CN103924079A

CN103924079A - Method for increasing organic saponification degree and improving extraction separation factor for samarium and zinc in ammonium chloride system

Info

Publication number: CN103924079A
Application number: CN201410098860.3A
Authority: CN
Inventors: 郝先库; 张瑞祥; 李向阳; 刘海旺; 王士智; 马显东; 赵永志; 斯琴毕力格; 许宗泽
Original assignee: JINGRUI NEW MATERIAL CO Ltd BAOTOU; Baotou Rare Earth Research Institute
Current assignee: JINGRUI NEW MATERIAL CO Ltd BAOTOU; Baotou Rare Earth Research Institute; Santoku Corp
Priority date: 2014-03-18
Filing date: 2014-03-18
Publication date: 2014-07-16

Abstract

The invention relates to a method for increasing an organic saponification degree and improving an extraction separation factor for samarium and zinc in an ammonium chloride system, belonging to the field of hydro-metallurgy of rare earth. According to the invention, NH4Cl with a concentration of 3 mol/L is added into a samarium and zinc feed liquid; as increase of the organic saponification degree, the extraction separation factor for Sm3+ and Zn2+ is increased from 5.42 to 21.11; an organic saponification degree of 0.54 mol/L is selected and is consistent with extraction separation of rare earth, which facilitates linking with an extraction separation process for rare earth and enables a high separation factor to be obtained; thus, stages of extraction separation in industrial production can be reduced, extraction separation cost for samarium and zinc can be decreased, and a samaria product can be improved.

Description

Improve the method that organic saponification deg increases samarium and zinc extracting and separating factor in ammonium chloride system

Technical field

The present invention relates to a kind of method that improves organic saponification deg increase samarium and zinc extracting and separating factor in ammonium chloride system, belong to rare-earth wet method field of metallurgy.

Background technology

Most domestic enterprise adopts europium in zinc powder reduction Sm Eu Gd concentrate solution at present, obtains rich europium and two kinds of intermediates of samarium gadolinium enriched substance, after extraction europium, contains Zn ²⁺the feed liquid that separates as samarium gadolinium of samarium gadolinium enriched substance solution, through P ₅₀₇extracting and separating, Zn ²⁺with Sm ³⁺flow out from raffinate together, raffinate is ZnCl ₂and SmCl ₃solution, no matter adopt bicarbonate of ammonia or oxalic acid as precipitation agent, Zn ²⁺also together with samaric carbonate or samaric oxalate precipitation, affect Samarium trioxide quality product, in order to ensure Samarium trioxide quality product, need carry out Sm ³⁺and Zn ²⁺separate, the zinc that CN1715430A patent and document Li Hui qin are shown and the preparation of Rare Earth Separation and zinc subcarbonate, rare earth, 2006,27 (6): 62-64, a kind of zinc and Rare Earth Separation method are provided, utilize N ₂₃₅realize Zn ²⁺and RE ³⁺separate; Japanese Patent JP2001151743 has reported in the mixing solutions of rare earth and zinc, adds after three (2-amino-ethyl) amine and salicylic aldehyde reaction, only has rare earth to crystallize out, thereby has realized separating of rare earth and zinc; Rare earth separates with zinc also can adopt and adds excess of ammonia water or sodium hydroxide, and rare earth forms precipitation of hydroxide, and Zn ²⁺form ZnO ₂ ^2-stay in solution, this method shortcoming is that rare earth hydrate precipitation easily forms colloid, is difficult to filter, and very easily carries Zn secretly in precipitation simultaneously ²⁺, operation sequence is loaded down with trivial details in addition, uneconomical again, is difficult to implement in industrial production.

Summary of the invention

The present invention seeks to improve the method for organic saponification deg increase samarium and zinc extracting and separating factor in ammonium chloride system, reduce the extracting and separating production cost of samarium and zinc, improve Samarium trioxide quality product.

Technical solution:

The present invention is the method that improves organic saponification deg increase samarium and zinc extracting and separating factor in ammonium chloride system.To containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, saponification deg is 0-0.54 mol/L, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.0278-0.1794 mol/L, Zn ²⁺concentration is 0.0025-0.0128 mol/L, and the separation factor of samarium and zinc is 5.42-21.11.

The organic saponification deg of optimal selection of the present invention is 0.54 mol/L, adds NH in feed liquid ₄cl concentration is 3 mol/L, after single-stage extraction, obtains Sm in organic phase ³⁺concentration is 0.1794 mol/L, Zn ²⁺concentration is 0.0128 mol/L, and the separation factor of samarium and zinc is 21.11.

invention effect

(1) the NH that the present invention adds in feed liquid ₄cl and Zn ²⁺generate complex anion [ZnCl ₄] ^2-, in feed liquid, samarium does not generate complex anion, exist in feed liquid with positively charged ion, and P in organic phase ₅₀₇belong to cation extractant, only positively charged ion in feed liquid is extracted, in feed liquid, add NH ₄cl has improved Sm ³⁺percentage extraction, has reduced Zn ²⁺percentage extraction, has increased the separation factor of samarium and zinc;

(2) in feed liquid of the present invention, add NH ₄when Cl concentration is 3 mol/L, along with the rising of organic saponification deg, Sm ³⁺and Zn ²⁺extracting and separating factor is also along with increase, and not saponification organic phase and organic saponification deg are on the low side, extracts to Sm in organic phase ³⁺concentration is lower, the separation factor of samarium and zinc is also lower, organic phase saponification deg is too high, extraction process there will be emulsion, and organic saponification deg optimal selection 0.54 mol/L is consistent with rare earth extraction separation, be convenient to be connected with rare-earth extraction separating process, there is higher separation factor simultaneously, be conducive to shorten the progression of extracting and separating in suitability for industrialized production, reduce extracting and separating acid and alkali consumption amount;

(3), when the organic saponification deg of the present invention is 0.54 mol/L, in feed liquid, do not add NH ₄cl, Sm ³⁺and Zn ²⁺extraction maximum separation factor is 12.32, and NH in feed liquid ₄when Cl concentration is 3 mol/L, under identical organic saponification deg, separation factor reaches 21.11;

(4) the NH adding in feed liquid ₄cl is that samarium gadolinium extracting and separating rear earth saponification section waste water process is concentrated, crystalline, NH ₄cl joins in feed liquid and can not exert an influence to the purity of samarium, realizes the NH reclaiming ₄cl recycling.

Embodiment

embodiment 1

To containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, saponification deg is 0.5371 mol/L, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.1794 mol/L, Zn ²⁺concentration is 0.0128 mol/L, and the separation factor of samarium and zinc is 21.11.

embodiment 2

To containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, saponification deg is 0.4192 mol/L, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.1383 mol/L, Zn ²⁺concentration is 0.0067 mol/L, and the separation factor of samarium and zinc is 19.92.

embodiment 3

To containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, saponification deg is 0.3043 mol/L, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.1030 mol/L, Zn ²⁺concentration is 0.0042 mol/L, and the separation factor of samarium and zinc is 18.20.

embodiment 4

To containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, organic not saponification, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.0278 mol/L, Zn ²⁺concentration is 0.0025 mol/L, and the separation factor of samarium and zinc is 5.42.

Claims

1. the method that improves organic saponification deg increase samarium and zinc extracting and separating factor in ammonium chloride system, is characterized in that, to containing SmCl ₃and ZnCl ₂the raffinate of samarium gadolinium extracting and separating in add NH ₄cl is as feed liquid, SmCl in feed liquid ₃concentration is 0.6071 mol/L, ZnCl ₂concentration is 0.2698 mol/L, NH ₄cl concentration is 3 mol/L, and feed acidity is 0.15 mol/L, and organic phase is by 1.5 mol/L P ₅₀₇-kerosene composition, saponification deg is 0-0.54 mol/L, organic phase and feed liquid are in a ratio of 2.5:1, utilize single-stage extraction, obtain Sm in organic phase ³⁺concentration is 0.0278-0.1794 mol/L, Zn ²⁺concentration is 0.0025-0.0128 mol/L, and the separation factor of samarium and zinc is 5.42-21.11.

2. the organic saponification deg of raising according to claim 1 increases the method for samarium and zinc extracting and separating factor in ammonium chloride system, it is characterized in that, the organic saponification deg of optimal selection is 0.54 mol/L, adds NH in feed liquid ₄cl concentration is 3 mol/L, after single-stage extraction, obtains Sm in organic phase ³⁺concentration is 0.1794 mol/L, Zn ²⁺concentration is 0.0128 mol/L, and the separation factor of samarium and zinc is 21.11.

3. the organic saponification deg of raising according to claim 1 increases the method for samarium and zinc extracting and separating factor in ammonium chloride system, it is characterized in that, saponification deg is 0.5371 mol/L.

4. the organic saponification deg of raising according to claim 1 increases the method for samarium and zinc extracting and separating factor in ammonium chloride system, it is characterized in that, saponification deg is 0.3043 mol/L.