CN109112293A - A method of the selective enrichment scandium from Bayer process red mud - Google Patents
A method of the selective enrichment scandium from Bayer process red mud Download PDFInfo
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Abstract
The method of the invention discloses a kind of from Bayer process red mud selective enrichment scandium, using Bayer process red mud as raw material, suitable quantity of water, which is added, is sufficiently humidified so as to red mud, make red mud sulfation with the concentrated sulfuric acid, then it is roasted at high temperature, by the ground carry out mechanical activation of solid roasting product, then level Four water logging and washing are carried out, obtains rich scandium leachate, rich scandium washing lotion and low alkali richness scum.This method leaches scandium largely, and impurity iron and aluminium leaching rate are low, and silicon and titanium-based originally do not leach, and avoid the formation of siliceous colloid in leachate, are conducive to the selective absorption and extraction of scandium in subsequent leachate；The sulfur dioxide and sulfur trioxide of generation, which can be back to, prepares sulfuric acid recycling, avoids the generation of a large amount of spent acid；The pH of low alkali richness scum can be used for smelting iron, the industries such as adsorbent, ceramics, building, provide one kind new approach for the extraction of scandium and the comprehensive utilization of red mud close to neutrality.
Description
Technical field
The invention belongs to solid waste comprehensive utilization and mineral resource processing technical fields, and in particular to a kind of from Bayer
The method of selective enrichment scandium in method red mud.
Background technique
Scandium is a kind of important strategic resource, is widely used in the high-tech such as optics, electronics, aviation, automobile, superconduction neck
Domain.Scandium belongs to association rare and scatter element, in nature without independent mineral deposit, mainly from produce other metals for example rare earth, aluminium,
It is recycled in the low alkali richness scum of titanium, tungsten, magnesium etc., tailing and waste liquid as byproduct.
Red mud is generation alkali solid waste residue during bauxite into alumina.It is estimated that every 1 ton of aluminium oxide of production produces
Raw 1-1.5 tons of red muds.Annual in the world probably to generate 1.5 hundred million tons of red muds, the red mud in China adds up volume of cargo in storage more than 500,000,000 at present
Ton.Red mud is hoarded on soil after dehydration as a kind of industrial residue, can not only occupy a large amount of land area, high alkalinity
It causes to seriously endanger to ambient enviroment with content dusty, therefore, effectively a large amount of reasonable utilization red muds have become global oxidation
The urgent need to solve the problem of aluminium industry.Red mud is a kind of available secondary resource, closely rich in elements such as scandium, iron, titanium, rare earths
Scandium is mentioned in Nian Laicong red mud has become one of red mud comprehensive utilizating research hot spot.
Chinese patent CN1844421A discloses a kind of method of Extracting Scandium from Red Mud, is generated with bauxite into alumina red
Mud is raw material, is stripped using salt Ore Leaching, P2O4 extraction, pickling impurity removal, sodium hydroxide, adds ammonia water modifier water after dissolving with hydrochloric acid
The techniques such as the heavy scandium of titanium zirconium, oxalic acid and medium temperature calcining are released, the scandium oxide that purity is 99.9% is obtained.Chinese patent CN
105331837A discloses a kind of method of scandium-enriched from red mud, using the red mud of bauxite into alumina generation as raw material,
By the way that additive agglomeration-reduction roasting-iron removal by magnetic separation is added, phosphoric acid leaching removes silicon, sodium hydroxide solution is leached after removing aluminium and obtained
Filter residue containing scandium, the overall recovery of scandium is up to 90% or more.Chinese patent CN106086436A discloses one kind from Bayer process red mud
The method of Selectively leaching scandium and sodium, is mixed using the concentrated sulfuric acid, after low temperature sulfation, then carries out medium temperature roast, water logging obtains
The low iron washing lotion of rich scandium sodium.
But there are still some problems for the recycling of scandium in red mud: (1) most of extracting method is all using direct at present
Acidleach handles red mud, and silicon largely dissolves out in red mud during direct acidleach, forms silica gel, cause to be separated by solid-liquid separation it is difficult, and
Silicone content is excessively high in solution, and when extracting scandium is also easy to produce a large amount of emulsion, keeps organic phase separation difficult, increases the difficulty of subsequent technique
Degree.(2) iron content is higher in red mud, the recycling of the common influence of extraction scandium of iron, such as carries out separation and culture to iron in red mud, existing
There is process route complex, energy consumption is higher, and the consumption of soda acid is larger, increases the cost of processing.(3) existing processing side
Formula is after extracting valuable metal in red mud, since other compositions remain in slag in red mud, still have a large amount of waste residues to be discharged, by
Alkaline scrap material originally becomes acid waste residue, and without fundamentally solving the problems, such as waste residue mass storage, and acid is not recyclable again
It utilizes, generates a large amount of spent acid, cause the pollution to underground water and the destruction of environment.
Summary of the invention
In view of the above shortcomings of the prior art, the present invention provides a kind of side of selective enrichment scandium from Bayer process red mud
Method.The Selective Separation of scandium and silicon, iron, aluminium, titanium may be implemented in this method, can scandium in efficiently concentrating Bayer process red mud, mention
The concentration of scandium in the leaching rate and leachate of high scandium, is conducive to the selective absorption and extraction of scandium in subsequent leachate, and rich scandium is washed
The recycling of liquid further improves the overall recovery of scandium, and the sulfur dioxide and sulfur trioxide of generation, which are back to, prepares concentrated sulfuric acid circulation
It uses, avoids the generation of a large amount of spent acid, low alkali richness scum can be applied to the row such as ironmaking, adsorbent, ceramics, building close to neutrality
Industry realizes the zero-emission of red mud, meets the requirement of environmental protection with sustainable development.
The present invention solves above-mentioned technical problem, the technical solution adopted is as follows:
A method of the selective enrichment scandium from Bayer process red mud, using Bayer process red mud as raw material, suitable quantity of water, which is added, to be made
Red mud is sufficiently humidified so as to, and is made red mud sulfation with the concentrated sulfuric acid, is then roasted at high temperature, and solid roasting product is ground
Mechanical activation is carried out, then carries out level Four water logging and washing, obtains rich scandium leachate, rich scandium washing lotion and low alkali richness scum.
The above method, comprising the following steps:
S1. suitable quantity of water is added into Bayer process red mud is sufficiently humidified so as to red mud；
S2. the concentrated sulfuric acid that mass fraction is 95%~98% is added in the obtained slurry of step S1 carry out it is heat aging,
Make red mud sulfation, curing temperature is 80~150 DEG C, and the curing time is 20~60min；
S3. red mud sulfation product step S2 obtained carries out high-temperature roasting, obtains solid roasting product and generates
Sulfur dioxide and sulfur trioxide；Roasting condition are as follows: maturing temperature is 800~850 DEG C, and calcining time is 20~75min；
S4. the solid roasting product that step S3 is obtained being fully ground carry out mechanical activation, milling time is 10~
40min；
S5. the solid roasting product after step S4 mechanical activation is subjected to selective water logging, leaching condition are as follows: reaction temperature
It is 25~95 DEG C, the reaction time is 15~90min, and mixing speed is 200~600r/min, and the ratio of water and red mud is 4~12:
1mL/g；Gained leaching slurry is separated by solid-liquid separation, leached mud and level-one richness scandium leachate are obtained；Water is added into leached mud
It is washed, agitated, filtering obtains level-one richness scandium washing lotion and low alkali richness scum；
S6. the level-one richness scandium leachate obtained using step S5 carries out the solid roasting product after step S4 mechanical activation
It leaches, leaching condition is identical as the leaching condition of step S5, and the loss of water is supplemented by equivalent amount of water in leaching process, then using step
The level-one richness scandium washing lotion that rapid S5 is obtained washes leached mud, and the loss of water is supplemented by equivalent amount of water in water-washing process；It obtains
Second level richness scandium leachate and second level richness scandium washing lotion repetitive operation；Obtained three-level richness scandium leachate and three-level richness scandium washing lotion repeats to grasp
Make；Obtain level Four richness scandium leachate, level Four richness scandium washing lotion and low alkali richness scum.
Preferably, in the step S1 partial size of Bayer process red mud less than 74 μm.
Preferably, the ratio of water and red mud is 0.4~0.8mL/g in the step S1.
Preferably, in the step S2 concentrated sulfuric acid additional amount in the ratio of the concentrated sulfuric acid and red mud be 0.75~1.50mL/
g。
Preferably, the washing in the step S5 is 4~8mL/g in the ratio of water and red mud.
Preferably, the sulfur dioxide and sulfur trioxide that the step S3 is generated are back to dense sulphur used in preparation step S2
Acid.
Preferably, the level Four richness scandium leachate and level Four richness scandium washing lotion that the step S6 is obtained be used as scandium selective absorption and
The low alkali richness scum that the raw material of extraction, step S5 and step S6 are obtained is used as the raw material of ironmaking.
Technical principle of the invention is as follows:
When directly leaching red mud using sulfuric acid, scandium, iron, aluminium, titanium and sulfuric acid in red mud mineral react, and obtain
Ammonium acetate is complicated, increases the difficulty of scandium absorption or extraction in subsequent leachate, and generate a large amount of spent acid, makes to equipment
At heavy corrosion, spent acid is non-recyclable and reusable.More most of all, element silicon is in cancrinite phase directly in acidleach process red mud
In largely dissolution generate silicic acid H4SiO4, H in acid condition4SiO4With the H in solution+Ions binding generates H5SiO4 +,
H4SiO4With H5SiO4 +Following polymerization reaction occurs in the presence of water:
H3Am ++H2An→H3A+ m+n+2H2O
Wherein AmIt is expressed as [Sim(OH)4m+2]2-, AnIt is expressed as [Sin(OH)4n+2]2-
The silica gel that above-mentioned reaction is formed is suspended in solution, makes to be separated by solid-liquid separation difficult, silica gel package ore particles after leaching
Influence the leaching of scandium.In addition, the presence of silicon also has a huge impact the absorption and extraction of scandium in leachate, so in scandium
The leaching of silicon is avoided in removal process as far as possible.
Suitable water, which is added, before 95%~98% concentrated sulfuric acid is added is sufficiently humidified so as to red mud, mixes the concentrated sulfuric acid and red mud
Must be more uniform, sulfuric acid slaking reaction is more complete, and the leaching rate of scandium during water logging can be improved, and reduces making for sulfuric acid
With.Each essential element is all converted to corresponding sulfate in maturing process in red mud, and reaction equation is as follows:
Na8Al6Si6O24(OH)2(H2O)2+13H2SO4→4Na2SO4+3Al2(SO4)3+6H4SiO4+4H2O
Fe2O3+3H2SO4→Fe2(SO4)3+3H2O
AlO(OH)+3H2SO4→Al2(SO4)3+3H2O
CaTiO3+2H2SO4→CaSO4+TiOSO4+2H2O
CaCO3+H2SO4→CaSO4+CO2↑+H2O
TiO2+H2SO4→TiOSO4+H2O
Sc2O3+3H2SO4→Sc2(SO4)3+3H2O
In high-temperature calcination process, as maturing temperature increases, unstable sulphate decomposition is corresponding oxide,
Following reaction occurs for 800~850 DEG C of next coming in order:
H4SiO4→SiO2+2H2O↑
TiOSO4→TiO2+SO3↑
Al2(SO4)3→Al2O3+3SO3↑
Fe2(SO4)3→Fe2O3+3SO3↑
In the case where maturing temperature is lower than 850 DEG C, scandium is with Sc2(SO4)3It is present in roasting sample, when maturing temperature is
At 800~850 DEG C, silicon, iron, aluminium and titanium sulphate decomposition after exist in the form of the oxide, calcium and sodium are with the shape of sulfate
Formula is retained in roasting sample.
It will be fully ground carry out mechanical activation after the roasting of red mud sulfation product, grinding can reduce particle size, increase
Its big specific surface area can carry out more fully ion exchange with the leachate of surrounding, to accelerate leaching process.
Level Four water logging and washing are carried out to the solid roasting product after mechanical activation, scandium and sodium enter in leachate, silicon,
Iron, aluminium and titanium mainly stay in leached mud in the form of the oxide, and most of calcium sulfate enters leached mud；Scandium is dense in level-one washing lotion
It spends low, cannot act as the absorption of next step, lead to the loss of scandium, the rate of recovery reduces, and level Four water logging and washing can recycle
The soluble scandium being adhered on leached mud, improves the concentration of scandium in leachate and washing lotion, and further scandium-enriched is conducive to subsequent scandium
Selective absorption and extraction, make adsorbent adsorption site and scandium ions binding probability increase, adsorption effect improve.If
It is further added by leaching series, although the concentration of scandium can increase again in leachate, because of the reasons such as change of pH value in leachate, four
Scandium concentration increase is no longer obvious in leachate after grade, and with the increase of scandium concentration in washing lotion, scandium loss increases, under overall recovery
Drop.Level Four water logging and washing have reached the concentration requirement of the selective absorption of scandium in subsequent leachate, have preferable absorption effect
Fruit, and scandium maintains the higher rate of recovery, level Four is optimal selection.
Since most sodium enter in leachate, so leached mud significantly weakens relative to former red mud alkalinity, connect
Weakly acidic pH, therefore can be using leached mud as the raw material of ironmaking, or it is applied to the industries such as adsorbent, ceramics, building.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention uses water-wet profit-sulfation-high-temperature roasting-mechanical activation-level Four water logging and washing process, leads to
Control roasting and leaching condition are crossed, scandium is dissolved out, and silicon, iron, titanium and aluminium stay in leached mud.It can be avoided silicon in leaching process
The formation and iron of glue, aluminium and titanium are to the interference of scandium selective absorption and extraction in leachate.Under level-one leaching and washing conditions,
The leaching rate of scandium is up to 85~92%, and the leaching rate of iron is lower than 0.5%, and the leaching rate of aluminium is lower than 10%, and titanium and silicon do not leach.Four
The adsorption rate of scandium reaches 98% or more in grade leachate and level Four washing lotion.
(2) suitable water be first added be sufficiently humidified so as to red mud before 95%~98% concentrated sulfuric acid is added, make the concentrated sulfuric acid and
Red mud mixes more uniform, and sulfuric acid slaking reaction is more complete, and the leaching rate of scandium during water logging can be improved, while reducing sulphur
The use of acid.
(3) it being fully ground carry out mechanical activation after the roasting of red mud sulfation product, grinding can reduce particle size,
Increase its specific surface area, scandium can be improved to accelerate leaching process with the leachate of surrounding progress more fully ion exchange
Leaching rate.
(4) level Four water logging and washing are used, level Four water logging and washing can recycle the soluble scandium being adhered on leached mud,
The concentration of scandium in leachate and washing lotion is improved, further scandium-enriched is conducive to the selective absorption and extraction of subsequent scandium, makes adsorbent
Adsorption site and scandium ions binding probability increase, adsorption effect improve.The concentration of scandium reaches in level Four grade richness scandium leachate
18mg/L or more, the concentration of scandium reaches 12mg/L or more in level Four richness scandium washing lotion, and overall recovery reaches 73% or more.The same terms
Under, using the adsorbent of equal quality number, in level Four richness scandium leachate scandium adsorbance be 2.5 times of level-one richness scandium leachate with
On, the adsorption rate of scandium reaches 98% or more in level Four richness scandium leachate and level Four richness scandium washing lotion.
(5) method and process process of the invention is short, and operation is simple, the SO generated in removal process2And SO3, sulphur may be implemented
The recycling of acid, save the cost avoid the generation of a large amount of spent acid and non-environmental-pollution, are expected to realize the big of Bayer process red mud
Scale resource utilization.
(6) present invention obtains rich scandium leachate and rich scandium washing lotion can be used as the original of subsequent scandium selective absorption and extraction
Material.Since most sodium enter in leachate, so leached mud significantly weakens relative to former red mud alkalinity, in
Property, it can be used as the raw material of ironmaking, or be applied to the industries such as adsorbent, ceramics, building.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
Use raw material for Bayer process red mud, main component and mass percentage are Fe in red mud2O326.70%, Al2O3
23.46%, CaO 14.66%, SiO211.09%, TiO25.75%, Na2O 5.41%, Sc 0.008%.
1. Bayer process red mud is dry, levigate to sub-sieve is crossed, obtain solid powder of the partial size less than 74 μm；By water with it is red
The ratio of mud is that 0.5mL/g addition water is sufficiently humidified so as to red mud；
2. being 1. slurry that 1.0mL/g is obtained to step in the ratio of the concentrated sulfuric acid (mass fraction 95-98%) and red mud
The middle addition concentrated sulfuric acid, cures 30min at 100 DEG C, makes red mud sulfation；
3. 2. red mud sulfating product that step is obtained carries out high-temperature roasting, roasting condition are as follows: 850 DEG C of maturing temperature,
Calcining time 60min；It obtains solid roasting product and generates sulfur dioxide and sulfur trioxide；
4. 3. solid roasting product that step obtains is fully ground carry out mechanical activation, milling time 30min；
5. the solid roasting product after mechanical activation is carried out selective water logging, leaching condition are as follows: reaction temperature is 60 DEG C,
Reaction time is 40min, mixing speed 400r/min, and the ratio of water and red mud is 8:1mL/g；Gained is leached slurry to carry out
It is separated by solid-liquid separation, obtains leached mud and level-one richness scandium leachate；It is that distillation is added into leached mud by 5mL/g in the ratio of water and red mud
Water is washed, and agitated, filtering obtains level-one richness scandium washing lotion and low alkali richness scum.
6. the level-one richness scandium leachate 5. obtained using step carries out the solid roasting product after step 4. mechanical activation
It leaches, leaching condition is identical as the leaching condition of step 5., and the loss of water is supplemented by equivalent amount of water in leaching process, makes leaching process
Middle liquid-solid ratio is consistent；Then, water is carried out using the leached mud that 5. level-one richness scandium washing lotion that step obtains leaches second
It washes, the loss of water is supplemented by equivalent amount of water in water-washing process, is consistent rich scandium washing lotion and the liquid-solid ratio of red mud in water-washing process；
Obtained second level richness scandium leachate and second level richness scandium washing lotion repeats above operation, obtained three-level richness scandium leachate and three-level richness scandium
Washing lotion repeats above operation；Obtain level Four richness scandium leachate, level Four richness scandium washing lotion and low alkali richness scum.
3. sulfur dioxide or sulfur trioxide that step generates is back to the preparation step 2. used concentrated sulfuric acid.
6. level Four richness scandium leachate and level Four richness scandium washing lotion that step obtains is used as the raw material of scandium selective absorption and extraction,
5. 6. low alkali richness scum that step is obtained with step can be used as the raw material of ironmaking close to neutrality.
Under level-one water logging and washing conditions, the leaching rate of scandium is 91.43%, and the leaching rate of iron is 0.3%, the leaching rate of aluminium
It is 6.22%, titanium is not leached with silicon, and the concentration of scandium is 9.63mg/L in level-one richness scandium leachate, and scandium is dense in level-one richness scandium washing lotion
Degree is 2.54mg/L, overall recovery 74.20%.
Under level Four water logging and washing conditions, the leaching rate of scandium is 80.22%, and the leaching rate of iron is 0.21%, the leaching of aluminium
Rate is 5.14%, and titanium is not leached with silicon, and the concentration of scandium is 26.02mg/L, scandium in level Four richness scandium washing lotion in level Four richness scandium leachate
Concentration be 14.35mg/L, overall recovery 75.22%.
Under the same terms, using the adsorbent of equal quality number, scandium adsorbance is level-one richness in level Four richness scandium leachate
The adsorption rate of scandium reaches 98% or more in 2.73 times of scandium leachate, level Four richness scandium leachate and level Four richness scandium washing lotion.
If being further added by leaching series, although the concentration of scandium can increase again in leachate, because of pH value in leachate
The reasons such as change, scandium concentration increase is no longer obvious in leachate after level Four, and with the increase of scandium concentration in washing lotion, scandium loss increases
It is more, overall recovery decline.Level Four water logging and washing have reached the concentration requirement of the selective absorption of scandium in subsequent leachate, have
Preferable adsorption effect, and scandium maintains the higher rate of recovery, level Four is optimal selection.
Embodiment 2
Use raw material for Bayer process red mud, main component and mass percentage are Fe in red mud2O326.70%, Al2O3
23.46%, CaO 14.66%, SiO211.09%, TiO25.75%, Na2O 5.41%, Sc 0.008%.
1. Bayer process red mud is dry, levigate to sub-sieve is crossed, obtain solid powder of the partial size less than 74 μm；By water with it is red
The ratio of mud is that 0.4mL/g addition water is sufficiently humidified so as to red mud；
2. being 1. slurry that 1.5mL/g is obtained to step in the ratio of the concentrated sulfuric acid (mass fraction 95-98%) and red mud
The middle addition concentrated sulfuric acid, cures 60min at 80 DEG C, makes red mud sulfation；
3. 2. red mud sulfating product that step is obtained carries out high-temperature roasting, roasting condition are as follows: 825 DEG C of maturing temperature,
Calcining time 20min；It obtains solid roasting product and generates sulfur dioxide and sulfur trioxide；
4. 3. solid roasting product that step obtains is fully ground carry out mechanical activation, milling time 40min；
5. the solid roasting product after mechanical activation is carried out selective water logging, leaching condition are as follows: reaction temperature is 25 DEG C,
Reaction time is 90min, mixing speed 200r/min, and the ratio of water and red mud is 4:1mL/g；Gained is leached slurry to carry out
It is separated by solid-liquid separation, obtains leached mud and level-one richness scandium leachate；It is that distillation is added into leached mud by 8mL/g in the ratio of water and red mud
Water is washed, and agitated, filtering obtains level-one richness scandium washing lotion and low alkali richness scum.
6. the level-one richness scandium leachate 5. obtained using step carries out the solid roasting product after step 4. mechanical activation
It leaches, leaching condition is identical as the leaching condition of step 5., and the loss of water is supplemented by equivalent amount of water in leaching process, makes leaching process
Middle liquid-solid ratio is consistent；Then, water is carried out using the leached mud that 5. level-one richness scandium washing lotion that step obtains leaches second
It washes, the loss of water is supplemented by equivalent amount of water in water-washing process, is consistent rich scandium washing lotion and the liquid-solid ratio of red mud in water-washing process；
Obtained second level richness scandium leachate and second level richness scandium washing lotion repeats above operation, obtained three-level richness scandium leachate and three-level richness scandium
Washing lotion repeats above operation；Obtain level Four richness scandium leachate, level Four richness scandium washing lotion and low alkali richness scum.
3. sulfur dioxide or sulfur trioxide that step generates is back to the preparation step 2. used concentrated sulfuric acid.
6. level Four richness scandium leachate that step obtains is used as the raw material of scandium selective absorption and extraction, step 5. with step 6.
Obtained low alkali richness scum can be used as the raw material of ironmaking close to neutrality.
Under level-one water logging and washing conditions, the leaching rate of scandium is 90.03%, and the leaching rate of iron is 0.47%, the leaching of aluminium
Rate is 7.62%, and titanium is not leached with silicon, and the concentration of scandium is 17.89mg/L, scandium in level-one richness scandium washing lotion in level-one richness scandium leachate
Concentration be 2.31mg/L, overall recovery 68.05%.
Under level Four water logging and washing conditions, the leaching rate of scandium is 78.32%, and the leaching rate of iron is 0.35%, the leaching of aluminium
Rate is 5.94%, and titanium is not leached with silicon, and the concentration of scandium is 45.22mg/L, scandium in level Four richness scandium washing lotion in level Four richness scandium leachate
Concentration be 12.08mg/L, overall recovery 73.31%.
Under the same terms, using the adsorbent of equal quality number, scandium adsorbance is level-one richness in level Four richness scandium leachate
The adsorption rate of scandium reaches 98% or more in 2.52 times of scandium leachate, level Four richness scandium leachate and level Four richness scandium washing lotion.
If being further added by leaching series, although the concentration of scandium can increase again in leachate, because of pH value in leachate
The reasons such as change, scandium concentration increase is no longer obvious in leachate after level Four, and with the increase of scandium concentration in washing lotion, scandium loss increases
It is more, overall recovery decline.Level Four water logging and washing have reached the concentration requirement of the selective absorption of scandium in subsequent leachate, have
Preferable adsorption effect, and scandium maintains the higher rate of recovery, level Four is optimal selection.
Embodiment 3
Use raw material for Bayer process red mud, main component and mass percentage are Fe in red mud2O326.70%, Al2O3
23.46%, CaO 14.66%, SiO211.09%, TiO25.75%, Na2O 5.41%, Sc 0.008%.
1. Bayer process red mud is dry, levigate to sub-sieve is crossed, obtain solid powder of the partial size less than 74 μm；By water with it is red
The ratio of mud is that 0.8mL/g addition water is sufficiently humidified so as to red mud；
2. being 1. slurry that 0.75mL/g is obtained to step in the ratio of the concentrated sulfuric acid (mass fraction 95-98%) and red mud
The middle addition concentrated sulfuric acid, cures 20min at 150 DEG C, makes red mud sulfation；
3. 2. red mud sulfating product that step is obtained carries out high-temperature roasting, roasting condition are as follows: 800 DEG C of maturing temperature,
Calcining time 75min；It obtains solid roasting product and generates sulfur dioxide and sulfur trioxide；
4. 3. solid roasting product that step obtains is fully ground carry out mechanical activation, milling time 10min；
5. the solid roasting product after mechanical activation is carried out selective water logging, leaching condition are as follows: reaction temperature is 95 DEG C,
Reaction time is 15min, mixing speed 600r/min, and the ratio of water and red mud is 12:1mL/g；By gained leach slurry into
Row is separated by solid-liquid separation, and obtains leached mud and level-one richness scandium leachate；It is that steaming is added into leached mud by 4mL/g in the ratio of water and red mud
Distilled water is washed, and agitated, filtering obtains level-one richness scandium washing lotion and low alkali richness scum.
6. the level-one richness scandium leachate 5. obtained using step carries out the solid roasting product after step 4. mechanical activation
It leaches, leaching condition is identical as the leaching condition of step 5., and the loss of water is supplemented by equivalent amount of water in leaching process, makes leaching process
Middle liquid-solid ratio is consistent；Then, water is carried out using the leached mud that 5. level-one richness scandium washing lotion that step obtains leaches second
It washes, the loss of water is supplemented by equivalent amount of water in water-washing process, is consistent rich scandium washing lotion and the liquid-solid ratio of red mud in water-washing process；
Obtained second level richness scandium leachate and second level richness scandium washing lotion repeats above operation, obtained three-level richness scandium leachate and three-level richness scandium
Washing lotion repeats above operation；Obtain level Four richness scandium leachate, level Four richness scandium washing lotion and low alkali richness scum.
3. sulfur dioxide or sulfur trioxide that step generates is back to the preparation step 2. used concentrated sulfuric acid.
6. level Four richness scandium leachate that step obtains is used as the raw material of scandium selective absorption and extraction, step 5. with step 6.
Obtained low alkali richness scum can be used as the raw material of ironmaking close to neutrality.
Under level-one water logging and washing conditions, the leaching rate of scandium is 88.93%, and the leaching rate of iron is 0.49%, the leaching of aluminium
Rate is 8.85%, and titanium is not leached with silicon, and the concentration of scandium is 6.55mg/L in level-one richness scandium leachate, scandium in level-one richness scandium washing lotion
Concentration is 2.67mg/L, overall recovery 75.18%.
Under level Four water logging and washing conditions, the leaching rate of scandium is 79.22%, and the leaching rate of iron is 0.37%, the leaching of aluminium
Rate is 7.15%, and titanium is not leached with silicon, and the concentration of scandium is 18.68mg/L, scandium in level Four richness scandium washing lotion in level Four richness scandium leachate
Concentration be 15.48mg/L, overall recovery 75.71%.
Under the same terms, using the adsorbent of equal quality number, scandium adsorbance is level-one richness in level Four richness scandium leachate
The adsorption rate of scandium reaches 98% or more in 2.79 times of scandium leachate, level Four richness scandium leachate and level Four richness scandium washing lotion.
If being further added by leaching series, although the concentration of scandium can increase again in leachate, because of pH value in leachate
The reasons such as change, scandium concentration increase is no longer obvious in leachate after level Four, and with the increase of scandium concentration in washing lotion, scandium loss increases
It is more, overall recovery decline.Level Four water logging and washing have reached the concentration requirement of the selective absorption of scandium in subsequent leachate, have
Preferable adsorption effect, and scandium maintains the higher rate of recovery, level Four is optimal selection.
Comparative example 1
Unlike the first embodiment, the roasting condition of step 3. are as follows: 875 DEG C of maturing temperature, calcining time 60min.Other
When process conditions are all identical, obtained result is as follows:
Under level-one water logging and washing conditions, the leaching rate of scandium is 10.93%, and the leaching rate of iron is 0.23%, the leaching of aluminium
Rate is 4.55%, and titanium is not leached with silicon, and the concentration of scandium is 1.55mg/L in level-one leachate, and the concentration of scandium is in level-one washing lotion
0.46mg/L, leachate and scandium concentration in washing lotion are too low, cannot act as the absorption of next step.
Under level Four water logging and washing conditions, the leaching rate of scandium is 8.12%, and the leaching rate of iron is 0.17%, the leaching rate of aluminium
It is 3.25%, titanium is not leached with silicon, and the concentration of scandium is 4.23mg/L in level Four leachate, and the concentration of scandium is in level Four washing lotion
1.55mg/L, level Four leachate and scandium concentration in level Four washing lotion are too low, cannot act as the absorption of next step.
Sc when maturing temperature is 875 DEG C, in sample2(SO4)3It is converted into Sc2O3, Sc2O3It is not readily dissolved in water, Wu Fa
Link is leached to leach.So maturing temperature should be controlled at 850 DEG C hereinafter, can control scandium just with Sc2(SO4)3Form be present in
Roast sample.
Comparative example 2
Unlike the first embodiment, the roasting condition of step 3. are as follows: 750 DEG C of maturing temperature, calcining time 60min.Other
When process conditions are all identical, obtained result is as follows:
Under level-one water logging and washing conditions, the leaching rate of scandium is 91.73%, and the leaching rate of iron is 26.74%, the leaching of aluminium
Rate is 39.26%, and the leaching rate of titanium is 8.71%, the leaching rate of silicon is 2.3%, and the concentration of scandium is in level-one richness scandium leachate
17.89mg/L.The concentration of titanium is 1660mg/L in level-one richness scandium washing lotion, is not able to achieve selective separation, impurity element is serious
Influence the absorption of next step scandium.
Al when maturing temperature is 750 DEG C, in sample2(SO4)3、Fe2(SO4)3Not yet it is fully converted to Al2O3、
Fe2O3, Al2(SO4)3、Fe2(SO4)3It is soluble easily in water.In leaching process, scandium has a higher leaching rate, but foreign metal iron, aluminium,
Titanium enters in leachate with scandium, is not able to achieve Selective Separation.
Comparative example 3
Unlike the first embodiment, step 1. in be added without water and be sufficiently humidified so as to red mud.Other process conditions are all identical
When, obtained result is as follows:
Under level-one water logging and washing conditions, the leaching rate of scandium is 67.11%, and the leaching rate of iron is 1.22%, the leaching of aluminium
Rate is 5.82%, and titanium is not leached with silicon, and the concentration of scandium is 7.02mg/L in level-one richness scandium leachate, scandium in level-one richness scandium washing lotion
Concentration is 1.89mg/L, overall recovery 52.5%.
Under level Four water logging and washing conditions, the leaching rate of scandium is 56.82%, and the leaching rate of iron is 0.97%, the leaching of aluminium
Rate is 4.77%, and titanium is not leached with silicon, and the concentration of scandium is 19.03mg/L, scandium in level Four richness scandium washing lotion in level Four richness scandium leachate
Concentration be 10.02mg/L, overall recovery 52.52%.
Under the same terms, using the adsorbent of equal quality number, scandium adsorbance is level-one richness in level Four richness scandium leachate
The adsorption rate of scandium reaches 98% or more in 2.71 times of scandium leachate, level Four richness scandium leachate and level Four richness scandium washing lotion.
It is sufficiently humidified so as to red mud due to not having water is first added, the concentrated sulfuric acid and red mud mixing are uneven, and agglomeration is serious, and sulfuric acid is ripe
Change reaction not exclusively, leads to the leaching rate of scandium, the concentration of scandium and the overall recovery of scandium are equal in the concentration, washing lotion of scandium in leachate
Decline.
Comparative example 4
Unlike the first embodiment, without " step 4.: by 3. solid roasting product that step obtains be fully ground into
Row mechanical activation, milling time 30min ", the solid roasting product for directly 3. obtaining step carry out selective water logging.Other
When process conditions are all identical, obtained result is as follows:
Under level-one water logging and washing conditions, the leaching rate of scandium is 69.21%, and the leaching rate of iron is 0.23%, the leaching of aluminium
Rate is 5.77%, and titanium is not leached with silicon, and the concentration of scandium is 7.42mg/L in level-one richness scandium leachate.Scandium in level-one richness scandium washing lotion
Concentration is 1.73mg/L, overall recovery 58.43%.
Under level Four water logging and washing conditions, the leaching rate of scandium is 60.12%, and the leaching rate of iron is 0.17%, the leaching of aluminium
Rate is 4.67%, and titanium is not leached with silicon, and the concentration of scandium is 20.08mg/L, scandium in level Four richness scandium washing lotion in level Four richness scandium leachate
Concentration be 11.92mg/L, overall recovery 57.72%.
Under the same terms, using the adsorbent of equal quality number, scandium adsorbance is level-one richness in level Four richness scandium leachate
The adsorption rate of scandium reaches 98% or more in 2.7 times of scandium leachate, level Four richness scandium leachate and level Four richness scandium washing lotion.
Due to not grinding to solid roasting product, the partial size of product is larger, and the leachate with surrounding cannot be abundant
Contact leads to the leaching rate of scandium, the concentration of scandium and the overall recovery of scandium decline in the concentration, washing lotion of scandium in leachate.
Claims (8)
1. a kind of method of the selective enrichment scandium from Bayer process red mud, which is characterized in that using Bayer process red mud as raw material, be added
Suitable quantity of water is sufficiently humidified so as to red mud, makes red mud sulfation with the concentrated sulfuric acid, is then roasted at high temperature, solid roasting is produced
The ground carry out mechanical activation of object, then level Four water logging and washing are carried out, obtain rich scandium leachate, rich scandium washing lotion and low alkali richness iron
Slag.
2. the method according to claim 1, wherein the following steps are included:
S1. suitable quantity of water is added into Bayer process red mud is sufficiently humidified so as to red mud；
S2. the concentrated sulfuric acid that mass fraction is 95%~98% is added in the obtained slurry of step S1 and carries out heat aging, made red
Mud sulfation, curing temperature are 80~150 DEG C, and the curing time is 20~60min；
S3. red mud sulfation product step S2 obtained carries out high-temperature roasting, obtains solid roasting product and generates dioxy
Change sulphur and sulfur trioxide；Roasting condition are as follows: maturing temperature is 800~850 DEG C, and calcining time is 20~75min；
S4. the solid roasting product that step S3 is obtained is fully ground carry out mechanical activation, milling time is 10~40min；
S5. the solid roasting product after step S4 mechanical activation is subjected to selective water logging, leaching condition are as follows: reaction temperature 25
~95 DEG C, the reaction time is 15~90min, and mixing speed is 200~600r/min, and the ratio of water and red mud is 4~12:1mL/
g；Gained leaching slurry is separated by solid-liquid separation, leached mud and level-one richness scandium leachate are obtained；Water is added into leached mud to carry out
Washing, agitated, filtering, obtains level-one richness scandium washing lotion and low alkali richness scum；
S6. the solid roasting product after step S4 mechanical activation is soaked using the level-one richness scandium leachate that step S5 is obtained
Out, leaching condition is identical as the leaching condition of step S5, and the loss of water is supplemented by equivalent amount of water in leaching process, then uses step
The level-one richness scandium washing lotion that S5 is obtained washes leached mud, and the loss of water is supplemented by equivalent amount of water in water-washing process；Two obtained
The rich scandium leachate of grade and second level richness scandium washing lotion repetitive operation；Obtained three-level richness scandium leachate and three-level richness scandium washing lotion repeats to grasp
Make；Obtain level Four richness scandium leachate, level Four richness scandium washing lotion and low alkali richness scum.
3. according to the method described in claim 2, it is characterized in that, the partial size of Bayer process red mud is less than 74 μ in the step S1
m。
4. according to the method described in claim 2, it is characterized in that, in the step S1 ratio of water and red mud be 0.4~
0.8mL/g。
5. according to the method described in claim 2, it is characterized in that, in the step S2 concentrated sulfuric acid additional amount by the concentrated sulfuric acid with
The ratio of red mud is 0.75~1.50mL/g.
6. according to the method described in claim 2, it is characterized in that, washing in the step S5, in the ratio of water and red mud
For 4~8mL/g.
7. according to the method described in claim 2, it is characterized in that, sulfur dioxide and sulfur trioxide that the step S3 is generated return
It is used to prepare the concentrated sulfuric acid used in step S2.
8. according to the method described in claim 2, it is characterized in that, level Four richness scandium leachate and level Four that the step S6 is obtained
Rich scandium washing lotion is used as the raw material of scandium selective absorption and extraction, and the low alkali richness scum that step S5 and step S6 are obtained is used as ironmaking
Raw material.
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| CN110331289A (en) * | 2019-07-02 | 2019-10-15 | 广西大学 | A method of recycling scandium and sodium sulphate from Bayer process red mud |
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