CN1133346A - Sorting cerium process by extraction from rare-earth sulfate solution containing fluorine - Google Patents
Sorting cerium process by extraction from rare-earth sulfate solution containing fluorine Download PDFInfo
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Abstract
The present invention relates to an extraction-separation method for preparing cerium compound. Said invention uses the fluorine-containing rare earth sulfate extract made up by using hamartite or hamartite and monazite mixed mineral aggregate as feed liquid, uses P507-paraffin or dimethyl benzene to form organic phase to implement the extraction-separation of tetravalence cerium, thorium, iron and trivalence rare earth. Said invention uses the mixed solution containing 0.2-50g/l of fluoro complexing agent, 0.2-15% of reduction agent and 0.5-6N of acid as back-extractant of cerium to make extraction-separation of cerium and thorium and iron. Said method can produce the cerium dioxide with various purities, and its yield is more than 95%.
Description
The present invention relates to a kind of preparation method of rare earth compound, a kind of more precisely reparation technology of cerium compound extracting and separating.
The method for preparing cerium compound from hamartite mainly contains extraction process, double salt precipitation method.
The double salt precipitation method is that hamartite is carried out oxidizing roasting, and dilute sulphuric acid leaches, and obtains fluorine-containing rare earth sulfate solution, through double salt precipitation trivalent rare earth element is separated with quadrivalent cerium.Quadrivalent cerium solution carries out double salt precipitation again, transform through alkali, dissolving with hydrochloric acid, neutralization removes thorium, uses oxalic acid precipitation at last, calcination and 99.5% cerium dioxide.The weak point of this technology is the technical process complexity, and the cerium dioxide yield is lower than 80%.Chemical raw material consumption is big, and technological process all is solid-liquid operations, is difficult for serialization, and the purity of cerium dioxide also is difficult to improve.CeO in the trivalent rare earth
2/ REO＞10% also needs chemical method to remove cerium.
Contain fluorine owing in the sulfuric acid to leach liquid of hamartite, in extraction, reextraction process, easily generate the rare earth fluoride precipitation and make organic phase generation emulsification, bring very big difficulty to extraction quadrivalent cerium from this leaching liquid.
The investigator who has had once studied the ceric technology of extraction from the fluorine-containing sulphuric leachate that hamartite makes.Its consisting of of stock liquid as water contains ∑ R
xO
y～60 grams per liters, ∑ Ce
xO
y～30 grams per liters, CeO
227 grams per liters, ThO
20.24 grams per liter, Fe 1.5～1.7 grams per liters, F 3.8 grams per liters, Ca
2+2.9 grams per liter, B 0.4 grams per liter, the about 3NH of free acid
2SO
4With 1.0MP
204+ 0.2M TBP-kerosin is an organic phase, extracts.With 2N nitric acid is pickle solution, and extraction section is 7 grades, and the pickling section is 3 grades, organic phase: feed liquid: pickle solution is 2: 1: 0.3, and raffinate is a trivalent rare earth, carries out double salt precipitation, becomes few cerium rare earth hydrate after alkali transforms; Organic phase is to contain 2%H
2O
2, 3N sulfuric acid is the solution of reextraction cerium, the reextraction cerium, and 6 grades, organic phase: water is 6: 1.Anti-cerium liquid carries out double salt precipitation, transforms through alkali and generates cerous hydroxide.Through the organic phase of reextraction cerium, with containing 12% yellow soda ash, 4% sodium hydroxide single-stage back extraction iron and thorium carry out acidification to the organic phase behind reextraction thorium, the iron again, recycle.The purity of resulting cerium dioxide＞99.97%.Though in this technology, adopted TBP, borax to suppress the detrimentally affect of fluorion, poor effect.Emulsification does not take place in extraction at short notice, but makes organic phase generation emulsification through beginning to occur the rare earth fluoride precipitation after continuous for some time, and time lengthening emulsification is more serious, and the operation of extracting cerium can not be gone on.And during with 12% yellow soda ash, 4% sodium hydroxide solution reextraction thorium, iron, produce ferric hydroxide colloid and also make organic phase produce serious emulsion, the organic phase behind its reextraction iron, the thorium need be with the sulfuric acid acidation of 4N, and the acid and alkali consumption amount is big.
Other has investigator's (rare earth extraction data compilation---national rare earth extraction meeting material 95-102 for the first time, in July, 1976) with P
507-sulfonated kerosene is an organic phase, has carried out extracting in the never fluorine-containing sulphuric acid soln trivalent rare earth element, thorium, scandium and ceric research.The percentage extraction that the result shows trivalent rare earth element is along with the increase of water sulfuric acid concentration descends fast, and the percentage extraction of quadrivalent cerium and thorium also descends with the increase of sulfuric acid concentration, and is very slow but ceric percentage extraction descends.Use P
507The order of above-mentioned each element of extraction is Sc＞Ce (1V)＞Th＞RE, so use P
507Be extraction agent, quadrivalent cerium can be separated with trivalent rare earth element.
Purpose of the present invention just is to work out a kind of novel method of mixing extracting and separating cerium the fluorine-containing sulfuric acid rare earth leaching liquid that the ore deposit makes from hamartite or hamartite and monazite, make its technology easy, easy handling, when the rate of recovery of cerium is high, in the process of continuous extraction for a long time, back extraction cerium emulsification does not take place, the technological process of extracting and separating cerium can be carried out smoothly.
The technology of a kind of extracting and separating cerium of the present invention, with hamartite or hamartite and monazite to mix the fluorine-containing rare earth sulfate solution that the ore deposit makes be stock liquid, (be called for short P with di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester
507) be extraction agent, with the alkane that contains 6 carbon atoms to the alkane that contains 12 carbon atoms, a kind of alkane wherein is thinner, the also available alkane of 5 carbon atoms that contains is to the alkane that contains 20 carbon atoms, wherein the mixture of two or more alkane or dimethylbenzene are that thinner is formed organic phase, carry out quadrivalent cerium, thorium, the extracting and separating of iron and trivalent rare earth element, organic phase, feed liquid, the stream ratio of washing lotion is 0.2～10: 1: 0.1～2, washing lotion is the sulfuric acid of 0.5-8N, hydrochloric acid, nitric acid a kind of acid wherein, washing section progression is 0-6 grades, and the extraction back forms contains quadrivalent cerium, thorium, the organic phase of iron and the raffinate that contains trivalent rare earth element.The raffinate that contains trivalent rare earth element is used for the raw material of Rare Earth Separation.
With the fluorine complexing agent that contains 0.2-50 grams per liters, 0.2 the mixing solutions of the reductive agent of～15% (weight percentage) and the hydrochloric acid of 0.5-6N, nitric acid, sulfuric acid a kind of acid wherein is as ceric anti-stripping agent, the organic phase that contains quadrivalent cerium, thorium, iron is carried out back extraction, quadrivalent cerium is stripped in the strip liquor, thorium, iron are stayed in the organic phase, and cerium is separated with iron, thorium.
With the known method of the those of ordinary skill under this area, the mining oxidizing roasting with mixing of monazite with hamartite or hamartite-sulfuric acid leaches makes fluorine-containing rare earth sulfate solution, or making fluorine-containing various fluorine-containing rare earth sulfate solutions such as rare earth sulfate solution as stock liquid with yellow soda ash sintering-sulfuric acid to leach method, but the fluorine-containing rare earth sulfate solution made from oxidizing roasting-sulfuric acid to leach as stock liquid for well.The CeO that contains 2-80 grams per liters in the fluorine-containing rare earth sulfate solution as stock liquid
2, CeO
2/ REO (REO is the rare earth oxide total content) is 5～60% (weight percentage), contains 0.5-15 grams per liter F, the ThO of 0.01-1 grams per liter
2, 0.05-2 grams per liter Fe, acidity is 0.2-3N.In stock liquid again to contain 15-50 grams per liter CeO
2, CeO
2/ REO47～50%, 0.5-8 grams per liter F, 0.1-0.3 grams per liter ThO
2, 0.1-1.4 grams per liter Fe, the boric acid of 0.2-50 grams per liters, borax, Tai-Ace S 150 a kind of fluorine complexing agent wherein, acidity 0.4-2N is good.If with borax is the complexing agent of fluorine, its concentration is 0.2-30 grams per liters.In stock liquid as in the boric acid of fluorine complexing agent, borax, Tai-Ace S 150, titanium sulfate, the zirconium sulfate with boric acid for well.Introduce other metal ions in extraction systems because add other complexing agents, thus in the raw material with the boric acid that contains 0.2-10 grams per liters for better.Acidity is too low in stock liquid, the cerium dioxide facile hydrolysis; Acidity is too high, is higher than 3N, and the consumption of acid is too big, influences the extracting and separating of trivalent rare earth, thus the acidity in the stock liquid with 0.4-2N for well.It is better to contain 0.1-0.5 grams per liter Fe in the stock liquid.
When the extraction quadrivalent cerium, used extracting process is fractionation extraction or counter-current extraction.Used extraction agent is that di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (is called for short P
507), extraction agent P
507Concentration in thinner is 0.2-2 mol for well, again with the P of 0.5-1.5 mol
507For better.With the alkane that contains 6 carbon atoms to the alkane that contains 12 carbon atoms, a kind of alkane wherein is as thinner, can also be to the alkane that contains 20 carbon atoms with the alkane that contains 5 carbon atoms, wherein two or more mixed alkanes or dimethylbenzene are that thinner is formed organic phase.Used washing lotion is sulfuric acid, nitric acid, the hydrochloric acid a kind of acid wherein of 0.5-8N, and sulfuric acid, nitric acid, the hydrochloric acid a kind of acid wherein with 1-5N is good again.The acidity of washing lotion increases, and the purity of cerium dioxide increases, but the recovery of extraction of cerium reduces.Used stream is than being organic phase: feed liquid: washing lotion=0.2～10: 1: 0.1～2, and again with 1～6: 1: 0.2～1 is good.Used extraction section progression is 1～5 grade, is advisable with 1～3 grade, and washing section progression is 0～6, and washing section progression increases, and the purity of cerium dioxide increases.So the progression of adjustment washing section or the acidity of washing lotion can obtain the cerium dioxide of different purity.Washing lotion is returned and is leached the ore deposit or enter extraction section.Extraction mixing-time 2-10 minutes was good with 3-6 minutes again, and settling time was controlled at 2-20 minutes, was advisable with 4-10 minutes again.Extraction mixing-time and settling time are long more, and throughput is low more.
After quadrivalent cerium, thorium, iron is extracted into organic phase, with the boric acid that contains 0.2-50 grams per liters, borax, Tai-Ace S 150, titanium sulfate, zirconium sulfate a kind of fluorine complexing agent wherein, 0.2 the mixed solution of the reductive agent of～15% (weight percentage) and the hydrochloric acid of 0.5-6N, sulfuric acid, nitric acid a kind of acid wherein is as ceric anti-stripping agent, the organic phase that contains quadrivalent cerium, thorium, iron is carried out back extraction with adverse current or adverse current band from the mode that refluxes, quadrivalent cerium is stripped in the anti-stripping agent.As if its concentration of complexing agent that with borax is fluorine is 0.2-30 grams per liters.Used reductive agent contains wherein a kind of of the hydrogen peroxide of 0.2～15% (weight percentage), water-soluble divalent iron salt, S-WAT, sulfurous acid in the ceric anti-stripping agent of stripping, be good with hydrogen peroxide, sulfurous acid as reductive agent especially.With divalent iron salt, S-WAT is that reductive agent is brought in the extraction system metallic impurity into.Used hydrogen peroxide is commercially available 30% hydrogen peroxide, and therefore used reductive agent is the best with the hydrogen peroxide that contains 0.5～10% (weight percentage) in the ceric anti-stripping agent of stripping.Used fluorine complexing agent is wherein a kind of of boric acid, borax, Tai-Ace S 150, titanium sulfate, zirconium sulfate, is good with the boric acid that contains 0.2-30 grams per liters again.Acidity in the anti-stripping agent is sulfuric acid, nitric acid, the hydrochloric acid a kind of acid wherein of 0.5-6N, and its acidity is advisable with sulfuric acid, nitric acid, the hydrochloric acid a kind of acid wherein of 0.7-5N again.The progression of stripping is 1～6 grade, again with 2～5 grades for well.Stream is than being organic phase: anti-stripping agent is 1～20: 1, and again with 1～10: 1 is good.The reextraction blended time is 2-30 minutes, again with 3-10 minutes for well, settling time is 2-30 minutes, is good with 5-15 minutes again.
Cerium in the strip liquor is made into Cerium II Chloride, cerous nitrate with the method that the technician under this area all knows, can also be neutralized to PH2-0.5N with yellow soda ash, bicarbonate of ammonia, ammonium hydroxide a kind of strip liquor that will contain cerium wherein, be heated to 30-98 ℃, add oxalic acid after being preferably 60-70 ℃, cerium is precipitated.The amount that adds oxalic acid is oxalic acid/cerium dioxide=1.2～1.8 (weight ratios), again with 1.25～1.4 for well.Precipitation after filtration, washing back is 700-900 ℃ of calcinations 1-3 hours, and obtain the product cerium dioxide.
Cerium in the strip liquor can also be made cerous carbonate, its method is with strip liquor yellow soda ash, bicarbonate of ammonia, ammonium hydroxide a kind of reagent wherein, be neutralized to PH1～4, be heated to 30-98 ℃ then, add bicarbonate of ammonia again, make the acidity of solution reduce to PH7～9, make the cerium precipitation, precipitation obtains the product cerous carbonate after the washing after filtration.
For the technology that makes extracting and separating cerium of the present invention forms closed cycle, will contain the organic phase of cerium, thorium, iron, after stripping with ceric anti-stripping agent, cerium is stripped to strip liquor (water).Its organic phase that contains thorium, iron can be with wherein a kind of method reextraction thorium, iron in following two kinds of methods:
A kind of method be sulfuric acid, hydrochloric acid a kind of acid wherein with 4-10N as the anti-stripping agent of thorium, iron, thorium, iron are stripped to anti-stripping agent from the mode that refluxes with the adverse current band.Anti-stripping agent is good with sulfuric acid, the hydrochloric acid a kind of acid wherein of 6-8N again.The progression of stripping is 1～6 grade, is advisable with 2～4 grades again, and stream is than being organic phase: anti-stripping agent=1～30: 1, and it flows than again with 5～20: 1 for good.Extraction mixing-time is 2-15 minutes, and settling time also is 2-15 minutes.
Second method is that the oxalic acid solution with 2-30 grams per liters is an anti-stripping agent, is advisable as anti-stripping agent with the oxalic acid solution of 5-15 grams per liters again, adopts single-stage to strip, and its stream is than being organic phase: anti-stripping agent=1～10: 1, and it flows than again with 1～3: 1 for good.The thorium that back extraction is taken out, iron reclaim and obtain thorium dioxide.
Organic phase water behind reextraction iron, thorium or with the sulfuric acid of 0.1-1N, nitric acid a kind of acid wherein as washings, wherein a kind of acid of sulfuric acid, nitric acid with 0.3-0.8N is good again, organic phase is carried out extracting and washing, its stream is than being organic phase: washings=1～10: 1, and again with 1～5: 1 is advisable.Organic phase after extracting and washing recycles.
The extraction in above-mentioned technological process and the used equipment of stripping are with glass reinforced plastic or plastic box mixed settler extractor.Above-mentioned extraction or reextraction are all at room temperature carried out.
At the concentration EDTA complexometric titration of technological process middle-weight rare earths element of the present invention, acidity is the complexing agent complex rare-earth with EDTA-Ca, carries out titration with the standard hydrogen sodium oxide.The concentration of cerium dioxide can be measured with the ferrous ammonium sulphate redox titration.The purity of product cerium dioxide is measured with direct sunshine spectrometry or chemical spectroscopy.The thorium dioxide of constant EDTA volumetric determination, the trace thorium colorimetric method for determining.Iron is measured with the potassium permanganate oxidation reductometry.Fluorine is measured with perchloric acid distillation volumetric precipitation method.
The invention has the advantages that:
1. the method for extracting and separating cerium of the present invention is owing to adopted P
507Be extraction agent, with alkanes or dimethylbenzene etc. as thinner, the interference that the complexing agent that has added fluorine the has suppressed fluorion cerium that extracts, strips, in the process of extraction for a long time, reextraction, do not produce the rare earth fluoride precipitation, do not produce emulsification, the extraction process steady and continuous, easy handling.
2. the rate of recovery height of cerium dioxide and trivalent rare earth element, by adjusting cerium dioxide or the cerous carbonate that washing progression or washing lotion acidity can obtain two nine to six nine various purity, the stripping rate of thorium, the rate of recovery are all high, CeO in few cerium trivalent rare earth element
2The ratio of/REO is little.
3. technology of the present invention is simple, and chemical raw material consumption is few, and product cost is low.
Describe the present invention more specifically, in more detail with following non-limiting examples, will help understanding the present invention and advantage thereof.Protection scope of the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is decided by claim.
Embodiment 1
Hamartite (for example Mianning ore deposit) is made fluorine-containing rare earth sulfate solution as stock liquid with the oxidizing roasting sulfuric acid to leach, contain the CeO of 44.6 grams per liters in the stock liquid
2, CeO
2/ REO is 47.10%, and cerium oxidation ratio 99.12% contains 0.21g/ and rises ThO
2, contain the F of 6.5 grams per liters, 0.35 grams per liter Fe, acidity is 1.2N.Carry out separating of quadrivalent cerium and trivalent rare earth element with counter-current extraction.With 1.2 mol P
507(extraction agent) and C
9～C
12Mixed alkanes (thinner) is formed organic phase, and extraction section progression is 3 grades, and washing section is 0 grade.Stream is than for organic phase: feed liquid=3: 1, and extraction mixing-time (be organic phase and water duration of contact) is 5 minutes, settling time is 10 minutes.The raffinate that obtains containing the organic phase of cerium, thorium, iron and contain trivalent rare earth element.
With containing 20 grams per liter boraxs, the mixing solutions of 10% hydrogen peroxide (30%) (as reductive agent) and 4N hydrochloric acid is as ceric anti-stripping agent, the above-mentioned organic phase that contains quadrivalent cerium, thorium, iron is carried out the reextraction of adverse current band from reflux type, the reextraction cerium, the progression of stripping is 5 grades, and stream is than being organic phase: anti-stripping agent=10: 1, the mixing time of reextraction are 5 minutes, settling time is 10 minutes, obtains containing the organic phase of the strip liquor of cerium and thoriated, iron.
Cerium in the strip liquor is diluted with water to 45 grams per liter CeO
2, the strip liquor that will contain cerium with yellow soda ash is neutralized to PH3, is heated to 70 ℃, adds bicarbonate of ammonia again and makes the acidity of solution reduce to PH8, makes the cerium precipitation, and precipitation obtains the product cerous carbonate, its CeO after washing after filtration
2/ REO is 99.24%, and rare earth impurity is as follows: La
2O
3Pr
6O
11Nd
2O
3Sm
2O
3Y
2O
30.32% 0.086% 0.33% 0.062%＜0.003%
CeO in the raffinate behind the extraction quadrivalent cerium
20.30 grams per liter, CeO
2/ REO0.67%, the cerium dioxide recovery of extraction is 99.33%, its total yield is 97.25%.
The organic phase anti-stripping agent of the sulfuric acid of 6N that will contain thorium, iron as thorium, iron, the progression of reextraction thorium, iron is 4 grades, stream is than being organic phase: anti-stripping agent=15: 1, adopt the adverse current band from the extraction mode that refluxes, thorium, iron are stripped in the anti-stripping agent, the two-phase mixing time is 5 minutes, and settling time is 10 minutes.The percentage extraction of thorium, iron＞99.5%, its stripping rate are 95.3%, and about 5% thorium is in organic phase.
Organic phase behind reextraction thorium, iron is made washings with tap water organic phase is carried out extracting and washing, and extracting and washing progression is 1, and its stream is than being organic phase: tap water=3.75: 1, the organic phase after extracting and washing recycles.
Extraction, strip and all to carry out in box mixed settler extractor, show through nearly one month continuous experiment, extraction, reextraction two phase stratification are fast, no three-phase thing generation.
Embodiment 2
Its working method and equipment are substantially with embodiment 1, and only different is to contain 22.3 grams per liter CeO in the stock liquid
2, CeO
2/ REO is 50%, 0.12 grams per liter ThO
2, 4.3 grams per liter F, 0.23 grams per liter Fe, acidity 0.5N.The extraction of employing reflux type is carried out cerium and is separated with trivalent rare earth element, 0.5 mol P
507-octane is formed organic phase, 2 grades of extraction sections, 3 grades of washing sections, washing lotion is a 2N nitric acid, and reflux type is also used in washing, and stream is than being organic phase: feed liquid: washing lotion=1.5: 1: 0.5, the two-phase mixing time of extraction, washing is 5 minutes, settling time is 10 minutes, and the raffinate that obtains containing the organic phase of cerium, thorium, iron and contain trivalent rare earth element contains 0.11 grams per liter CeO in the raffinate
2, CeO
2/ REO is 0.48%.Washing lotion is returned the leaching roasted ore.
With containing 3 grams per liter boraxs, 1.5% hydrogen peroxide (30%), 0.8N the vitriolic mixing solutions is as ceric anti-stripping agent, the above-mentioned organic phase that contains quadrivalent cerium, thorium, iron is carried out the back extraction of reflux type, the reextraction cerium, the progression of stripping is 3 grades, stream is than being organic phase: anti-stripping agent=1.5: 1, reextraction two-phase mixing time is 5 minutes, settling time is 10 minutes, and cerium dioxide extraction yield 98.9% has 0.6% to enter washing lotion and return, the purity of cerium dioxide is 99.98%, and rare earth impurity is as follows:
La
2O
3 Pr
6O
11 Nd
2O
3 Sm
2O
3 Y
2O
3 ＜0.001％ 0.01％ ＜0.003％ ＜0.003％ ＜0.003％
As anti-stripping agent, stream is than being organic phase with the oxalic acid solution of 2 grams per liters for the organic phase that will contain thorium, iron: anti-stripping agent=3: 1, adopt the single-stage reextraction.The two-phase mixing time is 5 minutes, and settling time is 10 minutes, and the stripping rate of thorium, iron is 98.2%, and about 2% circulates in organic phase.
Organic phase behind reextraction thorium, iron is carried out extracting and washing as washings to organic phase with 0.3N sulfuric acid, and extracting and washing progression is 1 grade, and its stream is than being organic phase: 0.3N sulfuric acid=2: 1.
Embodiment 3
Its working method and equipment are substantially with embodiment 1, and only different is to contain 30.5 grams per liter CeO in the stock liquid
2, CeO
2/ REO is 45.0%, 0.17 grams per liter ThO
2, 5.5 grams per liter F, 0.41 grams per liter Fe, acidity 0.6N.The extraction of employing reflux type is carried out cerium and is separated with trivalent rare earth element.1 mol P
507-C
11～C
16Mixed alkanes is formed organic phase, 3 grades of extraction sections, and 4 grades of washing sections, washing lotion is a 5.5N sulfuric acid, and reflux type is also used in washing, and stream is than being organic phase: feed liquid: washing lotion=1.5: 1: 0.3.The two-phase mixing time of extraction, washing is 5 minutes, and settling time is 10 minutes, the raffinate that obtains containing the organic phase of cerium, thorium, iron and contain trivalent rare earth element, CeO in the raffinate
20.21 grams per liter, CeO
2/ REO 0.66%.Washing lotion is returned the leaching roasted ore.
With containing 5 grams per liter boric acid, 3% hydrogen peroxide (30%), the mixing solutions of 1.2N nitric acid carry out the back extraction of reflux type, the reextraction cerium as ceric anti-stripping agent to the above-mentioned organic phase that contains quadrivalent cerium, thorium, iron.The progression of stripping is 4 grades, and stream is than being organic phase: anti-stripping agent=2: 1.Reextraction two-phase mixing time is 5 minutes, and settling time is 10 minutes.The strip liquor that contains cerium is neutralized to 0.1N with bicarbonate of ammonia, be heated to 78 ℃, add oxalic acid, the amount that adds oxalic acid is: oxalic acid weight/cerium dioxide weight=1.3, the precipitation cerium filters the back in 800 ℃ of calcinations 2 hours, obtains the cerium dioxide product, purity is six nine, and the foreign matter content of rare earth is as follows: La
2O
3, Pr
6O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3＜0.1ppm＜0.1ppm＜0.1ppm＜0.1ppm＜0.01ppm Gd
2O
3, Tb
4O
7, Dy
2O
3, Ho
2O
3, Er
2O
3＜0.03ppm＜0.1ppm＜0.03ppm＜0.03ppm＜0.03ppm Tm
2O
3, Yb
2O
3, Lu
2O
3, Y
2O
3＜0.02ppm＜0.003ppm＜0.1ppm＜0.1ppm
Cerium dioxide extraction yield is 95.7%, and total recovery is 96.15%, 3.61% CeO
2Entering washing lotion returns.
Embodiment 4
Its working method and equipment are fully with embodiment 3, and only different is with 1 mol P
507-dimethylbenzene is formed organic phase.In stock liquid, contain 3 grams per liter boric acid.More than 20 day continuous experiment shows that two phase stratification is fast in the processes such as extraction, reextraction, washing, and the interface is clear.
Embodiment 5
Its working method and equipment are substantially with embodiment 1, and only different is to contain 44.6 grams per liter CeO in the stock liquid
2, CeO
2/ REO is 47.5%, 0.23 grams per liter ThO
2, 8.5 grams per liter F, 0.45 grams per liter Fe, 4 grams per liter Al
2(SO
4)
3, acidity 1.2N.The extraction of employing reflux type is carried out cerium and is separated with trivalent rare earth element.1.5 mol P
507-dimethylbenzene is formed organic phase, 4 grades of extraction sections, and 3 grades of washing sections, washing lotion is a 3N sulfuric acid, and reflux type is also used in washing, and stream is than being organic phase: feed liquid: washing lotion=2: 1: 0.7.The two-phase mixing time of extraction, washing is 5 minutes, and settling time is 10 minutes.Washing lotion is returned the leaching roasted ore.The raffinate that obtains containing the organic phase of cerium, thorium, iron and contain trivalent rare earth element.CeO in the raffinate
20.2 grams per liter, CeO
2/ REO 0.44%.
With containing 15 grams per liter boraxs, 7% hydrogen peroxide (30%), the mixed solution of 3N hydrochloric acid carries out the back extraction of reflux type to the above-mentioned organic phase that contains quadrivalent cerium, thorium, iron, and reextraction cerium, the progression of reextraction are 4 grades, and stream is than being organic phase: anti-stripping agent=5: 1.Reextraction two-phase mixing time is 5 minutes, and settling time is 10 minutes.Continuous experiment through more than 20 days shows that two phase stratification is fast in the processes such as extraction, washing, back extraction, and the interface is clear.Cerium dioxide extraction yield 97.9%, 1.65% returns in washing lotion, and cerium dioxide purity is 99.99%, and rare earth impurity is as follows:
La
2O
3 Pr
6O
11 Nd
2O
3 Sm
2O
3 Y
2O
3 ＜0.002％ ＜0.008％ ＜0.003％ 0.0015％ 0.001％
Embodiment 6
Its working method and equipment are substantially with embodiment 1, and only different is to contain 51.5 grams per liter CeO in the raw material
2, CeO
2/ EEO is 47.10%, 0.20 grams per liter ThO
2, 8.9 grams per liter F, 0.95 grams per liter Fe, 4 grams per liter H
2BO
3, acidity 1.2N.The extraction of employing reflux type is carried out cerium and is separated with trivalent rare earth element, 1 mol P
507-dodecane hydrocarbon is formed organic phase, 5 grades of extraction sections, and 5 grades of washing sections, washing lotion is a 4N sulfuric acid, and reflux type is also adopted in washing, and stream is than being organic phase: feed liquid: washing lotion=2.5: 1: 0.6.The two-phase mixing time of extraction, washing is 4 minutes, and settling time is 8 minutes.Washing lotion is returned the leaching roasted ore, the raffinate that obtains containing the organic phase of cerium, thorium, iron and contain trivalent rare earth element.CeO in the raffinate
20.18 grams per liter, CeO
2/ REO0.34%.
With containing 6 grams per liter boric acid, 3% hydrogen peroxide (30%), the mixed solution of 1.5N hydrochloric acid carries out the back extraction of reflux type, the reextraction cerium to the above-mentioned organic phase that contains quadrivalent cerium, thorium, iron, the progression of stripping is 4 grades, and stream is than being organic phase: anti-stripping agent=2.5: 1.Reextraction two-phase mixing time is 4 minutes, and settling time is 8 minutes, shows that through secular continuous experiment two phase stratification is fast in the processes such as extraction, washing, reextraction, and the interface is clear.The extraction yield of cerium dioxide is 97.5%, 2.15% to enter washing lotion and return.The purity of cerium dioxide is five nine, and rare earth impurity is as follows: La
2O
3Pr
6O
11Nd
2O
3Sm
2O
3Y
2O
3＜1ppm 1.06ppm＜1ppm＜1ppm＜1ppm
Embodiment 7
Its working method and equipment are fully with embodiment 2, and different is to adopt the fractionation extraction mode to carry out quadrivalent cerium to separate with trivalent rare earth, 2 grades of extraction sections, and 4 grades of washing sections, stream is than being organic phase: feed liquid: washing lotion=1.5: 1: 0.3.Obtained result substantially the same manner as Example 2.
Claims (24)
1. the technology of an extracting and separating cerium, with hamartite or hamartite and monazite to mix the fluorine-containing rare earth sulfate solution that the ore deposit makes be stock liquid, it is characterized in that,
(1) (is called for short P with di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester
507) be extraction agent, with the alkane that contains 6 carbon atoms to the alkane that contains 12 carbon atoms, a kind of alkane wherein is thinner, the also available alkane of 5 carbon atoms that contains is to the alkane that contains 20 carbon atoms, wherein the mixture of two or more alkane or dimethylbenzene are that thinner is formed organic phase, carry out quadrivalent cerium, thorium, the extracting and separating of iron and trivalent rare earth element, organic phase, feed liquid, the stream ratio of washing lotion is 0.2～10: 1: 0.1～2, washing lotion is the sulfuric acid of 0.5-8N, hydrochloric acid, nitric acid a kind of acid wherein, washing section progression is the 0-6 level, forms to contain quadrivalent cerium, thorium, the organic phase of iron and the raffinate that contains trivalent rare earth element;
(2) with the fluorine complexing agent that contains 0.2-50 grams per liters, 0.2 the mixing solutions of the reductive agent of～15% (weight percentage) and the hydrochloric acid of 0.5-6N, nitric acid, sulfuric acid a kind of acid wherein is as ceric anti-stripping agent, the organic phase that contains quadrivalent cerium, thorium, iron is carried out back extraction, quadrivalent cerium is stripped in the anti-stripping agent, thorium, iron are stayed in the organic phase, and cerium is separated with thorium, iron.
2. according to the technology of a kind of extracting and separating cerium of claim 1, it is characterized in that, be stock liquid with hamartite or hamartite with the fluorine-containing rare earth sulfate solution that mixes the leaching of ore deposit oxidizing roasting sulfuric acid of monazite or the fluorine-containing rare earth sulfate solution that leaches with hamartite sodium carbonate roasting sulfuric acid.
3. according to the technology of a kind of extracting and separating cerium of claim 1 or 2, it is characterized in that, as the CeO that contains 2-80 grams per liters in the stock liquid
2, CeO
2/ REO (REO is the rare earth oxide total content) is 5～60% (weight percentage, down together), contains 0.5-15 grams per liter F, the ThO of 0.01-1 grams per liter
2, 0.05-2 grams per liter Fe, acidity is 0.2-3N.
4. according to the technology of a kind of extracting and separating cerium of claim 3, it is characterized in that, as containing 15-50 grams per liter CeO in the stock liquid
2, CeO
2/ REO 47～50%, 0.5-8 grams per liter F, 0.1-0.3 grams per liter ThO
2, 0.1-1.4 grams per liter Fe, the fluorine complexing agent that the boric acid of 0.2-50 grams per liters, borax, Tai-Ace S 150, titanium sulfate, zirconium sulfate are wherein a kind of, acidity is 0.4-2N.
5. according to the technology of a kind of extracting and separating cerium of claim 4, it is characterized in that, contain the boric acid of 0.2-10 grams per liters in the stock liquid or contain 0.2-30 grams per liter boraxs.
6. according to the technology of a kind of extracting and separating cerium of claim 4, it is characterized in that, contain 0.1-0.5 grams per liter Fe in the stock liquid.
7. according to the technology of a kind of extracting and separating cerium of claim 1, it is characterized in that extraction agent P
507Concentration in thinner is 0.2-2 mol, with fractionation extraction or counter-current extraction.
8. according to the technology of a kind of extracting and separating cerium of claim 7, it is characterized in that extraction agent P
507Concentration in thinner is 0.5-1.5 mol.
9. according to the technology of a kind of extracting and separating cerium of claim 1, it is characterized in that used washing lotion is sulfuric acid, hydrochloric acid, the nitric acid a kind of acid wherein of 1-5N.
10. according to the technology of a kind of extracting and separating cerium of claim 1, it is characterized in that during the extraction quadrivalent cerium, used stream is than being organic phase: feed liquid: washing lotion=1～6: 1: 0.2～1.
11. the technology according to a kind of extracting and separating cerium of claim 1 is characterized in that, said in ceric anti-stripping agent the fluorine complexing agent be wherein a kind of of boric acid, borax, Tai-Ace S 150, zirconium sulfate, titanium sulfate.
12. the technology according to a kind of extracting and separating cerium of claim 11 is characterized in that, contains 0.2-30 grams per liters or boric acid is 0.2-30 grams per liters in the concentration of ceric anti-stripping agent in ceric anti-stripping agent as the borax of fluorine complexing agent.
13. the technology according to a kind of extracting and separating cerium of claim 1 is characterized in that, said reductive agent is wherein a kind of of hydrogen peroxide, water-soluble divalent iron salt, S-WAT, sulfurous acid.
14. the technology according to a kind of extracting and separating cerium of claim 13 is characterized in that, said reductive agent contains 0.5～10% hydrogen peroxide in the ceric anti-stripping agent of stripping.
15. the technology according to a kind of extracting and separating cerium of claim 1 is characterized in that, the acidity in the ceric anti-stripping agent of stripping is wherein a kind of of sulfuric acid, nitric acid, hydrochloric acid of 0.7-5N.
16. the technology according to a kind of extracting and separating cerium of claim 1 is characterized in that, the organic phase that contains quadrivalent cerium, thorium, iron is carried out the back extraction cerium with counter-current extraction or adverse current band from the method that refluxes.
17. the technology according to a kind of extracting and separating cerium of claim 1 is characterized in that, during the reextraction quadrivalent cerium, used stream is than being organic phase: anti-stripping agent=1～20: 1.
18. the technology according to a kind of extracting and separating cerium of claim 17 is characterized in that, used stream is than being organic phase: anti-stripping agent=1～10: 1.
19. technology according to a kind of extracting and separating cerium of claim 1, it is characterized in that, with the sulfuric acid of 4-10N, hydrochloric acid a kind of acid wherein anti-stripping agent as thorium, iron, the thorium, iron of staying organic phase are stripped into thorium, iron in the anti-stripping agent from the extraction mode that refluxes with the adverse current band, and stream is than being organic phase: anti-stripping agent=1～30: 1.
20. the technology according to a kind of extracting and separating cerium of claim 19 is characterized in that, with the sulfuric acid of 6-8N, the hydrochloric acid a kind of acid wherein anti-stripping agent as thorium, iron, its stream is than being organic phase: anti-stripping agent=5～20: 1.
21. technology according to a kind of extracting and separating cerium of claim 1, it is characterized in that, be the anti-stripping agent of thorium, iron with the oxalic acid solution of 2-30 grams per liters, adopts single-stage to strip, its stream is than being organic phase: anti-stripping agent=1～10: 1, thorium, the iron of staying organic phase is stripped in the anti-stripping agent.
22. the technology according to a kind of extracting and separating cerium of claim 21 is characterized in that, is the anti-stripping agent of thorium, iron with the oxalic acid solution of 5-15 grams per liters, its stream is than being organic phase: anti-stripping agent=1～3: 1.
23. technology according to a kind of extracting and separating cerium of claim 19 or 21, it is characterized in that, make washings through the organic phase water of reextraction thorium, iron or sulfuric acid, the nitric acid a kind of acid wherein of 0.1-1N, organic phase is carried out extracting and washing, its stream is than being organic phase: washings=1～10: 1.
24. the technology according to a kind of extracting and separating cerium of claim 23 is characterized in that, is washings with sulfuric acid, the nitric acid a kind of acid wherein of 0.3-0.8N, its stream is than being organic phase: washings=1～5: 1.
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| CN95103694A CN1045010C (en) | 1995-04-12 | 1995-04-12 | Sorting cerium process by extraction from rare-earth sulfate solution containing fluorine |
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|---|---|---|---|
| CN95103694A CN1045010C (en) | 1995-04-12 | 1995-04-12 | Sorting cerium process by extraction from rare-earth sulfate solution containing fluorine |
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| CN1045010C CN1045010C (en) | 1999-09-08 |
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| CN1098361C (en) * | 1998-11-13 | 2003-01-08 | 中国科学院长春应用化学研究所 | Process for extracting and separating cerium and thorium from hamartite leachate |
| CN100348747C (en) * | 2004-12-28 | 2007-11-14 | 北京有色金属研究总院 | Cerium reverse extracting method from cerium-carrying fluoric organic phase and cerium purifying method |
| CN101294244B (en) * | 2007-04-25 | 2010-09-01 | 北京有色金属研究总院 | Technique for extraction separation of quadravalence cerium, thorium, fluorine and cerium less tervalence rare earth from sulphuric acid rare earth solution |
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| DE69318315D1 (en) * | 1990-09-19 | 1998-06-04 | Union Oil Co | EXTRACTION OF CER FROM FLUORIDE CONTAINING ORES |
| CN1055394A (en) * | 1990-12-31 | 1991-10-16 | 冶金工业部包头稀土研究院 | Preparation of high-purity cerium compound by solvent extraction method |
| CN1027547C (en) * | 1992-01-16 | 1995-02-01 | 北京有色金属研究总院 | Emulsion-removing method in the process of extraction |
| CN1114365A (en) * | 1994-06-30 | 1996-01-03 | 郭西林 | Process for extracting high-valence cerium from ore leachate directly |
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1995
- 1995-04-12 CN CN95103694A patent/CN1045010C/en not_active Expired - Lifetime
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| CN1098361C (en) * | 1998-11-13 | 2003-01-08 | 中国科学院长春应用化学研究所 | Process for extracting and separating cerium and thorium from hamartite leachate |
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| CN101294244B (en) * | 2007-04-25 | 2010-09-01 | 北京有色金属研究总院 | Technique for extraction separation of quadravalence cerium, thorium, fluorine and cerium less tervalence rare earth from sulphuric acid rare earth solution |
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