄Cl is as feed liquid, SmCl in feed liquid₃Concentration is 0.45- 0.75 mol/L、ZnCl₂Concentration 0.06-0.12 mol/L, NH₄The mol/L of Cl concentration 4, when feed temperature reaches 80 DEG C, to feed liquid Middle addition precipitating reagent, the mol/L and NH of precipitating reagent medium-height grass acid concentration 1₄The mol/L of Cl concentration 4 mixed solution, SmCl₃Rubbed with oxalic acid You are than being 1:2.71, after adding precipitating reagent, then with solid ammonium bicarbonate mother liquor of precipitation of ammonium pH value is formulated to 6.8, Sm in feed liquid³⁺It is complete Complete to be converted into samaric oxalate precipitation, samaric oxalate precipitation is filtered, washs, calcination, obtains the Sm that ZnO content is less than 0.003%₂O₃Production Product.

Invention effect

Containing ZnCl₂SmCl₃NH is added in solution₄Cl concentration is that 4 mol/L are key problem in technology；If add NH₄Cl concentration 3 mol/L, Sm are increased to from 0₂O₃ZnO content is reduced to 0.05% from 3.85% in product；Add NH₄Cl concentration is 4 mol/L When, Sm₂O₃ZnO content is less than 0.003% in product；If add NH₄When Cl concentration is more than 4 mol/L, Sm₂O₃ZnO content in product Continue to reduce, but reduction amplitude is little, adds the NH of excessive concentrations₄Cl, NH₄Cl dissolves relatively slowly in the solution, or even there are portion Divide NH₄Cl is not dissolved, while can increase production cost yet；Containing ZnCl₂SmCl₃Most preferably addition NH in solution₄Cl concentration is 4 Mol/L, it is easy to implement industrialization.

Embodiment

Embodiment 1

2000 L SmCl are added in settling tank₃Concentration is 0.45 mol/L, ZnCl₂The mol/L's of concentration 0.0614 is molten Liquid, then add 428 kg solids NH₄Cl, solid NH₄After Cl dissolvings, solution is heated to 80 DEG C, adding 2441 L concentration of oxalic acid is 1 mol/L and NH₄Cl concentration is 4 mol/L mixed solution, then is formulated to mother liquor of precipitation of ammonium pH value with solid ammonium bicarbonate 6.8, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate precipitation is filtered, washs, calcination, and obtaining ZnO content is 0.0025% Sm₂O₃Product.

Embodiment 2

2000 L SmCl are added in settling tank₃Concentration is 0.6 mol/L, ZnCl₂The mol/L of concentration 0.12 solution, then Add 428 kg solids NH₄Cl, solid NH₄After Cl dissolvings, solution is heated to 80 DEG C, it is 1 to add 3255 L concentration of oxalic acid Mol/L and NH₄Cl concentration is 4 mol/L mixed solution, then mother liquor of precipitation of ammonium pH value is formulated into 6.8 with solid ammonium bicarbonate, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate precipitation is filtered, washs, calcination, obtains ZnO content as 0.0025% Sm₂O₃Product.

Embodiment 3

2000 L SmCl are added in settling tank₃Concentration is 0.6 mol/L, ZnCl₂The mol/L of concentration 0.0614 solution, 428 kg solids NH are added again₄Cl, solid NH₄After Cl dissolvings, solution is heated to 80 DEG C, it is 1 to add 3255 L concentration of oxalic acid Mol/L and NH₄Cl concentration is 4 mol/L mixed solution, then mother liquor of precipitation of ammonium pH value is formulated into 6.8 with solid ammonium bicarbonate, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate precipitation is filtered, washs, calcination, obtains ZnO content as 0.0025% Sm₂O₃Product.

Embodiment 4

2000 L SmCl are added in settling tank₃Concentration is 0.75 mol/L, ZnCl₂The mol/L of concentration 0.074 solution, 428 kg solids NH are added again₄Cl, solid NH₄After Cl dissolvings, solution is heated to 80 DEG C, it is 1 to add 4068 L concentration of oxalic acid Mol/L and NH₄Cl concentration is 4 mol/L mixed solution, then mother liquor of precipitation of ammonium pH value is formulated into 6.8 with solid ammonium bicarbonate, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate precipitation is filtered, washs, calcination, obtains ZnO content as 0.0003% Sm₂O₃Product.

Claims

1. from containing ZnCl₂SmCl₃Solution mesoxalic acid precipitation prepares Sm₂O₃Method, it is characterised in that containing ZnCl₂SmCl₃ NH is added in solution₄Cl is as feed liquid, SmCl in feed liquid₃Concentration is 0.45-0.75 mol/L, ZnCl₂Concentration 0.06-0.12 Mol/L, NH₄The mol/L of Cl concentration 4, when feed temperature reaches 80 DEG C, precipitating reagent, precipitating reagent medium-height grass acid concentration are added into feed liquid 1 mol/L and NH₄The mol/L of Cl concentration 4 mixed solution, SmCl₃It is 1 with oxalic acid mol ratio:2.71, after adding precipitating reagent, then Mother liquor of precipitation of ammonium pH value is formulated to 6.8 with solid ammonium bicarbonate, Sm in feed liquid³⁺Samaric oxalate precipitation is fully converted to, samaric oxalate sinks Form sediment it is filtered, washing, calcination, obtain ZnO content be less than 0.003% Sm₂O₃Product.