CN85106255A - Method of extract scandium from rare-earth mineral - Google Patents

Abstract

The invention discloses a kind of from rare-earth mineral method of extract scandium.This scheme belongs to the nonferrous metallurgy field, overall process is: carry the scandium mother liquor with the rare-earth mineral leaching, select extraction process enrichment scandium or rare earths such as naphthenic acid, P204, P507, P350, TBP, primary amine for use, select for use oxalic acid, ammonium oxalate, ammoniacal liquor, caustic soda, Hypophosporous Acid, 50, condensing crystal, scandium carbonate thorium carbonate to boil the precipitator method such as separation and from mother liquor, raffinate, strip liquor, reclaim scandium and rare earth oxide or salt.

Description

Method of extract scandium from rare-earth mineral

The invention belongs to the non-ferrous metallurgy technology field.

The scandium element is classified the dispersed elements mineral as in Ore Deposits.The present main comprehensive scandium (6, P85) (be reference numbers and number of pages, later on all with) that reclaims from the smelting residue of the wolframite, cassiterite and the uranothorite that contain scandium 0.01-0.05% in the world.Because the tungsten tin mine inadequate resource of rich scandium, in the world scandium roughly in 1,930,000 tons of the reserves in wolframite and cassiterite scandium only account for 0.06%, all the other low-grade reserves for being difficult at present utilize, so the metal scandium high price is expensive, world market valency per kilogram 8000-15000 dollar in 1981, and output is minimum, estimates 60 kilograms (6, P85) of metal scandium output ability, the world in 1980 according to the American.Yet from now on along with science and technology development, requirement increases day by day, and perhaps the annual production of scandium will reach several kilotons (25, P26).So scandium is a kind of big promising element, and the smelting of scandium also will be big promising industry.But according to nineteen eighty-two data report: the condition of planning to set up exploitation scandium mineral enterprise does not at present also possess (25, P22).

Seldom notice the problem whether the scandium association is wherein arranged during the former studies rare earth mineral deposit, even China's Ministry of Geology is issued in the sampling analysis standard also the failed call rare earth mineral deposit and is analyzed scandium, so do not have rare-earth mineral association scandium reserves (25 in the roughly reserves of scandium in the world, P23), do not see the report that the rare-earth mineral of associating is extracted scandium as yet yet.The author has not seen this patent documentation to the retrieval of GuangDong Patent department yet recently.I considered once that rare earth, scandium element character were close, found the rule in the inevitable association scandium of rare-earth mineral ore deposit after deliberation, and utilized this rule to occupy in benevolence first and found association scandium ore deposit in the rare earth mineral deposit.In order to explore the recovery problem of scandium in the rare-earth mineral, specially consulted the relevant documents in aspect such as geology, chemistry, rock-mineral analysis and rare earth metallurgy, utilize refining the helpful general data of scandium possibility, designed this programme.

The objective of the invention is to solve at rare-earth mineral (residue, mixed rare-earth oxide and salt after comprising association rare-earth mineral, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite.Later on all with) extract comprehensive oxide compound and the muriatic problem that reclaims scandium in rare earth or the rare earth grouping process, to enlarge the scandium resource, satisfy in the world to the increasing requirement of scandium requirement.

Task of the present invention is finished as follows:

1, geological and mineral foundation and ultimate principle

Scandium, yttrium and group of the lanthanides totally 17 elements belong on the periodictable III together and pay family-scandium and pay family, and its peripheral atoms or ionic structure are closely similar, so their chemical property are also closely similar, thereby form a rare earth extended family.Because the inevitable association scandium of rare-earth mineral ore deposit like this.This is that rare-earth mineral is refined the main geological and mineral foundation of scandium.The ultimate principle of refinement scandium and total technical conceive are from rare-earth mineral: utilize scandium, rare earth element chemical property close " general character ", the ore that will contain them is handled with chemical process, makes it separated, dissociates out, and enter into mother liquor jointly; Utilize its ordination number and ionic radius and chemical property to have " individual character " of difference again, select naphthenic acid, P for use ₂₀₄, P ₅₀₇, P ₃₅₀, extraction process such as TBP, primary amine to these components in the mother liquor extracted, separation and enrichment, select for use oxalic acid, ammonium oxalate, ammoniacal liquor, caustic soda, condensing crystal, scandium carbonate thorium carbonate to boil the precipitator method such as separation again to raffinate and strip liquor, reclaim the oxide compound and the chloride product of scandium, rare earth.

2, basic fundamental method

Rare-earth mineral and smelting equipment kind thereof are many, and its basic fundamental method is also different thereupon.Now division is as follows:

(1) leaching method of mother liquor

The total method of ore leaching mother liquor is: element such as scandium, rare earth is decomposed or dissociate out with electrolyte solution, enter into solution with salt or cationic form, promptly constitute the mother liquor that refines scandium, rare earth.Because of ore type is many, the mother liquor preparing process is different, so after being set forth in addition.

(2) extraction process

The main purpose of extraction is to separate and enrichment scandium and rare earth element from mother liquor, makes it to enter into raffinate or strip liquor, lays the first stone for the precipitator method reclaim product.Here design following 6 extraction basic technical schemes altogether:

A, naphthenic acid extraction process: the data report: naphthenic acid belongs to carboxylic acid extractant in the acid complexometric extraction system, and is cheap, has industrial utility value.It is with unit molecule HA(organic monoacid) and 2 atom and molecule H ₂A ₂Two kinds of forms exist, can be with the rare-earth cations in the cationic exchange form extraction solution, and react and be:

, or

${\mathrm{TR}}^{\mathrm{3+}}{}_{\mathrm{(）}}\mathrm{＋3H}{}_{2}A{}_2{}_{\mathrm{（）}}\mathrm{＝TR(HA}{}_2\mathrm{)3}{}_{\mathrm{(）}}\mathrm{＋3H}{}^{＋}{}_{\mathrm{（）}}$ .

The back extraction reaction that with HCI is example is:

${\mathrm{TRA}}_3{}_{\mathrm{(）}}\mathrm{＋3HCI=3HA}{}_{\mathrm{(）}}\mathrm{＋TRCI}{}_3\mathrm{(）}$ , or

${\mathrm{TR(HA}}_2){}_{\mathrm{3(）}}\mathrm{＋3HCI=3H}{}_{2}A{}_{\mathrm{2(）}}\mathrm{＋TRCI}{}_{\mathrm{3（）}}$ 。

The extracting rare-earth element sequence is the backward extraction in 10% naphthenic acid-10% alcohol-80% kerosene-HCI system (PH4.8): samarium＞neodymium＞praseodymium＞dysprosium＞ytterbium＞lutetium＞terbium＞holmium＞thulium＞erbium＞gadolinium＞lanthanum＞yttrium (16, P421).

According to above situation, above-mentioned sequence is the sequence consensus that reduces with ionic radius generally, and scandium is a rare earth intermediate ion radius reckling, so infer that scandium should be arranged in after the yttrium, be ∑ Ce＞∑ y＞Sc, be the most difficult collection taker, so can utilize this characteristics design to separate scandium technology.Promptly at first extracting rare-earth is in organic phase from mother liquor with naphthenic acid, and scandium is squeezed and enters into raffinate.The both obtains separating and concentration effect like this.

B, P ₂₀₄Extraction process: data report: P ₂₀₄Belong to acid phosphorus extraction agent in the acid complexometric extraction system, valency is cheap, widely industrial utilization.In non-polar solvent (as kerosene) normally with H ₂A ₂Form exist.Its extraction mechanisms and reaction formula and H ₂A ₂Naphthenic acid is similar.The partition ratio of its extracting rare-earth increases along with reducing of ionic radius, for positive sequence extraction (16, P ₄₁₃).

By this rule, infer that the extraction sequence is: Sc＞∑ y＞∑ Ce, promptly scandium is the easiest collection taker, and is just opposite with naphthenic acid.Therefore, the scandium priority enrichment then can design and adopt P to organic phase in the solution if desire to make ₂₀₄Extraction process.

C, P507 extraction process: data report: P507 character is similar to P204, but acidity and extracting power than P204 a little less than, and that back extraction is got up is easier and be difficult for emulsification than P204.

Extraction in nitric acid, hydrochloric acid soln: in nitric acid, hydrochloric acid medium, extraction order: Sc ≈ Th＞Ce ⁴⁺＞TR ³⁺(16, P537).The extraction curve of each element very similar (20, P23) under the different acidity.In nitric acid medium, during with the 0.94FP507-kerosene extraction at initial water HNO ₃Under concentration (M) 0.57,1.15,1.43,1.0,2.0,2.5,3.0,4.0, the 5.0 various situations, the scandium percentage extraction all is similar to 100%; The thorium percentage extraction is 99.3-99.0%; The cerium percentage extraction is 92.7-84.1%; The lutetium percentage extraction is 98.2-47.4% (20, P23).(find out thus what P507 do not have be strict with to scandium, the original aqueous phase acidity of thorium, can be dense can be rare; And to other elements, then be that the big percentage extraction of acidity reduces.）

Extraction in sulphuric acid soln: extracting power under different acidity, Sc＞Ce ⁴⁺＞Th＞TR ³⁺The percentage extraction of trivalent rare earth element is all with original water H ₂SO ₄The increase of concentration and descending, acidity is low more, and it is fast more to descend.The Ce(IV) and the percentage extraction of Th also with H ₂SO ₄Concentration increases and descends, but the Ce(IV) descend slower, at H ₂SO ₄Both equate during=1.5n, Ce(IV when＞1.5n) extracting power than Th height, Ce(IV when 5n) percentage extraction is 62%, Th is 32%.The percentage extraction of scandium is all greater than 98% when 0.8-5.5n, the Fe(III) all 20%.Because the extracting power difference of these elements is very big, so just might make Sc, Th, Ce(IV) with the TR(III) separate.Be extracted into the Ce(IV in the organic phase) can separate with Sc, Th by reduction reextraction.Th under higher acidity (as 〉=5nH ₂SO ₄) its percentage extraction only 35%, thereby might utilize reverse-extraction of high acid that Th is separated with Sc.In sulphuric acid soln, the Fe(III) at 1-5nH ₂SO ₄Down, its percentage extraction is similar to 20% and little with aqueous phase acidity variation relation, and this just provides uses H ₂SO ₄Back extraction Fe(III from P507) possibility (20, P24).

According to above-mentioned situation,, can design with the preferential extracting and enriching of P507 extraction process to organic phase to the scandium in the mother liquor.To containing the scandium raffinate behind the naphthenic acid extracting rare-earth, also can adopt the P507 extraction again, make it organic phase, promptly constitute naphthenic acid-P507 combined extraction, the former pushes away scandium, and the latter draws scandium, thus the more sharp effect that reaches separation and concentration.

D, P350 extraction process: the data report: the P350 extraction agent belongs to neutral complexometric extraction system, is neutral organic compound, and extract is a neutral inorganic, as TR(NO ₃) ₃, extraction agent and extract combine the generation neutral complex.With P350-HNO ₃System is an example, and its reaction is:

〔16，P394〕。With rare nitric acid (0.5nHNO ₃) reaction of back extraction is:

P ₃₅₀The extraction order of-HCI system: Fe ³⁺＞UO ₂ ²⁺＞Sc ²⁺＞Th ⁴⁺＞TR ³⁺Rare earth is arranged at last, is extracted hardly.P ₃₅₀-HNO ₃The extraction order of system: UO ²⁺ ₂＞Th ⁴⁺＞Sc ²⁺＞TR ³⁺＞Fe ³⁺, ferric iron be extracted hardly (16, P ₅₀₃).

Therefore, to the mother liquor of the uranium-bearing that makes by monazite, thorium, scandium, rare earth, iron, can adopt this law to extract scandium.

E, TBP extraction process: reported in literature: TBP is a tributyl phosphate, belongs to neutral complexometric extraction system extraction agent, has been industrial utilization, and price is low, easily buys.Its extract is a neutral inorganic, as TR(NO ₃) ₃, extraction mechanisms is complexing.With extracting rare-earth nitrate is example, reacts to be:

With rare nitric acid (0.5n) back extraction, react and be:

The ability of 100%TBP extracting metals in nitric acid medium is by following order: UO ²⁺ ₂＞Th ⁴⁺＞Sc ³⁺＞Y ³⁺＞TR ³＞Fe ³(16, P ₄₉₇).100%TBP extracts order in hydrochloric acid medium: Fe ³⁺＞UO ²⁺ ₂＞Sc ²⁺＞Th ⁴⁺＞TR ³⁺(16, P ₅₀₃).Scandium also may be extracted by TBP in the concentrated hydrochloric acid medium, and organic phase water or 1% dilute hydrochloric acid are stripped, and then scandium reenters water.Under the different salt acidacidities, the partition ratio of extracting scandium is:

Concentration of hydrochloric acid n	2.3	3.5	4.7	5.8	7.0	8.2	9.4	10.5
									Partition ratio has/water	0.02	0.07	0.26	1.4	7.6	36	110	>1000

Because partition ratio is big, thus available extraction process enrichment scandium, and can separate with elements such as rare earth, beryllium, aluminium, chromium (III), niobium, tantalum, copper, titaniums (19, P ₅₁₈).

According to above-mentioned data, can design this method of using to the extraction that contains the scandium in nitric acid or the hydrochloric acid mother liquor of producing by monazite, especially be more suitable for the concentrated hydrochloric acid system.

F, primary amine extraction process: the data report: primary amine belongs to amine extractant in the ion association extraction system.10% primary amine-4% alcohol mixture-86% kerosene is organic phase, the water sulfuric acid concentration is in the 0.1-1.5n scope, the percentage extraction of thorium, scandium＞99%, the percentage extraction 92% of cerium (IV), the percentage extraction of rare earth and iron (III) all increases with the water sulfuric acid concentration and descends, and the iron percentage extraction drops to about 25% during to 2n.Homemade primary amine N1923 is original organic phase at 10%N1923-4% alcohol mixture-86% kerosene, initial condition phase composite TRxOy 23g/l, ThO ₂0.18g/l, Fe 18g/l, P ₂O ₅7g/l, H ₂SO ₄Percentage extraction ThO during 1n ₂＞99%, TRxOy 32.9%, Fe 4.8%.At 1% N1923-1% ROH-98% kerosene is original organic phase, original water TRxOy 27.6g/l, ThO ₂0.12g/l, compare 1: 4, when sulfuric acid concentration is 0.69-1.5n, percentage extraction: ThO ₂98.1-97.9%, Fe 0.04-0.4%, TRxOy 0.15-0.16%, be that 1%N1923 collection thorium is very capable, the percentage extraction that aqueous phase acidity changes thorium does not have any influence, and the extracting power of rare earth and iron is all very low, therefore, N1923 is effective extraction agent of Separation of Thorium from rare earth and iron.The backwash rate of rare earth and iron increases and increases along with concentration of nitric acid, at 0.075nHNO ₃The time, the backwash rate of rare earth and iron all reaches 98-99%, and thorium almost can not wash, and works as HNO ₃During concentration＞0.4n, backwash rate＞98% of thorium, therefore available 0.06-0.08nHNO ₃Backwash rare earth and iron are used 0.4-0.6nHNO ₃Back extraction thorium (21, P11-13).The behavior of scandium in chemical reaction is similar to rare earth element, some again to thorium, zirconium similar (19, P518).

According to above-mentioned situation, can infer that the primary amine extraction is Th ≈ Sc＞Ce(IV in proper order)＞TR＞Fe, promptly the easiest extraction thorium, scandium, the most difficult extraction iron.Also the homemade primary amine N1923 of deducibility also must extracting scandium, and percentage extraction also should be very high, and aqueous phase acidity is at 0.1-1.5nH ₂SO ₄Extraction to scandium in the scope should not have much influences yet.Therefore, should be very suitable to the mother liquor extraction scandium of thoriated, the high sulfuric acid medium of iron.

(3) precipitator method

The precipitator method are precipitated components such as scandium in mother liquor or raffinate or the strip liquor, rare earth and reclaim.Here design following 6 kinds:

A, oxalate precipitation method: reported in literature: re chloride adds oxalic acid solution promptly the precipitation of rare earth oxalate (16, P616).So the refinement scandium mother liquor that has prepared can be placed container, add oxalic acid (H ₂C ₂O ₄2H ₂O) saturated solution is at PH ₂During the left and right sides, can produce the precipitation of rare-earth oxalate, its reaction should be:

Offer report in a separate paper: scandium and oxalic acid can form oxalic acid scandium precipitation, but precipitation easily generates complex ion and be dissolved in the excessive oxalic acid, also are soluble in the oxalate solution of basic metal or ammonium.The solubleness of oxalic acid scandium is 6 mg/litre, and because produce hypersaturated state and form complex compound so, when scandium (III) concentration during, can not produce precipitation (18, P687) less than 1.5 grams per liters.Judge in view of the above: must sneak into few part oxalic acid scandium in the above-mentioned rare-earth oxalate, and a large amount of scandiums remaines among the surplus liquid of precipitation with oxalate or complex form, its total reaction should be:

Therefore, the scandium in the mother liquor is by behind the oxalic acid precipitation, and few part enters in the oxalate precipitation thing of rare earth and scandium, and it in the liquid, is that further scandium, Rare Earth Separation enrichment lay the first stone so design this law that major part is but still stayed after precipitation.

B, the ammonium oxalate precipitator method: reported in literature: cerium group oxalate is insoluble to ammonium oxalate solution, and yttrium group oxalate dissolves in ammonium oxalate solution (22, P592).Can make the oxalate of some rare earth element generate soluble complex salt (12, P230) with ammonium oxalate.Its reaction may for:

The oxalic acid scandium forms soluble complexes (16, P260) in ammonium oxalate solution.Its reaction may for:

。

According to above-mentioned situation, can design, the rare-earth oxalate throw out that produces in the oxalic acid precipitation technological process is handled with ammonium oxalate solution, cerium group oxalate be left behind because of not dissolving, after filtration, hot wash, refilter and roasting after, promptly get cerium group oxide product.And after the precipitation in the liquid because of yttrium group and scandium complexing salt easily dissolving exists wherein, available laxative remedy recovery scandium, that is:

C, ammoniacal liquor (NH ₄OH) and caustic soda (NaOH) precipitator method: reported in literature: ammoniacal liquor can precipitate scandium quantitatively.The scandium hydroxide precipitation is insoluble to (19, P519) in the excessive ammonia.If in the solution of rare-earth salts, add NaOH or NH dropwise ₄OH promptly has M(OH) ₃Precipitation.Sedimentary order is Sc, Lu, Yb, Tm, Er, Ho, Dy, Tb, Sm, Gd, Eu, Y, Nd, Pr, Ce, La.It all is precipitation agent usually with ammonium hydroxide that the precipitation of hydroxide of scandium separates.Add sodium hydroxide solution in the Scium trichloride solution, begin precipitation in PH4.9, complete substantially in the PH5.45 precipitation; Rare-earth hydroxide will just begin precipitation (18, P685) at PH6.3.

According to above-mentioned situation, can design, liquid after behind the precipitation cerium group oxalate in the ammonium oxalate depositing technology is progressively added NH ₄OH or NaOH solution, making PH earlier is 4.9-5.45, with the precipitation scandium hydroxide, roasting is the Scium trioxide product again; Remaining fluid adds NH again ₄OH or NaOH solution increase to greater than 6.3 PH, and the precipitation of hydroxide of yttrium group is promptly arranged, through leach, roasting promptly gets yttrium group oxide product; Contain colloidal yttrium hydroxide in the surplus liquid this moment, destroys colloid and produce YCI after adding HCI ₃, the reconcentration crystallization promptly gets the Yttrium trichloride product.

D, the condensing crystal precipitator method: if contain scandium in mother liquor or raffinate or the strip liquor and rare-earth salts concentration is bigger, and need not reprocess to oxide compound the time, it is concentrated directly to heat, and makes it crystalline deposit and goes out scandium and rare-earth salts, as ScCI ₃Deng; And can make it that fractional crystallization goes out variant production under differing temps.

E, scandium carbonate thorium carbonate boil the precipitation separation method: reported in literature: containing ScCI ₃, ThCI ₄Hydrochloric acid soln in add 20% Na ₂CO ₃(alkali) solution promptly generates Sc2(CO ₃) ₃And Th(CO ₃) ₂Precipitation; Through boiling Th(CO ₃) ₂Dissolved, Sc2(CO ₃) ₃Do not dissolve, both can be separated after the filtration; Sc2(CO ₃) ₃Promptly to get Scium trioxide (3, P597) after dilute sodium carbonate solution washing, clarification, the roasting.Surplus liquid is after cooling, and promptly crystalline deposit goes out Th(CO ₃) ₂, promptly get Thorotrast after the roasting.Reaction should be:

Carbonatization:

According to above-mentioned situation, to containing the mother liquor of scandium and rare earth and thorium,, can design products such as carrying scandium with this law as mother liquor with the monazite preparation.

3, process scheme

Because of the rare earth ore type is many, appointed condition on an equal basis because of, it is also different thereupon to utilize rare-earth mineral to refine scandium technical process method.Although yet various process scheme difference because of scandium, rare earth character are close, can reclaim simultaneously, adopt basic extracting method similar, and have homogeny in essence.That is to say that these different flow schemes are to be combined into by actual needs by above-mentioned basic skills, so these technical process are included within the total inventive concept scope.Now with following different ores for being example, be described below:

(1) residue, mixed rare-earth oxide and salt refine scandium technology after ion adsorption type rare earth ore, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite

The geological and mineral foundation of scandium technology is refined in a, design

I, ion adsorption type rare earth ore: be decomposed for grouan, granite porphyry, acid volcanic rock wherein contain rare earth, scandium rock etc. after weathering, making mineral middle-weight rare earths, scandium atomic transformation is the free positively charged ion, and constitutes the mineral deposit for clay mineral absorption and the enrichment that forms after the weathering.The rare earth grade of ore is generally about 0.1-0.2%.This rare-earth mineral is easily extracted rare-earth products with hydrometallurgy, and is good in economic efficiency.Scandium content was not all measured in the past.Recently mensuration has been made in the Ren Ju ore deposit, Sc ₂O ₃Content: the granite porphyry protolith is 8.98PPM, its weathering crust ore average out to 12.68PPM, than 1.41 times of protolith enrichments, the partition value is 1.02% when doing partition calculating with 16 kinds of rare earth elements, weigh by international market price in 1981, the value ratio mixed rare earth oxide of Scium trioxide is worth big 3.2 times.

II, rich scandium subsiliceous rock (comprising gabbro, pyroxenolite, the green stone of brightness, basalt etc.) saprolite: reported in literature: subsiliceous rock on average contains rare earth 132.7PPM, scandium 30PPM (1, P40).The same after this kind rock decay with grouan, can form scandium ion and rare earth ion, and be that clay mineral is adsorbed.If scandium is arranged in the granite porphyry weathering crust of similar Ren Ju mining area than the phenomenon of 1.41 times of protolith enrichments, the then Sc of subsiliceous rock weathering crust ₂O ₃Content can reach 42.3PPM.And for example kernel occupies mining area Sc ₂O ₃Content 12.68PPM confirms really to be worth greatly than rare earth through practice, and then scandium also should have economic worth in the subsiliceous rock saprolite.Like this, can increase the resource of scandium greatly.

Residue after III, the aluminium metallurgy of rich scandium bauxite: data report: association scandium reserves account in the world 48% of 1,930,000 tons of scandium reserves roughly in the bauxite, and the scandium average grade is 50 gram/tons (25, P23).Often contain elements (26, P49) such as cerium in the bauxite.Used in Guangxi Pingguo Bauxite Project contains rare earth grade 0.1028% (28, P25) (having met the requirement of ion adsorption type rare earth ore industrial index).Contain a large amount of scandium resources in the Used in Guangxi Pingguo Bauxite Project, through evidence, raw ore substantially exceeds external recovery grade (0.002-0.005%) at present through washing post analysis scandium content, can foretell, if the scandium in the pingguo bauxite can effectively be reclaimed, will make the output of China's scandium occupy absolute advantage, this point in the world, should cause the attention (29, P17) of units concerned.Bauxite middle-weight rare earths, scandium may be adsorbed in sedimental surface (6, P96) with hydroxide form.According to above-mentioned situation, residue after the bauxite aluminium metallurgy (red mud) is because of through roasting, and wherein the occurrence status of scandium, rare earth should be respectively Sc2O ₃, TR2O ₃Form, and content must have certain enrichment, more taller than raw ore should have bigger economic implications, quite is worth recycling.In addition, document is also reported: bauxite deposit association still has a large amount of galliums, vanadium, uranium, thorium etc.Gallium more than 90 percent is from bauxite deposit in the world, and its reserves are 110,000 tons, and the gallium reserves of verifying in China's bauxite deposit just are 50,000 tons, and its grade mostly meets or exceeds the industrial utilization grade.Gallium, vanadium have 35% to enter into residue (29, P17) naturally in oxygenerating aluminium process.Therefore, the gallium in the red mud etc. and rare earth, scandium are the same, and higher content is all arranged, and design synthesis is reclaimed foundation.

IV, mixed rare-earth oxide and salt: rare-earth mineral association scandium, but do not reclaim, so rare earth intersexes product should contain scandium. in the past

Producing of b, mother liquor

The reparation technology flow process of mother liquor sees accompanying drawing 1-1 for details.Now division is as follows:

I, made of stones the getting of ion adsorption type rare earth ore are refined the scandium mother liquor:

The system mother liquor is invaded out in diafiltration: occupy the rare-earth mining area data with reference to benevolence, draw up this quadrat method, promptly put ore in the diffusion cell, add 3%NH ₄CI(or (NH ₄) SO ₄, NH ₄NO ₃) or 7%NaCI solution soaking, as have ready conditions and also can use sea water immersion, make it solid-to-liquid ratio=1kg: 0.5l, PH=6, then ammonium or sodium ion to solution, react ore middle-weight rare earths, scandium ion-exchange to be:

-2TR ³⁺·2Sc ³⁺+12NH ₄CI+6H ₂O→

-3H ⁺·6NH ⁺ ₄+2TRCI ₃+2ScCI ₃+6NH ₄OH+3H ⁺。

With NH ₄CI(or (NH ₄) ₂SO ₄) when soaking 55-90 minute for leaching agent, diafiltration goes out I section liquid, its PH=6, TR ₂O ₃0-0.0ng/l; When soaking 100-280 minute, diafiltration goes out II section liquid, its PH=3.5, TR ₂O ₃0h-ng/l; Be III section liquid when soaking 290-570 minute, PH=4.5-5, TR ₂O ₃＜1.6g/l.With NaCI is that the leaching agent immersion was an I section liquid in the time of 20-50 minute, PH=6-4, TR ₂O ₃0.00-0.53g/l; Be II section liquid when soaking 60-340 minute, PH=3.5-4, TR ₂O ₃1.09-6.44g/l; Be III section liquid when soaking 360-420 minute, PH=4, TR ₂O ₃1.09-1.53g/l.As leaching with seawater, because of wherein NaCI concentration is not high, the leaching of possible each section liquid takes and will grow.Above I section liquid returns the usefulness that mine tailing is washed in the leaching pond; II section liquid through clarify supernatant liquor, make the usefulness that mother liquor extracts rare earth, scandium etc.; III section liquid returns the usefulness of soaking the ore deposit after adding leaching agent.Leach TR according to data (24, P16) ₂O ₃When on average direct yield is with ammonium sulfate is 97.3%, is 96.76% during with sodium-chlor, so infer Sc2O ₃Direct yield should be similarly.

Dynamically leach and produce mother liquor: leaching agent and exchange mechanism are the same.Stir into mud with machinery, silt particle separated, will contain the mud clarification filtration of rare earth, scandium after, promptly get mother liquor.

II, rich scandium subsiliceous rock saprolite are produced and are refined the scandium mother liquor: similar to the above-mentioned ion adsorption type rare earth ore mother liquor method of getting made of stones.

Residue is produced and is refined the scandium mother liquor after III, the aluminium metallurgy of rich scandium bauxite: according to reported in literature: Sc2O ₃Dissolve in hot concentrated acid (27, P192), so leach this residue with hot concentrated hydrochloric acid, clarification filtration goes out insolubles, promptly gets to contain TRCI ₃, ScCI ₃, GaCI ₃Mother liquor.Reaction should be:

IV, mixed rare-earth oxide and salt are produced and refined the scandium mother liquor: salt is produced with water dissolution; Oxide compound is with leachings such as hydrochloric acid.

C, leaching-precipitator method are refined the scandium process scheme

See accompanying drawing 1-2.

Shown in accompanying drawing 1-2, the total flow process of this technology is: liquid after behind mother liquor oxalic acid precipitation rare earth and a small amount of scandium oxalate is added NH ₄OH(or NaOH) reclaim the main part of scandium in the mother liquor; Sedimentary rare earth and a small amount of scandium oxalate are leached with ammonium oxalate solution, residually go out cerium group oxalate, remaining fluid adds NH ₄OH(or NaOH), precipitation reclaims scandium (Sc(OH) when PH4.9-5.45 ₃) less important part, precipitation reclaims ∑ Y(OH in PH＞6.3 o'clock) ₃; Stay Y(OH at last) ₃Colloidal solution is handled with HCI, and the reconcentration crystallization goes out YCI ₃Product.To promptly getting its oxide product after above-mentioned scandium, rare-earth hydroxide and the oxalate roasting.

1-2 and above-mentioned situation with reference to the accompanying drawings, the maximum characteristics of this programme promptly are general in the past " oxalic acid precipitation rare-earth oxalate technology " as can be seen, have increased ammoniacal liquor and ammonium oxalate depositing technology and have extracted scandium.Owing to do not do like this, wasted to cause scandium in the past.This programme flow process is not long, and equipment is uncomplicated, can get on the job with indigenous methods, and can refine bid expensive Scium trioxide, yttrium oxide, can obtain yttrium group and cerium group oxide compound, so should belong to the scheme of economy and facility yet.

D, leaching-extraction-precipitator method are refined the scandium process scheme

See accompanying drawing 1-3 and accompanying drawing 1-4.

Consider scandium and rare earth, especially with the closer characteristics of heavy rare earths relation, reach " Xunwu rare-earth mineral P204 rare earth grouping technical process " with reference to " the extraction process separation of oxygenated yttrium technical process of one step of naphthenic acid nitric acid system " in " rare earth ", and design the technical process shown in accompanying drawing 1-3 and accompanying drawing 1-4.The original technical conceive of this step extraction process is to heavy rare earth mixture, directly extracts yttrium oxide without the extraction grouping.Promptly utilize naphthenic acid to the characteristics of yttrium than the difficult extraction of rare earth, be that 100% naphthenic acid is extracted into organic phase with rare earth, yttrium earlier with saponification degree, be that 90% naphthenic acid is done 108 grades fractionation extraction to this organic phase with saponification degree again, make the yttrium of difficult extraction enter raffinate, and separate out with oxalic acid precipitation, and roasting is highly purified yttrium oxide product; To the organic phase of the naphthenic acid extracting rare-earth second time, do to reclaim rare earth or make P507(P204) usefulness of rare earth grouping.See accompanying drawing 1-3 and accompanying drawing 1-4 for details.Consider that now scandium is than the more difficult characteristics with the naphthenic acid extraction of yttrium, think that the main part of the scandium in the raw material can be transferred in the raffinate behind the abandoned first time of the naphthenic acid extracting rare-earth in the past, so existing it is designed with P507 done 20 grades of fractionation extractions and enrichment, with the 6nHCI back extraction, again the strip liquor condensing crystal is gone out the Scium trichloride product.See accompanying drawing 1-3 for details.In addition, thinking still to have a small amount of scandium to enter into the raffinate of above-mentioned second time of naphthenic acid extracting rare-earth, so design adds ammoniacal liquor (or caustic soda soln) to be settled out Sc(OH to liquid after the yttrium oxalate post precipitation) ₃, roasting is the Scium trioxide product again.Because above-mentioned yttrium oxide is a high purity product, so infer that Scium trioxide also may be highly purified product herein.Organic phase as for above-mentioned second time of naphthenic acid extracting rare-earth also may still have a spot of scandium, if any recovery value, then can reclaim in P507 rare earth grouping technology.

E, extraction-precipitator method gallium extracting technology flow process

See accompanying drawing 1-3.

Extract the gallium that certainly will relate to association in scandium, the rare earth process, uranium, thorium, vanadium etc. with residue after the aluminium metallurgy of rich gallium bauxite.Select anxious scarce and very high gallium (the world market valency per kilogram 800-1100 dollar (10 in 1981 of price of our times herein, P37)), with reference to the pure gallium compound of gallium concentrate system produce flow process (30, P22), designed the extraction gallium technical process shown in accompanying drawing 1-3 in passing.This flow process is: with the mixed organic solvents of 30%A101-70% ethylbenzene, and the gallium in the extracting and enriching hydrochloric acid soln repeatedly; Then with rich gallium organic phase with the water back extraction, make it with GaCI ₃Form enters into strip liquor, separates out GaOH with ammoniacal liquor (or caustic soda soln) precipitation again, promptly gets product after the filtration.Reaction should be:

Ga(OH) ₃Be dissolved in and get gallic acid sodium (NaGaO in the NaOH solution ₂) alkaline electrolyte, put electrolyzer, under 50 °-60 ℃, carry out electrolysis, get liquid metal gallium (29.8 ℃ of the molten points of gallium) (30, P24) in the negative electrode place.

(2) Inner Mongol mixed rare earth concentrate sulfurization roasting-leaching-extraction-precipitator method are refined the scandium process scheme

See accompanying drawing 2-1 and accompanying drawing 2-2.

The geological and mineral foundation of scandium technology is refined in a, design

Contain R in all kinds of ores in Inner Mongol niobium-rare-earth-iron mineral deposit ₂O ₃About 1.92-9.78%, contain Sc ₂O ₃About 0.006-0.016%.Mixed rare earth concentrate is based on monazite, hamartite, eschynite, and inferior is ilmenorutile, and other impure minerals are fluorite, rhombohedral iron ore, quartz, phosphatic rock etc.The Inner Mongol monazite contains Sc ₂O ₃Abundance is 0.024%, and monazite concentrate Sc has been adopted in the world ₂O ₃Content is roughly 0.005% (25, P23), and the former is 4.8 times of the latter.The Sc of hamartite, eschynite, ilmenorutile ₂O ₃Content is respectively 0.047%, 0.023%, 0.154% (16, P108-112).The mixed rare earth concentrate grade, R ₂O ₃53.2-59.4%, average 56.3%; ThO ₂0.15-0.16%; Fe 7.5% (13, P19).The mixed rare earth concentrate in this mineral deposit is not done the analysis of scandium, now estimates as follows:

If the rare earth oxide total reserves is 8,000 ten thousand tons in the iron ore of mineral deposit, mixed rare earth concentrates average T R ₂O ₃Be 56.3%, monazite accounts for 35% in the mixed rare earth concentrates, and hamartite accounts for 65%, then:

Mineral total reserves=8,000 ten thousand ton ÷ 56.3%=14210 ton;

Ten thousand tons of monazite reserves=14,210 ten thousand ton * 35%=4973.5;

Ten thousand tons of hamartite reserves=14,210 ten thousand ton * 65%=9236.5;

Sc2O in the monazite ₃Reserves=4973.5 ten thousand ton * 0.024%

=11936.4 tons;

Sc in the hamartite ₂O ₃Reserves=9236.5 ten thousand ton * 0.047%

=43411.6 tons;

Sc in the concentrate ₂O ₃Reserves=11936.4 ton+43411.6 tons=55348 tons;

Sc2O in the concentrate ₃Grade=55348 ton+14,210 ten thousand tons=0.039%;

Sc2O in the concentrate ₃Partition=0.039 ÷ 56.339=0.069%;

TR in the concentrate per ton ₂O ₃Be worth=56.3% * 14 yuan=7882 yuan;

Sc2O in the concentrate per ton ₃Be worth=0.039% * 4396 yuan=1714 yuan;

Be worth ratio=Sc2O ₃1714 yuan of ÷ TR ₂O ₃7882 yuan=21.75%; Be Sc2O in the mixed rare earth concentrates ₃Value is TR ₂O ₃21.75% of value.

Illustrate thus this rare-earth mineral not only association scandium, and content is also quite high, contains Sc with general wolframite ₂O ₃Grade is close, answers tool comprehensively to extract value.Here it is, and the main foundation of scandium scheme is put forward in this ore deposit.

Concentrate is decomposed in b, sulfurization roasting

Data (13, P16-18) report:

Concentrated sulfuric acid roasting, in 300 °-350 ℃ of temperature various mineral and effect of sulfuric acid and decompose down, the rate of decomposition of rare-earth mineral reaches more than 95%.

The decomposition of hamartite:

The decomposition of monazite:

The decomposition of fluorite:

The reaction of iron mineral:

The phosphoric acid generation dehydration reaction that reaction process generates:

The roasting result generates vitriol such as rare earth soluble in water, thorium, iron and manganese, water-fast calcium sulfate and barium sulfate.Phosphoric acid, hydrogen fluoride, sulfuric acid water vapour are discharged with tail gas, and the undecomposed rare-earth mineral of minute quantity still is present in (13, P18) in the reactant.Because of in fact monazite and hamartite all contain Sc ₂O ₃, and its occurrence status should belong to class matter homophase, so certainly lead to Sc2(SO after the roasting ₄) ₃, its reaction is:

In monazite:

In hamartite:

C, water extraction mother liquor:

Above product of roasting water leaches, and soluble substance and insoluble material separately, obtains containing the sulfate liquor of impurity such as rare earth and iron, manganese, phosphorus after solid-liquid separation.The leaching yield of rare earth is 98% (13, P18).Decomposed solution roughly consists of RxOy 30-50 grams per liter, ThO ₂1.2-2 grams per liter, Fe ³⁺11-18 grams per liter and PO ^3- ₄Deng, the about 0.5-1.5nH of free acid ₂SO ₄(16, P519).As for Sc2O ₃Concentration, according to concentrate R ₂O ₃Grade (56.3%) is greater than Sc2O ₃The situation that grade is (0.039%) 1444 times is calculated to should be the 0.021-0.035 grams per liter.

D, technological principle and processing condition

Because of the Inner Mongol mixed rare earth concentrates adds the mother liquor iron content height that concentrated sulfuric acid roasting makes the mineral decomposition and becomes with water enchroachment (invasion), and one of key issue of extracting mishmetal with primary amine be rare earth with iron separate (21, P14), so utilize primary amine (N116 or N1923) to thorium, the easiest extraction of scandium and to the iron characteristic of difficult extraction, design pushes raffinate with iron, and thorium, scandium are extracted into organic phase, again with the sodium carbonate solution back extraction, make it to enter in the strip liquor with thorium, scandium carbonate form, and precipitate and with Rare Earth Separation and enrichment.Boil then, make wherein thorium carbonate dissolving, get back to original solution; Scandium carbonate does not dissolve, through clarification, filtration, roasting it, promptly get the Scium trioxide product.Promptly precipitate after the liquid cooling but after the post precipitation and separate out thorium carbonate, can contain the Thorotrast product of ThO2 95% after the roasting.This stage is the optimal state that scandium enters and reclaims, and contains the not high Thorotrast of ThO2 purity yet only reclaim in the past, misses the recovery Scium trioxide.If not so, then in the concentrate contained scandium again to where having gone? the major cause of scandium is missed in judgement in view of the above, promptly is not know to have scandium to exist wherein, consequently throw out is completely calculated to be thorium carbonate, and scandium carbonate is sneaked in 5% impurity scope.So promptly reduce the purity of ThO2 in the Thorotrast, also buried the Scium trioxide product.The primary amine raffinate is with iron reduction Fe ³⁺Be Fe ²⁺After, because of P204 does not extract Fe ²⁺, use P204(P507 again) and fish for rare earth and the grouping of substep back extraction carrying out rare earth, and can be again with one step of naphthenic acid extraction process separation of oxygenated yttrium, scandium to the heavy rare earths group of being told.This programme technical process and processing condition are seen accompanying drawing 2-1 and accompanying drawing 2-2.

This programme has just added the flow process of refining scandium to some producer's original production flow process, need not to put in addition a lot of equipment, so should have big realistic meaning.

In addition, also has the sodium carbonate roasting method, promptly with Na2CO ₃Roasting rare earth concentrate makes it to be rare earth oxide; Soluble impurity is removed in water, dilute hydrochloric acid washing then, makes rare earth highly enriched in filter cake, leaches the mother liquor that obtains rare earth with dilute sulphuric acid; Through the sodium sulfate double salt precipitation, remove impurity such as most iron, phosphorus again.This double salt just can reach the purpose of preparation mixed rare earth chlorides product through technologies such as alkali conversion and hydrochloric acid optimum solvations.This chloride soln can be concentrated most solubility oxalic acid scandium through oxalic acid precipitation in the remaining fluid, add ammoniacal liquor and promptly become Sc(OH) ₃And precipitation reclaims.

(3) Inner Mongol mixed rare earth concentrate caustic soda leaching-extraction-precipitator method are refined the scandium process scheme

See accompanying drawing 3.

The geological and mineral foundation of scandium technology is refined in a, design:

Ditto described, be omitted herein.

B, caustic soda decompose concentrate:

Data (13, P21-22) report:

The alkali of monazite decomposes:

The alkali of hamartite decomposes:

The alkali of fluorite decomposes:

The alkali of iron ore decomposes:

Because of in fact monazite, hamartite all contain scandium, and occurrence form should be class matter homophase, so certainly lead to Sc(OH with the caustic soda decomposition) ₃Its reaction is:

In monazite:

In hamartite:

C, system alkali cake and hydrochloric acid are excellent molten:

Above-mentioned mineral decompose through caustic soda, produce rare earth, thorium, scandium, calcium precipitation of hydroxide, make the alkali cake after filtration; Excellent molten with hydrochloric acid again, make it to become muriate and enter solution, and as the mother liquor that decomposes single rare earth.Reaction is:

Excellent molten slag is molten entirely with sulfuric acid, makes thorium, scandium, calcium and part rare-earth hydroxide change vitriol into,

That is:

Filter out the calcium sulfate precipitation thing, the i.e. conduct of remaining fluid is the mother liquor of rare-earth separating, thorium, scandium further.

The recovery of d, primary amine, naphthenic acid, P507 extraction and finished product:

Because iron content is higher in the mother liquor, the characteristic of the most difficult extraction iron makes most thorium and scandium enter organic phase so utilize the easiest extraction thorium of primary amine (N1923), scandium, makes most rare earth and iron enter raffinate.Earlier with 0.06-0.08nHNO ₃Back extraction makes rare earth and iron enter strip liquor and as the feed liquid of naphthenic acid extracting rare-earth and the grouping of P507 rare earth; Again with 0.4-0.6nHNO ₃Back extraction makes thorium, scandium enter raffinate with the nitrate form, through being concentrated in 1.24nHNO ₃, 118 ℃, thorium nitrate 99.99004323A8urity (Th(NO is separated out in crystallization during degree Beaume=75 °-76 ° ₃) ₄5.2H ₂O) (21, P13; 16, P514), promptly get the Scium trioxide product after the roasting, react and be:

Scium trinitrate is littler than thorium nitrate 99.99004323A8urity because of solubleness,, can continue this moment to concentrate its crystalline substance is gone out, and roasting is the Scium trioxide product in the liquid so stay after the thorium nitrate 99.99004323A8urity post precipitation.Because of some chemical property and the thorium of scandium are close, the scandium that former concentrate contains another and thorium enter feed liquid, and primary amine extraction thorium and scandium ability be bordering on equally, so this flow process is optimal state equally concerning scandium, certainly will accompany with thorium.But owing to reckon without this stage the existence of scandium was arranged in the past, and do not consider the Scium trinitrate crystallization condition, and excessively concentrated, so that both are mixed mutually, and Scium trinitrate is treated as the impurity of thorium nitrate 99.99004323A8urity product, also prediction examination, so that buried it; Perhaps it when crystallization is not separated out as yet, just with its with tail washings Abandoned it, wasted the scandium resource.As for the raffinate and the excellent molten solution of hydrochloric acid of primary amine (N1923), available P507 does the grouping of rare earth.Technical process of this programme and processing condition are seen accompanying drawing 3.

This programme has just been done a little modifications and has been added the flow process of refining scandium some rare earth producer original production flow process, need not to increase separately equipment, so should have bigger feasibility.

(4) the molten cake hydrochloric acid of solitary crystal soda leaching-extraction-precipitator method are refined the scandium process scheme

See accompanying drawing 4.

According to document, world's selecting and purchasing goes out Sc2O in the monazite concentrate ₃Roughly content is 50 gram/tons (0.005%) (25, P23), and monazite contains R ₂O ₃Average 65.13% (16, P67) can estimate in this monazite 16 rare earth elements when making full partition, Sc2O in view of the above ₃Partition be 0.008%.If by being worth relatively, it is 2.4% of mixed rare earth oxide that Scium trioxide is worth.Therefore, can slightly disregard fully contained scandium.If but consider and contain Sc2O ₃The phosphorite of 10 gram/tons, contain Sc2O ₃The bauxite of 50 gram/tons, contain Sc2O ₃They can be used as main scandium resource the ilmenite of 60 gram/tons, then contain Sc2O ₃Why not the monazite of 50 gram/tons classifies the scandium resource again as is considered! In addition monazite refines method, technical process and the equipment and a lot of identical places of having of refinement scandium of rare earth and thorium, and often enter some flow process simultaneously at monazite refinement rare earth process middle-weight rare earths and scandium, so only need flow process and equipment are adjusted a little, can reclaim in passing scandium, what also increase a little wealth, and are always much better than wasting.In other words, if the scandium in the monazite can not or be unworthy comprehensive reutilization, what then the scandium resource in ilmenite, bauxite, the phosphorite certainly will be same can not or be unworthy comprehensive reutilization.Like this, the exhausted major part of world's scandium prospective reserves also just can not or be unworthy comprehensive reutilization, and can consider in the just only remaining wolframite of the scandium resource utilized 360 tons, cassiterite 850 tons to have amounted to 1210 tons.Obviously this is not all right, therefore, must consider the comprehensive problem that reclaims scandium in rare-earth minerals such as these mineral and monazite., propose " the molten cake hydrochloric acid of solitary crystal soda leaching-extraction-precipitation method of extract scandium " herein for this reason, see accompanying drawing 4.This scheme is former to be the technical process (16 that monazite refines rare earth and thorium, P509), only utilize when P350 extracts, scandium and thorium must be extracted and with the dilute hydrochloric acid back extraction in strip liquor, and scandium and thorium must change the favourable condition of raffinate again over to when extracting with TBP again, and make scandium obtain separating and enrichment, and then to add alkaline solution commentariess on classics degree be thorium carbonate, scandium carbonate, and promptly get Scium trioxide and Thorotrast product with the processing of coctoprecipitinogen method.So on Processes and apparatus, increase seldom, but the possibility effect is better, has certain economic benefit.To this stage, owing to do not recognized the existence of scandium, gone in the thorium product, so that not only reduced the purity of thorium product, and buried the scandium resource in the past and it may be sneaked into; Also may after reclaiming thorium, scandium have been emitted with tail washings.

To evaluation of the present invention: precedingly address, the world produced only 60 kilograms of scandium amounts in 1980, and perhaps the annual production of scandium from now on will reach the needs that several kilotons could satisfy world market; But association scandium reserves are just 1210 tons in present world tungsten, the tin ore.This means, will be several ten thousand times of 1980 annual production to the needs of scandium in the future, and for this reason must could adapting to very fast tempo production, yet association scandium reserves will extract fully in tungsten, the tin ore even will have now, also only can satisfy the need in 1 year at that time.This shows that the old way of refining scandium now from tungsten, tin ore obviously is may not solve this contradiction, must find a way out in addition, sets up in a wide range the scandium source.From rare-earth mineral, refine scandium, be extremely abundant aspect Mineral resources, more important person is that scandium, rare earth can reclaim simultaneously with a set of equipment, technical process and equipment are not too complicated, having built rare-earth smelting factory can use off-the-shelf equipment to refine scandium, use the also few and easy purchase price facility of chemical feedstocks, investment is little, and economic benefit may be better.Therefore, refining scandium from rare-earth mineral should be coming industry, and it not only can open up the frontier of refining scandium, and may be the optimal path that solves " a large amount of, the cheap scandium that refines fast, " problem.Present design, test the relevant documents in aspect such as analysis and rare earth metallurgy with reference to some geology, chemistry, rock mineralising although be, and therefrom filter out available part and design, be valid, may not have much problems aspect technical conceive and the ultimate principle; But be the feasible scheme design after all, do not do corresponding simulated experiment, without practice test, lack concrete processing condition data, so before relevant department's enforcement from now on, fill this class as far as possible, so that improper among the design and weak point are revised, replenished and adjust, perfect to attain.

This specification sheets is accompanying drawing 8 width of cloth altogether, and it is described as follows:

1, residue, mixed rare-earth oxide and salt leaching-extraction after ion adsorption type rare earth ore stone of the present invention, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite-precipitator method are refined scandium process design figure, originally can make a width of cloth figure draws, but because of map sheet is limit, and do independent its branch and associated 4 width of cloth, wherein:

Fig. 1-the 1st, scandium mother liquor process design figure is refined in residue, mixed rare-earth oxide and salt preparation after ion adsorption type rare earth ore stone, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite;

Fig. 1-2 is that the precipitator method of carrying the scandium mother liquor of residue after ion adsorption type rare earth ore stone, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite, mixed rare-earth oxide and salt preparation are refined scandium process design figure;

Fig. 1-the 3rd, the extraction of the carrying the scandium mother liquor-precipitator method of residue, mixed rare-earth oxide and salt preparation are refined in the scandium technology and are mainly carried the scandium process design drawing after ion adsorption type rare earth ore stone, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite;

Fig. 1-the 4th, the extraction of the carrying the scandium mother liquor-precipitator method of residue, mixed rare-earth oxide and salt preparation are refined the less important scandium process design drawing of carrying in the scandium technology after ion adsorption type rare earth ore stone, rich scandium subsiliceous rock saprolite, the aluminium metallurgy of rich scandium bauxite;

2, scandium process design figure is refined in the Inner Mongol mixed rare earth concentrate sulfurization roasting-leaching of the present invention-extraction-precipitator method, can make a width of cloth figure originally and draw, but limit because of map sheet, makes the independence and associated 2 width of cloth and it is divided, wherein:

Fig. 2-the 1st, Inner Mongol mixed rare earth concentrate sulfurization roasting-leaching-extraction-precipitator method are refined in the scandium technology and are mainly carried the scandium process design drawing;

Fig. 2-the 2nd, Inner Mongol mixed rare earth concentrate sulfurization roasting-leaching-extraction-precipitator method are refined the less important scandium process design drawing of carrying in the scandium technology;

3, Fig. 3 is that Inner Mongol mixed rare earth concentrate caustic soda leaching-extraction-precipitator method are refined scandium process design figure;

4, Fig. 4 is that the molten cake hydrochloric acid of solitary crystal soda leaching-extraction-precipitator method are refined scandium process design figure.

The main reference document

(1) China Geological Univ geochemistry teaching and research room, 1979, geochemistry.The Geology Publishing House.

(2) Luan Shiwei, Fang Yaokui, Chen Shangdi, Wang Anguang, 1981, rare earth element geochemistry.Ministry of Geology rare mineral geology training class and Guangdong Province geology bureau seal.

(3) Guo Chengji, 1965, the rare element mineral chemistry.Science Press.

(4) Zhang Housheng translates, and 1977, scandium in Iceland's volcanics and yttrium.External total the 6th phase of geology bibliography.

(5) Guo Yongquan translates, and 1981, the reactivity of grouan alteration process middle-weight rare earths element.External geology bibliography rare earth geochemistry special edition.

(6) Zhang Taoshi, 1978, opinion contains the scandium mineral deposit.Geological and mineral research, 1978 the 3rd phases.

(7) Jiangxi 909 geology sections of geologic prospecting party, 1978, somewhere, Jiangxi volcanics weathering crust ion adsorption type cerium family rare earth mineral deposit geologic feature.Geological information (internal reference material), 1978 the 3rd phases, Jiangxi 909 geologic prospecting party's geological information groups are published.

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(10) Chen Deqian arrangement, 1981, the price recently of various rare metal products.Geological science and technology is dynamic, o. 11th in 1981.

(11) (breast) Bei Lafeigelaxi work, Liu Pikun translates, logic.Life reading new knowledge joint publishing publication.

(12) OA Song Qinna work, Tang's silks inscription, lijin are swelled and are translated rare metal.Higher Education Publishing House, 1958.

(13) Liu Yujiu compiles, rare metal knowledge " rare earth ".Metallurgical industry press 1983.

(14) Li Jiucheng work, opinion is looked for the scandium ore deposit with regard to rare-earth mineral.Guangdong Province rare earth association nineteen eighty-three rare-earth smelting is analyzed the symposium AC material; " Guangdong geological science and technology " first phase in 1985.

(15) Li Jiucheng work, the discovery and the meaning pre-test thereof of Guangdong Ren Ju rare-earth mineral association scandium element, 756 geology groups of Guangdong Province geology and minerals bureau print, and make the science that Guangdong Province geology and minerals bureau holds in December, 1984 and can hand over material.

(16) " rare earth " write group and write the rare earth first volume.Metallurgical industry press, 1978.

(17) " rare earth " write group and write the rare earth volume two.Metallurgical industry press 1978.

(18) the rare earth elemental analysis chemistry is write by department of chemistry of Wuhan University etc.Science Press, 1983.

(19) rock mineral analysis.The Geology Publishing House.

(20) the modest work that waits of the Li De of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences is in the rare earth chemistry collection of thesis " with the research of P507 extracting and separating rear earth element, cerium, scandium and thorium ".Science Press 1982.

(21) the modest work that waits of the Li De of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences is in the rare earth chemistry collection of thesis " with primary amine extracting and separating thorium and extraction mishmetal from baotite concentrated sulfuric acid roasting infusion ".Science Press 1982.

(22) Fu Yingzhu, the upper and lower volume of university general chemistry.People's Education Publishing House 1979.

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Claims (6)

1, the invention belongs to technical field of non-ferrous metallurgy.Scandium is to extract with the precipitator method from wolframite, cassiterite and uranothorite metallurgical slag at present, and is irrelevant with the present invention.Feature of the present invention is: utilize rare-earth mineral (to comprise the association rare-earth mineral; rich scandium subsiliceous rock saprolite; residue after the aluminium metallurgy of rich scandium bauxite; mixed rare-earth oxide; mixed rare earth chlorides) is raw material; select hydrochloric acid for use; sulfuric acid; ammonium chloride solution; ammoniumsulphate soln; scandium and rare earth mother solution are carried in the salt solution leaching; select naphthenic acid for use; P204; P507; P350; TBP; extraction process separation and concentration scandium and rare earths from mother liquor such as uncle's ammonium; select oxalic acid solution for use; ammonium oxalate solution; ammoniacal liquor; caustic soda soln; condensing crystal; the scandium carbonate thorium carbonate boils the precipitator method such as separation from mother liquor; raffinate; reclaim scandium and byproducts such as rare earth oxide or product salt and gallium in the strip liquor, so rare-earth mineral is refined the scope that the scandium genus is asked for protection.

2, according to claim 1; it is characterized in that with residue or mixed rare-earth oxide or mixed rare earth chlorides after ion adsorption type rare earth ore or rich scandium subsiliceous rock saprolite or the bauxite aluminium metallurgy be raw material; select for use leachings such as ammonium chloride solution, ammoniumsulphate soln, salt solution, hydrochloric acid, water to carry the scandium mother liquor; from mother liquor, reclaim scandium and rare earth oxide or product salt with methods such as oxalic acid solution, ammonium oxalate solution, ammoniacal liquor, caustic soda soln, condensing crystals, belong to the scope of asking for protection so refine scandium with above-mentioned raw materials and method.

3; according to claim 1; it is characterized in that with ion adsorption type rare earth ore; or rich scandium subsiliceous rock saprolite; or residue after the bauxite aluminium metallurgy; or mixed rare-earth oxide; or mixed rare earth chlorides is a raw material; select ammonium chloride solution for use; ammoniumsulphate soln; salt solution; hydrochloric acid; the scandium mother liquor is carried in leachings such as water; with one step of naphthenic acid extraction process and P507 or P204 extraction process separation and concentration scandium and rare earth; use oxalic acid solution; ammoniacal liquor or caustic soda soln; the precipitator method such as condensing crystal are from raffinate; reclaim scandium and rare earth oxide or chloride product in the strip liquor, belong to the scope of asking for protection so refine scandium with above raw material and method.

4, according to claim 1; it is characterized in that with the Inner Mongol mixed rare earth concentrate be raw material; add sulfuric acid baking; with the water extraction mother liquor, with primary amine extraction process separation and concentration scandium and rare earth, with the alkaline solution back extraction; make scandium carbonate precipitation recovery in the strip liquor to boil partition method; make thorium carbonate enter surplus liquid, and the recovery of cooling precipitation, the scope of asking for protection belonged to so refine scandium with above-mentioned raw materials and method.

5, according to claim 1, it is characterized in that with the Inner Mongol mixed rare earth concentrate be raw material, add soda boiling and make it to decompose and make the alkali cake, with the excellent molten alkali cake of hydrochloric acid, solution is done the grouping of P507 rare earth, excellent molten slag is carried the scandium mother liquor with complete molten the making of sulfuric acid,, utilize 0.06-0.08nHNO again with primary amine extracting scandium, thorium and rare earth ₃The back extraction rare earth is with 0.4-0.6nHNO ₃Back extraction scandium and thorium are in strip liquor, and heating concentrates, at 1.24nHNO ₃, crystalline deposit goes out the thorium nitrate 99.99004323A8urity product when 118 ℃, degree Beaume=75 °-76 °, the liquid condensing crystal gets Scium trinitrate after the post precipitation, after the roasting the Scium trioxide product, so refine the scope that the scandium genus is asked for protection with above-mentioned raw materials and method.

6, according to claim 1, it is characterized in that with the alkali cake of being made by monazite be raw material, invade with hydrochloric acid and make mother liquor; with P350 extracting scandium and thorium; with the hydrochloric acid back extraction, make it enter strip liquor, extract with TBP again; make it enter raffinate; go out scandium carbonate and thorium carbonate with alkali solution precipitate, boil and make thorium carbonate dissolved and leach, insoluble residue is scandium carbonate; just get the Scium trioxide product through roasting, belong to the scope of asking for protection so refine scandium with above-mentioned raw materials and method.

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