Background technology
In the ion adsorption type rare earth ore, REE is to be adsorbed on the clay mineral surface with ionic state.When the leaching ion type rareearth ore, a large amount of aluminum ions get in the leach liquor with rare earth in the clay mineral.When the concentrate of ion adsorption type rare earth ore prepares in early days, adopt the rare earth in the oxalic acid precipitation leach liquor, removed a large amount of non-rare earth impurities that comprise aluminium.Yet ion adsorption type rare earth ore leach liquor oxalic acid precipitation technology is progressively substituted by ammonium bicarbonate precipitation in recent years, though the cost of concentrate preparation is greatly descended, non-rare earth impurities such as the aluminium in the concentrate but do not obtain good pre-separation; Aluminium content is up to 4% (massfraction) in southern ion type rareearth concentrate, and the high hydrolysis easily of aluminium composition causes extraction agent emulsification in the rare earth ore concentrate, has increased difficulty not only for the later separation flow process; And charge capacity is descended, and cause processing power to descend, the separation that also influences rare earth is purified; It extensively distributes in P507-kerosene-hydrochloric acid system segregation section; Quite disperse all has in the outlet of elements such as Pr, Nd, Sm, Eu and to accumulate enrichment in various degree, especially with Nd, Sm for very; Aluminium content accounts for 3% of rare earth weight ratio up to 8g/l in the rare earth feed liquid.Because aluminium is close with rare-earth hydroxide deposition pH, and forms colloid, aluminium has both sexes, so aluminium is difficult to separate with rare earth in the rare earth feed liquid.Produce aluminum removing method upward commonly used at present and mainly contain alkaline process, acid system, hydrolysis method, extraction process etc.(1) alkaline process wherein: because aluminium generates soluble meta-aluminate under the highly basic condition; Rare earth then generates oxyhydroxide; Make aluminium and rare earth reach isolating purpose through leave standstill, filtration etc., but rare earth hydrate be the key in the operation of this method separating of mother liquor.This law is suitable for separating aluminium and rare earth in the rare-earth alkali conversion process, and the baotite alkaline process prepares and promptly comprised this step in the rare earth chloride step, and the effect of removing aluminium is general.(2) acid system: claim oxalate precipitation method again, add in the earth solution, because oxalic acid aluminium solubleness in acidic solution is bigger with oxalic acid; Aluminium is stayed in the solution; It is fine that this method is removed the aluminium effect, is suitable for separating the small amount of aluminum in a large amount of rare earths, and this method generally is used for the final step feed liquid and handles; Owing to need complicated transforming process, process links is many, the removal of impurities cost high, the oxalate solution loss is big, the oxalic acid wastewater treatment is difficult and the shortage practical significance for middle feed liquid.(3) hydrolysis method: the pH value with alkali lye or bicarbonate of ammonia adjustment rare earth feed liquid makes Al
3+Hydrolysis and removing.Because Al
3+With RE
3+The pH value of beginning hydrolysis is just quite approaching, thereby causes aluminium and rare earth hydrolytic precipitation simultaneously, and the gelatinous precipitate subsequent disposal that generates ten minutes difficulty.It is low that this method is removed aluminium efficient, and the rare earth loss is big, therefore can't effectively remove aluminium with hydrolysis method.(4) extraction process: traditional extraction process is that the use volume ratio is that 25% naphthenic acid-20% isooctyl alcohol-kerosene is formed organic phase, adds ammoniacal liquor or sodium hydroxide saponification earlier, and saponification value is 0.35M; Utilize the rare earth feed liquid of single-stage steel basin or multi-stage solvent extraction groove and pH value 3.0 to mix then; It is about 30% that aluminium extracts, but the rare earth extraction loss is greater than 10%, and it is general that this method is removed the aluminium effect; And the necessary strict control of the pH value of rare earth feed liquid, otherwise be prone to cause system emulsification that extraction process can't be carried out.
Summary of the invention
The present invention solves the deficiency that present rare earth feed liquid aluminum removing method exists, and provides a kind of effective except that aluminium, and it is low to remove the aluminium cost, and rare earth yield is high, convenient operation and control, and operation is simple, the rare earth feed liquid aluminum removing method that facility investment is few.
Technical scheme of the present invention is such: a kind of method of from rare earth feed liquid, removing aluminium comprises the steps:
(1) is 15~25% naphthenic acid-15~25% alcohol-kerosene preparation organic phase by volume;
(2) above-mentioned organic phase for preparing and rare earth feed liquid are added in steel basin by volume at 2~5: 1, open and stir, mix;
(3) under agitation condition, in the mixed solution of step (2) gained, add basic soln, the alkali total moles of adding is 50%~100% of a rare earth feed liquid middle-weight rare earths element total moles;
(4) add alkali and finish continued stirring for some time, stop then stirring, leave standstill for some time, solution separating is water and organic phase, and water is except that the rare earth feed liquid behind the aluminium.
Further, above-mentioned a kind ofly from rare earth feed liquid, remove in the method for aluminium, the alcohol described in the step (1) is selected from one of them of octanol or isooctyl alcohol or C8~C10 alcohol mixture; Rare earth feed liquid described in the step (2) is rare earth chloride liquid or sulfuric acid rare earth feed liquid; Basic soln described in the step (3) is one of them of ammoniacal liquor or aqueous sodium hydroxide solution or aqueous sodium carbonate or ammonium bicarbonate aqueous solution, and described basic soln volumetric molar concentration is 3~6mol/L; Churning time described in the step (4) is 10~30 minutes, and time of repose is 10~30 minutes.
Further; Organic phase described in the step (4) is under agitation condition; Regenerate with the acidic solution back extraction; The total moles of acid is 100~150% of a rare earth feed liquid middle-weight rare earths element total moles in the acidic solution that adds, and the regeneration organic phase that obtains recycles, and strip liquor reclaims REE wherein with oxalate precipitation method; Described acidic solution is one of them of hydrochloric acid soln or sulphuric acid soln; Described acidic solution concentration is 3~5mol/L.
The present invention compared with prior art has except that aluminium effectively, and it is low to remove the aluminium cost, and rare earth yield is high, and easy to operate, operation is simple, and facility investment is few, practical advantage.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but does not constitute any restriction of the present invention.
Embodiment 1
The mishmetal extraction divides into groups to separate post chlorization neodymium feed liquid 2500L, rare earth concentration 1.26mol/L, Al
2O
3Be 8232.2mg/L, containing Neodymium trioxide through calculating Neodymium trichloride feed liquid is 525.63Kg.At first prepare organic phase, organic phase consists of 25% naphthenic acid-25% alcohol mixture-kerosene by volume, and the 5000L organic phase is joined 10M
3In the steel basin; The Neodymium trichloride feed liquid that adds 2500L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 358L concentration is the ammoniacal liquor of 6mol/L; Ammoniacal liquor add finish after, continue to stir and stop after 30 minutes stirring, leave standstill phase-splitting in 30 minutes after, emit water, water is except that the Neodymium trichloride feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the hydrochloric acid soln back extraction of 716L as 5mol/L, volume, and organic phase recycles, and strip liquor reclaims neodymium with the oxalic acid precipitation method.
Removing and obtaining the Neodymium trichloride material liquid volume behind the aluminium is 2813L, through analyzing and testing: rare earth concentration 1.05 mol/L, Al
2O
3Be 1.2mg/L, containing Neodymium trioxide through calculating Neodymium trichloride feed liquid is 496.8Kg, and promptly rare earth yield is 94.51%, and aluminium clearance 99.98% removes the aluminium cost and is no more than 700 yuan/ton (in Neodymium trioxide).
Embodiment 2
The mishmetal extraction divides into groups to separate post chlorization praseodymium feed liquid 1250L, rare earth concentration 1.22 mol/L, Al
2O
3Be 2453mg/L, containing Praseodymium trioxide through calculating praseodymium chloride feed liquid is 259.56Kg.At first prepare organic phase, organic phase consists of 15% naphthenic acid-15% alcohol mixture-kerosene by volume, and the 5000L organic phase is joined 10M
3In the steel basin; The praseodymium chloride feed liquid that adds 1250L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 280L concentration is the sodium hydroxide solution of 3mol/L; Sodium hydroxide solution add finish after, continue to stir and stop after 30 minutes stirring, leave standstill phase-splitting in 20 minutes after, emit water, water is except that the praseodymium chloride feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the hydrochloric acid soln back extraction of 400L as 3mol/L, volume, and organic phase recycles, and strip liquor reclaims praseodymium with the oxalic acid precipitation method.
Removing and obtaining the praseodymium chloride material liquid volume behind the aluminium is 1503L, through analyzing and testing: rare earth concentration 0.95mol/L, Al
2O
3<0.1mg/L, containing Praseodymium trioxide through calculating praseodymium chloride feed liquid is 243.02Kg, and promptly rare earth yield is 93.63%, and aluminium clearance>99.996% removes the aluminium cost and is no more than 700 yuan/ton (in Praseodymium trioxides).
Embodiment 3
The mishmetal extraction divides into groups to separate post chlorization samarium feed liquid 2000L, rare earth concentration 1.18mol/L, Al
2O
3Be 6723mg/L, containing Samarium trioxide through calculating samarium trichloride feed liquid is 411.58Kg.At first prepare organic phase, organic phase consists of 20% naphthenic acid-20% isooctyl alcohol-kerosene by volume, and the 5000L organic phase is joined 10M
3In the steel basin; The samarium trichloride feed liquid that adds 2000L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 460L concentration is the ammonium bicarbonate aqueous solution of 3mol/L; Ammonium bicarbonate aqueous solution add finish after, continue to stir and stop after 20 minutes stirring, leave standstill phase-splitting in 20 minutes after, emit water, water is except that the samarium trichloride feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the hydrochloric acid soln back extraction of 700L as 4mol/L, volume, and organic phase recycles, and strip liquor reclaims samarium with the oxalic acid precipitation method.
Removing and obtaining the samarium trichloride material liquid volume behind the aluminium is 2436L, through analyzing and testing: rare earth concentration 0.92 mol/L, Al
2O
3Be 1.1mg/L, containing Samarium trioxide through calculating samarium trichloride feed liquid is 390.85Kg, and promptly rare earth yield is 94.96%, and aluminium clearance 99.98% removes the aluminium cost and is no more than 900 yuan/ton (in Samarium trioxides).
Embodiment 4
Mixed chlorinated rare earth feed liquid 2000L, rare earth concentration 1.52 mol/L, Al
2O
3Be 3533mg/L, through its partition of spectroscopic analysis and calculating, mixed chlorinated rare earth feed liquid include mixed rare earth oxide is 480.32Kg.At first prepare organic phase, organic phase consists of 25% naphthenic acid-25% isooctyl alcohol-kerosene by volume, and the 5000L organic phase is joined 10M
3In the steel basin; The mixed chlorinated rare earth feed liquid that adds 2000L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 380L concentration is the ammoniacal liquor of 6mol/L; Ammoniacal liquor add finish after, continue to stir and stop after 25 minutes stirring, leave standstill phase-splitting in 25 minutes after, emit water, water is except that the mixed chlorinated rare earth feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the hydrochloric acid soln back extraction of 900L as 5mol/L, volume, and organic phase recycles, and strip liquor reclaims its middle-weight rare earths with the oxalic acid precipitation method.
Removing and obtaining the mixed chlorinated rare earth material liquid volume behind the aluminium is 2351L, through analyzing and testing: rare earth concentration 1.19 mol/L, Al
2O
3<0.1mg/L is 442.04Kg through calculating mixed chlorinated rare earth feed liquid include mixed rare earth oxide, and promptly rare earth yield is 92.03%, and aluminium clearance>99.997% removes the aluminium cost and is no more than 900 yuan/ton (in mixed rare-earth oxides).
Embodiment 5
The mishmetal extraction divides into groups to separate back sulfuric acid pr-nd enriched product feed liquid 1500L, rare earth concentration 0.28 mol/L, Al
2O
3Be 3685mg/L, its partition of spectroscopic analysis is Pr
6O
1125.32%, Nd
2O
374.63%, containing the oxidation pr-nd enriched product through calculating sulfuric acid pr-nd enriched product feed liquid is 70.85Kg.At first prepare organic phase, organic phase consists of 18% naphthenic acid-18% isooctyl alcohol-kerosene by volume, and the 5000L organic phase is joined 10M
3In the steel basin; The sulfuric acid pr-nd enriched product feed liquid that adds 1500L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 80L concentration is the sodium hydroxide solution of 5mol/L; Sodium hydroxide solution add finish after, continue to stir and stop after 15 minutes stirring, leave standstill phase-splitting in 15 minutes after, emit water, water is except that the sulfuric acid pr-nd enriched product feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the sulphuric acid soln back extraction of 150L as 4mol/L, volume, and organic phase recycles, and strip liquor reclaims pr-nd enriched product with the oxalic acid precipitation method.
Removing and obtaining sulfuric acid pr-nd enriched product material liquid volume behind the aluminium is 1562L, through analyzing and testing: rare earth concentration 0.25mol/L, Al
2O
3<0.1mg/L, containing the oxidation pr-nd enriched product through calculating sulfuric acid pr-nd enriched product feed liquid is 65.88Kg, and promptly rare earth yield is 92.98%, and aluminium clearance>99.997% removes the aluminium cost and is no more than 700 yuan/ton (in oxidation pr-nd enriched products).
Embodiment 6
Mix sulphur acid rare earth feed liquid 1000L, rare earth concentration 0.32 mol/L, Al
2O
3Be 3826mg/L, through its partition of spectroscopic analysis and calculating, mix sulphur acid rare earth feed liquid include mixed rare earth oxide is 101.12Kg.At first prepare organic phase, organic phase consists of 22% naphthenic acid-22% alcohol mixture-kerosene by volume, and the 3000L organic phase is joined 5M
3In the steel basin; The mix sulphur acid rare earth feed liquid that adds 1000L is opened and is stirred to steel basin, mixes; Under agitation condition, adding 80L concentration is the sodium carbonate solution of 3mol/L; Sodium carbonate solution add finish after, continue to stir and stop after 10 minutes stirring, leave standstill phase-splitting in 10 minutes after, emit water, water is except that the mix sulphur acid rare earth feed liquid behind the aluminium; Under agitation condition, organic phase uses concentration to regenerate as the sulphuric acid soln back extraction of 120L as 4mol/L, volume, and organic phase recycles, and strip liquor reclaims its middle-weight rare earths with the oxalic acid precipitation method.
Removing and obtaining mix sulphur acid rare earth material liquid volume behind the aluminium is 1062L, through analyzing and testing: rare earth concentration 0.28 mol/L, Al
2O
3<0.1mg/L is 93.97Kg through calculating mix sulphur acid rare earth feed liquid include mixed rare earth oxide, and promptly rare earth yield is 92.93%, and aluminium clearance>99.997% removes the aluminium cost and is no more than 1000 yuan/ton (in mixed rare-earth oxides).
Show from analytical results: the present invention has except that aluminium effective, and it is low to remove the aluminium cost, and rare earth yield is high, and easy to operate, operation is simple, and facility investment is few, practical characteristics.