Rare earth oxalates separation

Separation and Recovery of Rare-Earth Elements. Because rare-earth oxalates have low solubihty in acidic solutions, oxaUc acid is used for the separation and recovery of rare-earth elements (65). For the decomposition of rare-earth phosphate ores, such as mona ite and xenotime, a wet process using sulfuric acid has been widely employed. There is also a calcination process using alkaLine-earth compounds as a decomposition aid (66). In either process, rare-earth elements are recovered by the precipitation of oxalates, which are then converted to the corresponding oxides. 

Heating the ore with sulfuric acid converts neodymium to its water soluble sulfate. The product mixture is treated with excess water to separate neodymium as soluble sulfate from the water-insoluble sulfates of other metals, as well as from other residues. If monazite is the starting material, thorium is separated from neodymium and other soluble rare earth sulfates by treating the solution with sodium pyrophosphate. This precipitates thorium pyrophosphate. Alternatively, thorium may be selectively precipitated as thorium hydroxide by partially neutralizing the solution with caustic soda at pH 3 to 4. The solution then is treated with ammonium oxalate to precipitate rare earth metals as their insoluble oxalates. The rare earth oxalates obtained are decomposed to oxides by calcining in the presence of air. Composition of individual oxides in such rare earth oxide mixture may vary with the source of ore and may contain neodymium oxide, as much as 18%. 

Insoluble silica residues are removed by filtration. The solution now contains beryllium, iron, yttrium, and the rare earths. The solution is treated with oxalic acid to precipitate yttrium and the rare earths. The precipitate is calcined at 800°C to form rare earth oxides. The oxide mixture is dissolved in an acid from which yttrium and the rare earths are separated by the ion-exchange as above. Caustic fusion may be carried out instead of acid digestion to open the ore. Under this condition sihca converts to sodium sihcate and is leached with water. The insoluble residue containing rare earths and yttrium is dissolved in an acid. The acid solution is fed to an ion exchange system for separating thuhum from other rare earths. 

Ytterbium oxide is produced as an intermediate in recovering ytterbium from minerals (See Ytterbium). After opening the ore by digestion with concentrated sulfuric acid or caustic soda solution at high temperatures, rare earths are separated by ion exchange, solvent extraction, or fractional precipitation. Ytterbium fraction is treated with oxahc acid or sodium oxalate to precipitate jdterbium oxalate, which is ignited to yield ytterbium oxide. 

An emulsion liquid membrane (ELM) system has been studied for the selective separation of metals. This system is a multiple phase emulsion, water-in-oil-in-water (W/O/W) emulsion. In this system, the metal ions in the external water are moved into the internal water phase, as shown in Fig. 3.4. The property of the ELM system is useful to prepare size-controlled aiKl morphology controlled fine particles such as metals, carbonates/ and oxalates.Rare earth oxalate particles have been prepared using this system, consisting of Span83 (sorbitan sesquioleate) as a surfactant and EHPNA (2-ethyl-hexylphospholic acid mono-2-ethylhexyl ester) as an extractant. In the case of cerium, well-defined and spherical oxalate particles, 20 - 60 nm in size, are obtained. The control of the particle size is feasible by the control of the feed rare earth metal concentration and the size of the internal droplets. Formation of ceria particles are attained by calcination of the oxalate particles at 1073 K, though it brings about some construction of the particles probably caused by carbon dioxide elimination. 

Use Making oxalic acid and organic oxalates, glazes, rare-earth-metal separations. 

Separation. — The separation of thorium from the rare earth metals with which it is still mixed may be accomplished by three methods (1) the carbonate separation depends on the fact that thorium carbonate is much more soluble in sodium carbonate than the carbonates of the rare earth metals (2) by the fractional crystallization of the mixed sulfates at 15°-20°, crystals of Th(S04)2 8 H20 are obtained at the insoluble end of the series (3) thorium oxalate forms a soluble double salt with ammonium oxalate, while the rare earth oxalates are almost insoluble in this reagent. Some other methods which have been suggested are fractionation of the chromates,4 of the hydrogen alkyl sulfates,5 of the acetates, by the use of sebacic add 6 and hydrogen peroxide. 

An alternative American process uses a feed produced by oxalate precipitation of thorium and rare earths. This precipitate is calcined to the oxides and dissolved in nitric acid for extraction with undiluted TBP. After stripping with 8N nitric acid, a high proportion of cerium extracts with the thorium, but the other rare earths are eliminated. The cerium is then back-washed in a separate extractor by means of 0 1 N sodium nitrite solution, which reduces it to the solvent-insoluble cerous condition. Thorium is then backwashed in the last extractor with either water or 2 per cent sulphuric acid. In order to make this process economic it was necessary to devise an efficient system of oxalic acid recovery. This was based upon treatment of the thorium and rare earth oxalates with sodium hydroxide and recycling the resulting sodium oxalate to the precipitation stage. 

Probably the most important chemical procedure in the determination of the rare earths is the determination of total rare earths in some matrix which usually involves the precipitation of the rare earth oxalates and ignition to the oxides, R2O3. This procedure also serves to separate the rare earth group from other elements present in solution prior to the determination of the individual rare earths by other methods such as flame emission spectrometry. Chemical methods can also be employed to separate the light rare earth fraction from the heavy rare earth fraction with minimum difficulty. Chemical methods such as solvent extraction are also quite useful in the preconcentration of the rare earths where they are present at extremely low concentrations prior to their determination by other methods. 

Uses of oxalic acid ia each region are summarized in Table 5 (58). The demand for agrochemical/pharmaceutical production and for separation/recovery of rare-earth elements in each region has been increasing. The use for marble polishing in western Europe is unique to the region. 

The pH effect in chelation is utilized to Hberate metals from thein chelates that have participated in another stage of a process, so that the metal or chelant or both can be separately recovered. Hydrogen ion at low pH displaces copper, eg, which is recovered from the acid bath by electrolysis while the hydrogen form of the chelant is recycled (43). Precipitation of the displaced metal by anions such as oxalate as the pH is lowered (Fig. 4) is utilized in separations of rare earths. Metals can also be displaced as insoluble salts or hydroxides in high pH domains where the pM that can be maintained by the chelate is less than that allowed by the insoluble species (Fig. 3). 

Nuryono, Huber, C. G., and Kleboth, K., Ion-exchange chromatography with an oxalic acid-alpha-hydroxyisobutyric acid eluent for the separation and quantitation of rare-earth elements in monazite and xenotime, Chromatograph-ia, 48, 407, 1998. 

Americium may be separated from other elements, particularly from the lanthanides or other actinide elements, by techniques involving oxidation, ion exchange and solvent extraction. One oxidation method involves precipitation of the metal in its trivalent state as oxalate (controlled precipitation). Alternatively, it may be separated by precipitating out lanthanide elements as fluorosilicates leaving americium in the solution. Americium may also he oxidized from trivalent to pentavalent state by hypochlorite in potassium carbonate solution. The product potassium americium (V) carbonate precipitates out. Curium and rare earth metals remain in the solution. An alternative approach is to oxidize Am3+ to Am022+ in dilute acid using peroxydisulfate. Am02 is soluble in fluoride solution, while trivalent curium and lanthanides are insoluble. 

In one acid digestion process, monazite sand is heated with 93% sulfuric acid at 210°C. The solution is diluted with water and filtered. Filtrate containing thorium and rare earths is treated with ammonia and pH is adjusted to 1.0. Thorium is precipitated as sulfate and phosphate along with a small fraction of rare earths. The precipitate is washed and dissolved in nitric acid. The solution is treated with sodium oxalate. Thorium and rare earths are precipitated from this nitric acid solution as oxalates. The oxalates are filtered, washed, and calcined to form oxides. The oxides are redissolved in nitric acid and the acid solution is extracted with aqueous tributyl phosphate. Thorium and cerium (IV) separate into the organic phase from which cerium (IV) is reduced to metalhc cerium and removed by filtration. Thorium then is recovered from solution. 

Various processes separate rare earths from other metal salts. These processes also separate rare earths into specific subgroups. The methods are based on fractional precipitation, selective extraction by nonaqueous solvents, or selective ion exchange. Separation of individual rare earths is the most important step in recovery. Separation may be achieved by ion exchange and solvent extraction techniques. Also, ytterbium may be separated from a mixture of heavy rare earths by reduction with sodium amalgam. In this method, a buffered acidic solution of trivalent heavy rare earths is treated with molten sodium mercury alloy. Ybs+ is reduced and dissolved in the molten alloy. The alloy is treated with hydrochloric acid, after which ytterbium is extracted into the solution. The metal is precipitated as oxalate from solution. 

After separation from other rare earths, ytterbium is usually obtained as its oxide, Yb203. If separated as oxalate, oxalate is converted into oxide by high temperature. Ytterbium oxide is reduced to metallic ytterbium by heating with lanthanum metal in high vacuum. The metal is purified by sublimation and collected over a condenser plate. Aluminum, zirconium, and cerium also are effective reducing agents and may be used instead of lanthanum. 

Yttrium oxide is produced as an intermediate in recovery of yttrium from xenotime and monazite (See Yttrium, Recovery). The oxide is produced after separation of rare earth sulfates obtained from digesting the mineral with sulfuric acid on a cation exchange bed, precipitating yttrium fraction as oxalate, and igniting the oxalate at 750°C. 

It has been found that from a homogeneous solution the oxalate of samarium is preferentially precipitated over oxalates of other rare earths and yttrium falls behind all of them. Thus, in a separation process Sm is concentrated to a greater extent at the head section and Y at the tail section [45]. 

Oxalic acid is used in various industrial areas, such as textile manufacture and processing, metal surface treatments leather tanning, cobalt production, and separation and recovery of rare-earth elements. Substantial quantities of oxalic add are also consumed in the production of agrochemicals, pharmaceuticals, and other chemical derivatives... 

Homogeneous precipitation may be more useful in precipitation separation of rare earths. This involves addition of reagents which release the precipitating agent slowly in solution. Addition of trichloroacetic acid and dimethyl oxalate in place of Na2CC>3 and... 

---