CN87101822A

CN87101822A - Medium-gadolinium and rich-europium ion type rare-earth mineral rare earth complete-separation process

Info

Publication number: CN87101822A
Application number: CN 87101822
Authority: CN
Inventors: 游宏亮; 刘渺生; 饶哲明; 颜子亮
Original assignee: GANZHOU NONFERROUS METALLURGICAL INSTITUTE
Current assignee: GANZHOU NONFERROUS METALLURGICAL INSTITUTE
Priority date: 1987-03-07
Filing date: 1987-03-07
Publication date: 1988-09-21

Abstract

A kind of from the full rare-earth separating technology of medium-gadolinium and rich-europium ion type rare-earth mineral, belong to the hydrometallurgy field.Gate ring alkanoic acid saponification deg of the present invention is 0.4～0.5N, washing lotion acidity 0.6～0.7N, under the condition of feed liquid 120g/L, the lanthanum yttrium with staying in aqueous phase and with other Rare Earth Separation, to non-lanthanum aluminate rare earth, carry out extraction chromatography again through three sections groupings, can get single rare earth oxide compounds such as high-purity samarium, europium, gadolinium, terbium.The present invention is simple, can reduce production costs remarkable in economical benefits.

The present invention is applicable to the full rare-earth separating of medium-gadolinium and rich-europium ion type rare-earth mineral.

Description

The invention belongs to the hydrometallurgy field.

The ion adsorption type rare earth ore that China finds first, at present widely development and use light rare earths ore deposit and heavy rare earths ore deposit two big classes are arranged.Lanthanum accounts for 30% in the light rare earths, and yttrium accounts for about 10%, adopts P usually ₂₀₄Or P ₅₀₇Extraction agent carries out earlier gently, in, heavily extract four groupings or therein between certain two element extracting and separating come, after carry out little grouping more respectively, extract straight product with extraction chromatography; The content of yttrium accounts for more than 50% in the heavy rare earths, generally adopts naphthenic acid to make extraction agent and earlier yttrium is separated separately, isolates the rare earth behind the yttrium, uses P ₂₀₄Or P ₅₀₇Extract grouping, extract the straight product or the high purity product of each element again with extraction chromatography.

The rich europium rare earth of middle yttrium is a kind of novel type ion type rareearth ore of finding at Jiangxi Gan Nan in recent years, and wherein yttrium content is about 30%, and lanthanum content is about 25%, and both total amounts are more than 50%.Gently, heavy rare earths half and half, so neither belong to heavy rare earths ore deposit type, do not belong to light rare earths ore deposit type yet.Complete-separation process to the special rare-earth mineral of this kind partition at home and abroad is not reported.The present invention is the breakthrough of the rich europium type of centering yttrium rare-earth mineral separation method.Adopt naphthenic acid to make extraction agent, extract yttrium and lanthanum under optimum conditions simultaneously, make both together with other Rare Earth Separation.

Accompanying drawing is the full separate blocks schema of medium-gadolinium and rich-europium ion type rare-earth mineral rare earth.It is by naphthenic acid extraction (1), water P ₂₀₄Extracting and separating La, y (2), organic phase half countercurrent reextraction (3), P ₂₀₄Extracting and separating Gd, Tb (4), P ₂₀₄Extraction Nd-Sm grouping (5) is washed Tb and is dragged for Dy (6), Pr, Nd exchange separation (7), Sm

U Gd carries

U (8), Sm Gd stratography operations such as (9) are formed.

Technical essential of the present invention is together to stay in the purpose of water with other Rare Earth Separation for reaching the lanthanum yttrium, utilize cascade extraction theoretical determine progression, when washing the parameter such as acid, the situations such as yield of the extraction factor when considering low pH value and assurance yttrium, select suitable aphthenic acids saponification degree, wash acid concentration and carry out fractional extraction. Its process conditions are: rare earth oxide is adjusted feed liquid PH4.5～5.5 and is left standstill filtering and impurity removing, the rare earth concentration 120g/L after the purification with 1: 2～2.5 dissolving with hydrochloric acid after purifying; With the preparation in 20: 20: 60 by volume of aphthenic acids, mixed alcohol, kerosene, saponification to 0.4～0.5N is as extractant; Washing lotion is made into 0.6～0.7N to purify hydrochloric acid, and extraction is in a ratio of organic phase: feed liquid: washing=4.67: through 20 grade extraction 25 grade washings mix 8～10 minute after at 1: 2.08, the lanthanum yttrium namely together stays in aqueous phase.

Lanthanum yttrium water after the naphthenic acid extracting and separating, the about 20g/L of rare earth concentration adopts P ₂₀₄Extracting and separating, because of lanthanum, yttrium at P ₂₀₄One belongs to light rare earths in the extraction system, one belongs to heavy rare earths, separation factor is very big, just in lanthanum yttrium mixing test solution, still have a small amount of praseodymium neodymium to exist, for make the lanthanum grade reach more than 95% and improve praseodymium neodymium yield as far as possible, when extracting and separating lanthanum yttrium, add praseodymium neodymium washing section one, make one group of test solution obtain three kinds of products, promptly greater than 95～99% La by three outlets ₂O ₃Product, the y greater than 99% ₂o ₃Product and greater than 80% praseodymium neodymium mixture product.

The naphthenic acid extraction removes the organic phase behind the lanthanum yttrium, and behind half countercurrent reextraction, rare earth concentration reaches 300g/L, and the content of terbium is 1.5～1.7%.For obtaining pure terbium as early as possible, be raw material with this strip liquor, carry out the grouping of gadolinium terbium, rare earth accounts for 25% of total rare earth (TRE) amount behind terbium and the terbium at this moment.Terbium obtains relative enrichment in organic phase.Processing condition are: feed liquid RECl ₃160g/LPH2～2.5; 1MP ₂₀₄Saponification 0.35～0.37N; Washing lotion 2～2.5N hydrochloric acid; Compare organic phase: feed liquid: washing=7.3: 1: 1.8, through 9 grades of extractions, 7 grades of washings mixed after 5 minutes, and the gadolinium terbium promptly is divided into two groups, and terbium content is less than 0.3% in the boundary element gadolinium, and gadolinium concentrations is less than 0.3% in the terbium, and the yield of terbium is more than 95%.

Use P ₂₀₄It is 6% that the organic phase of extracting and separating output contains terbium, with acid terbium is washed water and adds new P simultaneously ₂₀₄Fish for the dysprosium that washes water, this moment, the grade of terbium was enriched to more than 80% by 6%.Processing condition are: the P that contains rare earth ₂₀₄Feed liquid, the wherein about 6g/L of rare earth concentration; The new P of 1M ₂₀₄, saponification 0.35～0.36N; Washing lotion acidity 3～3.5N hydrochloric acid; Be in a ratio of new organic phase: feed liquid: washing lotion=60: 52: 20: progression is 18 grades, wherein extracts 11 grades, 8 grades of washing lotions; Mixing time: 5 minutes.

P ₂₀₄The gadolinium terbium separates the preceding water of gadolinium, the about 50g/L of rare earth concentration, and contained rare earth element mainly is praseodymium neodymium and sm-eu-gd, uses P ₂₀₄Carry out extracting and separating at neodymium samarium place again, obtain two groups of enriched substance of praseodymium neodymium and sm-eu-gd, the praseodymium neodymium advances the single product that ion-exchange obtains the praseodymium neodymium, and the further separation of sm-eu-gd enriched substance also can get three kinds of products.Its processing condition are: organic phase is 1M P ₂₀₄, saponification 0.35～0.36N; Feed liquid contains Pr, Nd, Sm, Eu, Gd, washing lotion 0.8～1N; Progression: extract 9 grades, wash 7 grades, mixing time: 5 minutes.

Subsequent technique extracts the high purity single oxide with methods such as exchange, extraction chromatography separation.

Technical characterstic of the present invention: (1) adopts the naphthenic acid extraction to make the lanthanum yttrium with staying aqueous phase, and organic phase does not contain the lanthanum yttrium.The extraction quantity of organic phase is less than half of test portion amount, has both reduced the extraction load of organic phase, when having avoided again in non-lanthanum yttrium, extracting single rare earth, and the interference of lanthanum yttrium in light, heavy rare earths.(2) being separated in of lanthanum and yttrium is easy on the technology realize, the yttrium after the SEPARATION OF La is produced the y of fluorescence level for further purifying ₂o ₃, flow process is fairly simple, and progression can significantly reduce, and helps reducing production costs.(3) non-lanthanum aluminate rare earth of SEPARATION OF La yttrium carries out extraction chromatography again through three sections groupings (progression sum 50 grades), get final product single element products such as high-purity samarium, europium, gadolinium, terbium.Separable programming is simple.

The present invention is applicable to that medium-gadolinium and rich-europium ion type rare-earth mineral rare earth separates entirely.

Claims

1, a kind of medium-gadolinium and rich-europium ion type rare-earth mineral complete-separation process is made up of operations such as extraction, grouping, half countercurrent reextraction, exchange separation, stratographies.It is characterized in that: the dissolving with hydrochloric acid of rare earth oxide after 1:2～2.5 purify, and after transferring the PH purification and impurity removal, be made into the 120g/L feed liquid, with the naphthenic acid alcohol mixture kerosene by volume ratio preparation in 20: 20: 60 is extraction agent, saponification to 0.4～0.5N, extraction is in a ratio of organic phase: feed liquid: washing=4.67: 1: 2.08, through 25 grades of washings of 20 grades of extractions, after mixing 8～10 fens clock times, the lanthanum yttrium together stayed in aqueous phase separate with other rare earth element.

2, separating technology according to claim 1 is characterized in that: the water of lanthanum yttrium adopts P ₂₀₄During extracting and separating lanthanum yttrium, add praseodymium neodymium washing section one, can obtain containing La ₂o ₃Greater than 95～99%, contain y ₂o ₃Greater than 99% with greater than three kinds of products of praseodymium neodymium mixture of 80%.

3, separating technology according to claim 1 is characterized in that: except that the organic phase behind the lanthanum yttrium,, strip liquor is carried out the grouping of gadolinium terbium through half countercurrent reextraction, and the feed concentration height, pH value is low, uses 1MP ₂₀₄, saponification 0.35～0.37N, washing lotion 2～3N hydrochloric acid, be in a ratio of organic phase: feed liquid: washing=7.3: 1: 1.8,, mix that the gadolinium terbium is divided into two groups after 5 minutes through 7 grades of washings of 9 grades of extractions, contain terbium less than 0.3% in the boundary element gadolinium, contain gadolinium in the terbium less than 0.3%, the yield of terbium is more than 95%.

4, according to claim 1,3 described separating technologies, it is characterized in that the terbium that contains of extracting and separating output is 6% organic phase, with acid terbium is washed water and adds new P simultaneously ₂₀₄To fish for the dysprosium that washes aqueous phase.Washing lotion acidity 3～3.5N hydrochloric acid is in a ratio of new organic phase: feed liquid: washing=60: 52: 20, through 8 grades of washings of 11 grades of extractions, to mix after 5 minutes, and the grade of terbium can be enriched to more than 80% by 6%.

5, separating technology according to claim 1 is characterized in that: use P ₂₀₄The place carries out extracting and separating at the neodymium samarium, and its processing condition are organic phase 1MP ₂₀₄Saponification 0.35～0.36N, aqueous-phase concentration 50g/L, washing lotion 0.8～1N hydrochloric acid through 6 grades of washings of 9 grades of extractions, mixes after 5 minutes, can get two groups of enriched substance of praseodymium neodymium and sm-eu-gd.