CN106868325A - A kind of method of scandium-enriched in hydrochloric acid leaching ilmenite production rich-titanium material flow - Google Patents
A kind of method of scandium-enriched in hydrochloric acid leaching ilmenite production rich-titanium material flow Download PDFInfo
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- CN106868325A CN106868325A CN201710057056.4A CN201710057056A CN106868325A CN 106868325 A CN106868325 A CN 106868325A CN 201710057056 A CN201710057056 A CN 201710057056A CN 106868325 A CN106868325 A CN 106868325A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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Abstract
The invention discloses the method for scandium-enriched in a kind of hydrochloric acid leaching ilmenite production rich-titanium material flow, belong to field of hydrometallurgy.Ferrotianium material obtains leachate through hydrochloric acid leaching, and leachate is concentrated into preconcentrator；Leachate after concentration is cooled down into cooling bath, then separates FeCl through filter2·4H2O is crystallized, and the cooling medium of cooling bath is the NaOH back washing agents that need to be preheated；Concentration leachate extractant Sc extraction after treatment, the cleaning solution prepared with regeneration hydrochloric acid purifies load organic phases, is stripped with hot NaOH solution, and rich scandium solids is obtained after separation of solid and liquid；Extraction lean solution and FeCl2·4H2O crystallizations return to the incinerator in rich-titanium material production procedure；Scrub raffinate returns to the first grade absorption tower of HCl recovery system.The various intermediate products that rationally make use of in hydrochloric acid leaching ilmenite production rich-titanium material flow of the invention, stripping process takes full advantage of the heat of concentration leachate, extraction lean solution and scrub raffinate return to rich-titanium material production procedure, with extremely low material cost, realize the zero-emission of pollutant.
Description
Technical field
The invention belongs to field of hydrometallurgy, and in particular to be enriched with a kind of hydrochloric acid leaching ilmenite production rich-titanium material flow
The method of scandium.
Background technology
Content of the scandium in the earth's crust is simultaneously many, but simply excessively disperses, and its Independent Mineral is rare, and reserves are small.Scandium master
It is present in the iron-magnesium mineral of basic rock and ultrabasic rock, Sc2O3Content is generally 5 × 10-4-100×10-4%, its concentration
Increase with the acidity of mineral ore and reduce, scandium is more in rock and mineral to be existed with oxide, silicate and phosphatic form, is not had
It is found the scandium mineral of sulfide, arsenide or native metal.The mineral containing scandium have had found kind more than 800 in nature, in flower
Scandium can be nearly all found in the by-pass product of hilllock pegmatite type, but content is little, is typical rare and scatter element, as scandium
Independent Mineral at present only find have scandium yttrium ore deposit, water phosphorus scandium ore deposit, bazzite and the dilute gold mine of titanium silicic acid etc. a few, its grade
Sc2O3The ore resources of ＞ 0.05% are more rare, therefore scandium does not have independent resource.Therefore, scandium is in all kinds of scandium contained minerals of integrated treatment
Shi Jinhang synthetical recoveries, whether rationally, the extraction depending on the content, main mineral constituent of scandium in raw material adds for the recovery of association scandium
Work scale, the intermediate products containing scandium of output or cost of the enrichment degree of scandium and process of enriching etc. in waste material.In production process
During middle synthetical recovery scandium, distribution of the scandium in major product concentrates extremely important, and the enrichment in waste material (solution, slag, slag mud)
During with extracting scandium, in addition to enrichment degree of the scandium to be made in waste material is improved as far as possible, also to ensure not destroying the suitable of main flow
Row and balance.
At present, China mainly carries scandium from tungsten slag, chlorination flue dust and titanium white waste acid.The vanadium titano-magnetite of Panzhihua Region is
One of three famous big mineral intergrowths of China, symbiosis has iron, vanadium, three kinds of main beneficial elements of titanium in ore, while being also associated with
Cobalt, nickel, chromium, manganese, copper, sulphur, gallium, scandium and platinum family element.The partially recycled utilization of vanadium and titanium elements is only realized at present.Panzhihua
0.0028%-0.0032% containing scandium in raw ore, iron ore concentrate is 0.0009%-0.0015% containing scandium, and ilmenite concentrate is containing scandium
0.0038%-0.0043%, this explanation scandium is close titanium elements and is enriched in ilmenite concentrate.Researcher has carried out a large amount of from titanium white
The research work of scandium is directly proposed in spent acid, blast furnace slag and Tailing of titanium separation, eventually because cost recovery is higher, fails to realize industrialization.
It is more deep to the enrichment the technique of extracting of scandium at present, it is suitable for carrying raw material mainly titanium white waste acid, the chlorine of scandium
Slugging and blast furnace slag.Chloride slag use water or watery hydrochloric acid (concentration of hydrochloric acid 5%-15%) leaching mode make scandium be dissolved in hydrochloric acid and with
Scandium ion (Sc3+) form is present, blast furnace slag is then needed with the sulfuric acid of higher concentration or hydrochloric acid (acidity 15%~30%) specific
At a temperature of carry out leaching and carry scandium, therefore scandium leached from waste residue not only need acid and water, but also wastewater treatment need to be carried out.Relatively
In reclaiming scandium from waste residue, the cost that scandium is reclaimed from titanium white waste acid is then much lower, three kinds of raw materials in the cost recovery of scandium
Sequentially it is：Blast furnace slag ＞ chloride slag ＞ titanium white waste acids.
When being further enriched with to scandium from solution, existing technique is all to use extracting process, extractant formulation phase not to the utmost
Together, the extraction system for but mainly using all is acid phosphorus oxygen kind of extractants (such as P204, P507), and the extraction system is in washing impurity-removing
During all need to use the new hydrochloric acid of a large amount of 2~4mol/L, this part eo-acid cost accounts for 80% or so of Sc extraction cost,
Also being needed containing acid waste liquid after washing carries out neutralisation treatment by lime slurry, and this further increased the material cost for carrying scandium.
It is also acid content (10%~30%) waste liquid higher that the raffinate after scandium is extracted is carried using above-mentioned three kinds of raw materials in addition, need to be carried out
Neutralisation treatment, the fee of material of neutralisation treatment accounts for the 10%~13% of total material cost.
Chinese patent CN1010579B describes the titanium liquid with ilmenite sulfuric acid decomposition through the spent acid after hydrolysis analysis titanium, uses
Acid Phosphorus and neutral phosphorus extractant synergic solvent extraction scandium, organic phase is not scrubbed after extraction is directly stripped with NaOH, hydrochloric acid
Dissolving, then through the extracting resin chromatographic isolation purification scandium of neutral phosphorus extractant, last extracting and refining scandium oxide.Although the patent
Load organic phases to the initial stage are not washed, and can save substantial amounts of detergent cost and follow-up harmless treatment cost, but
Traditional lime neutralisation treatment mode is still used to the raffinate treatment after extraction.Chinese patent CN1005565B is a kind of from artificial
The method that scandium oxide is extracted in rutile, extracted by sulfuric acid leaching synthetic rutile, organic solvent, the method for oxalic acid precipitation from
Scandium in the Ore Leaching mother liquor of peracid titanium high, the patent is also adopted by the treatment side of lime neutralization to the raffinate containing acid
Method, claim point is then the link of extraction process.Chinese patent application CN102312090A is leaching of being pressurizeed from scandium contained mineral
Go out to extract the method for scandium, the invention sulfuric acid solution of 90~120g/L is with liquid-solid ratio 4：1,150~300 DEG C of temperature, pressure 2~
Under conditions of 3Mpa in autoclave leaching mineral, leach mother liquor filtering after extracted with P507 extractants, load organic phases
Solid primary richness scandium thing is obtained after scrubbed, back extraction, then secondary dissolving is carried out to primary richness scandium thing with hydrochloric acid, addition precipitating reagent makes
Scandium is precipitated, and the rich scandium sediment for obtaining is enriched with using mode solvent extraction again, and finally calcining obtains thick scandium oxide, and this is special
Though the technique for also taking pressure leaching scandium contained mineral of profit, the enrichment flow to scandium only lays particular emphasis on the choosing of solvent extraction technology
Select, the recyclability aspect of economy and various materials to overall flow does not all optimize reasonably.
The another kind of different flow and method that scandium is extracted from mineral, such as Chinese patent ZL89109624.8 extracts from ore
The method for taking scandium, the method is the method for the extracting scandium from zircon, and zircon sand is sent into one about 1000 DEG C of fluidization
Bed chlorinator, to produce a steam phase (mainly zirconium chloride and silicon chloride) and solid residue, leaches this and consolidates with acid water
State residue, the leaching mother liquor is extracted with the organic matter containing octyl phosphate, being stripped out the sediment of scandium with amine salt solution,
Roasting sediment obtains scandium oxide, and the patent goes back emphasis to fluidised chlorination stream in addition to claim is carried out to extraction process
Cheng Jinhang patent protections.
It is that raw material is extracted outside the method for scandium divided by mineral, an also class is by industry of the leaching containing scandium using titanium white waste acid
Waste residue or scandium contained mineral extract the patented method of scandium.As Chinese patent application CN102030355A describes to utilize titanium dioxide
The spent acid of factory extracts the technique of scandium oxide from zinc ore, and the technical characterstic of the patent is in the spent acid leachate of zinc ore
By the precipitate and separate for recycling the pH value of spent acid and lime slurry control solution to realize different component, scandium then will be contained
The new sulfuric acid dissolution of precipitation, after adjustment pH value, with the heavy scandium of oxalic acid, sediment containing scandium is through dissolving with hydrochloric acid twice, and oxalic acid precipitation is last
Calcining obtains scandium oxide.The characteristics of patent is to control to realize the dissolving and leaching of valuable metal in zinc ore using pH value
Go out the precipitation of scandium in liquid, but due to containing iron concentration higher in titanium white waste acid, the process for adjusting pH also may require that consumption
Substantial amounts of lime slurry, whether this is economically reasonable, and the patent does not have data to compare.Chinese patent application CN102011010A
It is the method for using titanium dioxide hydrolysis waste acid dip v-bearing steel slag extracting vanadium, gallium and scandium, the patent leaches v-bearing steel slag with titanium white waste acid,
Again with the vanadium in acid phosphorus and neutral phosphorus extractant extraction leachate, gallium and scandium, then vanadium and gallium are stripped by dilution heat of sulfuric acid,
Scandium is stripped by NaOH+ ethanol solutions, CaO in v-bearing steel slag is made full use of in leaching process consumption titanium white waste acid
H2SO4, in order to avoid the neutralisation treatment cost of raffinate, with obvious economic advantages, but waste residue after acidleach needs for using lime
Neutralize and stack standard to reach discarded object.
Illustrated by the above-mentioned description that scandium technique is put forward to existing three kinds of different materials, even under synthetical recovery mode,
It is also very high that existing technique carries scandium cost.The invention provides a kind of scandium work is put forward than what above-mentioned three kinds of modes had more economy
Skill, i.e., enrichment carries scandium from the leaching mother liquor of hydrochloric acid leaching ferrotianium material production rich-titanium material flow.
China with hydrochloric acid leaching ferrotianium material research oneself have the history of more than 30 years, direct weighting hydrochloric acid leaching process is
Wherein more ripe method, at present existing commercial application.It is main using spraying burning method (or Ruther in the technique
Method) to Cl in leaching mother liquor-Carry out recycling.Scandium element enters leaching mother during hydrochloric acid pressure leaching ferrotianium material
In liquid so that the mother liquor that leaches containing scandium turns into the material liquid of further richness scandium.Due to the product of general hydrochloric acid method rich-titanium material production line
Gauge mould is all than larger, and the liquid-solid ratio that leaching technology is used in addition is (generally 2.5~4) also higher, therefore, in production procedure
Substantial amounts of leaching mother liquor will be produced, the scandium that high value is extracted from mother liquor is leached is also just more meaningful.
In rich-titanium material flow is produced, after ilmenite is through hydrochloric acid pressure leaching, by solid-liquid separating machine (such as barrier film press filtration
Machine) leaching mother liquor is separated with solid material, leach mother liquor and enter HCl recovery system, made by CIU of spraying therein
HCl is regenerated, and regenerated acid is by for the leaching process next time of ilmenite.Its flow is in patent application CN102352437A
It has been described in detail in " a kind of method for processing hydrochloric acid leachate of ferrotitanium materials ", concrete technology flow process is shown in accompanying drawing 1.At this
In flow, the extraction that the burning leaching mother liquor that the present invention will enter after spraying CIU preconcentrator carries scandium as enrichment is former
Liquid, scandium is carried using extraction enrichment, obtains rich scandium solids.
The content of the invention
Deficiency of the present invention for high cost in existing scandium enrichment process, there is provided a kind of hydrochloric acid leaching ilmenite production is rich
The method of scandium-enriched in titanium stream journey, it is characterised in that comprise the steps：
A () ferrotianium material obtains leaching mother liquor 1 after the pressurization of leaching liquid 12 leaching, separation of solid and liquid, leach mother liquor 1 and be split into
Mother liquor 2 is leached in circulating leaching mother liquor 3 and burning；
B () concentrates and cooling：Burn leaching mother liquor 2 to be concentrated into preconcentrator, the extraction stoste obtained after concentration
7, extraction stoste 7 enters the cooling of coil pipe crystallisation by cooling groove, and FeCl is removed through separation of solid and liquid after crystallisation by cooling2·4H2O crystallizations 8, obtain
To extract 13, the cooling medium of the crystallisation by cooling groove is the NaOH solution 14 of 1-3mol/L, and the NaOH solution 14 is in heat exchange
Recycled as back washing agent afterwards；
C () extracts：Extract 13 uses salt pickling using extractant extraction, separating load organic phase 16 and extraction lean solution 15
The wash load organic phase 16 of agent 9 is washed, load organic phases 17 are purified after washing；Scrub raffinate 10 returns to HCl recovery system one
Level absorption tower；The FeCl of the extraction lean solution 15 and crystallisation by cooling2·4H2O crystal 8 returns to the hydrochloric acid in production rich-titanium material flow
The incinerator of recovery system；The hydrochloric acid detergent 9 is the regeneration hydrochloric acid of HCl recovery system two-level absorption tower；
D () is stripped：Purification load organic phases 17 are stripped with the NaOH solution 14 of 1-3mol/L, and filtering strip liquor is obtained
Rich scandium solids, the alkaline filtrate after filtering returns to heat exchanger and is used further to back extraction.
Ferrotianium material described in step (a) is TiO2The ilmenite containing scandium of content 40-50wt% is direct by ferrotianium containing scandium
The titanium slag of reduction new technological process production.
Step (a) leaching liquid 12 is hydrochloric acid solution, and wherein HCl concentration is 15~20wt%, and leaching solid-to-liquid ratio is 2.5
~4g/mL, it is 120~150 DEG C, 0.1~0.4Mpa of pressure, 2~6h of leaching time that leaching process controls temperature；It is described to leach mother
Sc in liquid2O3Concentration is 18~25mg/L, and HCl concentration is 0.9~1.6mol/l.
Preconcentrator described in step (b) is gas-liquid mixed evaporator, from venturi, burns and leaches mother liquor 2 and burn
The high-temperature gas 6 that stove is produced mixes in venturi, and moisture is by evaporation 25~30%, venturi air inlet in burning is leached mother liquor 2
Temperature is 250~450 DEG C, and venturi delivery temperature is not more than 96 DEG C, and the temperature of extraction stoste 7 for obtaining is 85~91 DEG C.
The temperature that step (b) the cooling medium NaOH solution 14 goes out cooling bath is 50~70 DEG C, and extraction stoste 13 goes out cold
But the temperature of groove is 30~40 DEG C；Sc in the extract 132O3Concentration is 24~31mg/L, 2.2~3.2mol/L of HCl concentration.
The composition of step (c) extractant is：The volumetric concentration of P507 or P402 is 3-12%, sec-octyl alcohol volumetric concentration
It is 1.5-3.5%, balance of sulfonated kerosene；Than O/A=0.2~0.8, wherein O is organic phase to extraction phase, and A is water phase, extracts level
1~3 grade of number；The concentration of hydrochloric acid detergent 9 is 2~4mol/L, and O/A=2~4 are compared in washing, wash 2~4 grades of series.
Step (d) the back extraction temperature is 50~70 DEG C, and O/A=1~3 are compared in back extraction, is stripped 1~3 grade of series.
The present invention has advantages below：
(1) the various intermediate products in rationally make use of hydrochloric acid leaching ilmenite to produce rich-titanium material flow
The regenerated acid in rich-titanium material flow will be produced is used to prepare the hydrochloric acid detergent of 2~4mol/L, is extracted with P507
In extraction process based on agent, the material cost of washing acid accounts for 80% or so of total material cost, because the method for the present invention
It is that regeneration hydrochloric acid is more with low cost than eo-acid, and washing is useless on the basis of depending on hydrochloric acid leaching ilmenite production rich-titanium material technique
Liquid is circulated in the production procedure of rich-titanium material by the way that HCl recovery flow is again renewable, therefore, the material cost of washing will be than it
His technique it is with low cost a lot, be the 5%~10% of other techniques；
Material liquid of the mother liquor as extracting and enriching scandium is leached with the burning after concentration, mother liquor can be leached with higher than original
Acidity value and Sc2O3Concentration value, is conducive to the raising of scandium extraction yield.Table 1 lists the pass between concentration of hydrochloric acid and the scandium rate of recovery
System, such as：Mother liquor (HCl=1mol/l) is leached for raw material abstraction scandium with burning, and single-stage extraction rate is 47.4%, and burning with concentration
It is raw material abstraction scandium to burn mother liquor (HCl=2.5mol/l), and single-stage extraction rate brings up to 81.7%.
Relation between the concentration of hydrochloric acid of table 1 and the scandium rate of recovery
| HCl concentration (mol/L) in mother liquor | 1 | 1.5 | 2 | 2.5 |
| Sc extraction yields (%) | 47.4 | 77.6 | 79.3 | 81.7 |
(2) heat energy is made full use of
Back washing agent NaOH solution is cooled down into extraction stoste as the cooling medium of heat exchanger, extraction stoste can not only be made
Temperature reaches the temperature requirement of extraction process, also makes the requirement of the similarly suitable stripping process of temperature of back washing agent, thus saves
The energy individually to back washing agent heating is saved.
(3) extraction lean solution can return to not cause secondary pollution in rich-titanium material production procedure
Extractant is acid phosphorus oxygen kind of extractants, and the reaction of its extraction process is：
Sc3++ 3HL (O)=ScL3(O)+3H+
Reactional equation explanation extraction process extractant will not extracting HCl, can discharge H+ ions on the contrary, therefore extraction lean solution
Acidity will not reduce, the incinerator for so extracting the lean solution HCl recovery system that can be directly entered rich-titanium material production line is carried out
Regeneration is processed, and need not carry out neutralization emission treatment.The damage of organic extractant can be more or less caused in extraction process simultaneously
Lose in lean solution is extracted, and extraction lean solution is returned to incinerator burning and reduces the dirt to environment of organic extractant by the present invention
Dye.
Brief description of the drawings
Fig. 1 is conventional ferrotianium material hydrochloric acid leaching and leaches mother liquid disposal flow chart；
Fig. 2 is the flow chart that the present invention is combined with hydrochloric acid method leaching ilmenite production rich-titanium material technique；
Fig. 3 is to burn the flow chart for leaching mother liquor extracting and enriching scandium.
Specific embodiment
The invention provides the method for scandium-enriched in a kind of hydrochloric acid leaching ilmenite production rich-titanium material flow, with reference to attached
The invention will be further described with embodiment for figure, it is not intended that limitation of the present invention.
The method of scandium-enriched of the present invention comprises the following steps as shown in accompanying drawing 2 and accompanying drawing 3：
1st, ferrotianium material is through hydrochloric acid pressurization leaching, the leaching mother liquor set-up procedure of separation of solid and liquid
A, the preparation of leaching liquid 12 are formed by the recovery hydrochloric acid containing iron ion with the mixed in hydrochloric acid newly added, in leaching liquid
Free concentration of hydrochloric acid be 15-25wt%, the Fe in leaching liquid 122++Fe3+Concentration is 30-60g/L, and a bit simultaneously, leaching liquid
Contain calcium, magnesium, aluminium, manganese plasma；
The ratio of b, mixing ilmenite and leaching liquid 12, ilmenite and leaching liquid 12 is 1g ﹕ 2.5-4ml, preheating leaching, 12
Enter leaching reactor to 70 DEG C~100 DEG C, then, by Leach reaction by the way of steam or indirectly heat is passed directly into
Temperature control keeps its reaction temperature 2-6 hours at 120 DEG C~150 DEG C；
, through separation of solid and liquid, gained liquid is leaching mother liquor 1 for c, reaction paste；
D, leaching mother liquor 1 are split into the circulation burned and leach mother liquor 2 and HCl recovery system according to iron ion equilibrium concentration
Leach mother liquor 3；Iron concentration leaching mother liquor high enters burning, and the low leaching mother liquor of iron concentration enters HCl recovery system
System, the iron for keeping the leaching of ferrotianium material to bring system into the iron and organic extraction raffinate of hydrochloric acid system is equal to shunting and burns row
The iron of desalination acid system, iron concentration boundary is set to 100~160g/L, preferably 140~150g/L.
Hydrochloric acid in step a in leaching liquid 12 mostlys come from regeneration of hydrochloric acid, the Fe in leaching liquid2+And Fe3+Come from leaching
Go out being recycled back into for mother liquor 1, other concentration of impurity (calcium, magnesium, aluminium etc.) in leaching liquid 12 depend on handled ilmenite
Impurity content.
Step b needs to preheat leaching liquid 12 to 70~100 DEG C before leaching liquid mixes with ilmenite, and preheating purpose is to use up
Amount shortens the heat time, reduces the possibility that leaching liquid is diluted, and leaching 12 mixes with ilmenite to be held in a reaction for closing
Carried out in device.
Step c is filtered again when filtering, it is necessary to reaction solution is first cooled into 80-90 DEG C, and filtering can be using any one
Form, such as vacuum filtration or press filtration.
When step d is shunted, iron is female equal to leaching is burned into the total amount of system during the leaching mother liquor of gained presses leaching process
The total amount shunting of iron in liquid.
2nd, burn leaching mother liquor 2 to be concentrated into the preconcentrator of waste hydrochloric acid recovery system, cooling bath is entered after concentration
Cooling, FeCl is removed after cooling through filter again2·4H2O is crystallized
A. the gas that 370~450 DEG C are arranged outside incinerator carries out solid and gas separation into cyclone clasfficiator, and soild oxide is returned
Incinerator is returned, high-temperature gas 6 mixes into Venturi preconcentrator with leaching mother liquor 2 is burned, and burns the moisture leached in mother liquor
By evaporation 25~30%, Venturi preconcentrator exit gas is no more than 96 DEG C, burns and leaches mother liquor through the liquid after pre-concentration
Claim extraction stoste 7, extraction stoste 7 temperature is 85-91 DEG C；
B. extraction stoste 7 enters coil pipe cooling bath, and it is carried out to be cooled to 30~40 DEG C, and coolant is used by back extraction
NaOH solution, while NaOH solution is heated into 50~70 DEG C；
C. when containing Fe2+After the extraction stoste 7 of 120-170g/L is cooled to 30~40 DEG C, FeCl can be produced2·4H2O is crystallized
8, after separation of solid and liquid, solid FeCl2·4H2Incinerator is sent in O crystallizations 8 after merging with extraction lean solution 15, filtrate is extract 13,
Sc therein2O3Concentration is 24-31mg/L, HCl concentration 2.2-3.2mol/L.
3rd, extraction and the isolated rich scandium solids of back extraction；
A. extract：Extract 13 is mixed with extractant, the formula of extractant is：The volumetric concentration of P507 is 3-7%, its
Middle diluent is sec-octyl alcohol and sulfonated kerosene, and its volumetric concentration is respectively 1.5-3.5% and 89.5-96.5%, and extraction phase compares O/A
=0.5, extract 2 grades of series；
B. separate：In extraction process, scandium migrates into organic phase rear organic load organic phases that match to extract, through sedimentation
Or load organic phases 16 and extraction lean solution 15 are obtained after centrifugation, extract lean solution 15 and FeCl2·4H2O crystallizations 8 are returned after merging
CIU.
C. wash：Load organic phases 16 in addition to scandium is loaded with also entrainment of other impurity, with two grades of the HCl recovery system mat woven of fine bamboo strips
The watery hydrochloric acid of adsorption tower is made into the hydrochloric acid detergent 9 of 2~4mol/L, and its wash conditions is compared to O/A=3：1, wash series 3
Level, it is separated after, washing useless 10 returns to HCl recovery system mat woven of fine bamboo strips primary adsorption towers, and purification load organic phases 17 enter back extraction and make
Industry.
D. it is stripped：Purification load organic phases 17 are stripped, and it is back washing agent to use NaOH solution 4, and NaOH solution concentration is 1
~3mol/L, back extraction temperature is 50~70 DEG C, and O/A=2 is compared in back extraction：1,2 grades of series is stripped, the organic phase after back extraction returns to extraction
It is taken as industry.
E. filter：Strip liquor after back extraction contains scandium and precipitate metal hydroxides and remaining NaOH solution, strip liquor warp
It is filtrated to get rich scandium solids and NaOH solution.
4th, lean solution 15 and FeCl are extracted2·4H2The mixing of O crystallizations 8 and regeneration of hydrochloric acid
Extraction lean solution 15 and FeCl2·4H2It is made into that to burn liquid into incinerator main purpose be to reclaim hydrochloric acid after O crystallizations 8 are mixed,
Burn and following hydrolysis occurs in the case where temperature is for 500~820 DEG C, decomposes and oxidation, burn liquid and sprayed by sour rifle from the furnace roof of incinerator
Mouth with it is vaporific penetrating stove in burned, and coal gas and air in a furnace portion with tangential direction enter stove in, burn liquid burning
Burning stove middle part is due to high temperature generation hydrolysis and decomposition reaction, generation hydrogen chloride gas and based on ferric oxide particle and contains
The particle of magnesia, calcium oxide etc..Most of solid particle falls incinerator bottom because of Action of Gravity Field, and is arranged from incinerator bottom
Go out, fraction solid particle is taken out by blower fan with the waste gas produced after hydrogen chloride gas, vapor and gas-fired from furnace roof portion
Go out, solid particle is most of after removing dust returns in stove, and waste gas enters Venturi preconcentrator.
The absorption of hydrogen chloride gas is that hydrogen chloride is separated from waste gas, makes the process of regeneration of hydrochloric acid, whole process
Completed in two grades of (or three-level) absorption towers.The waste gas containing hydrogen chloride gas come from Venturi preconcentrator initially enters one
The bottom of level absorption tower (I), by supporting the screen of filler, in the roundabout rising in the space of packing layer, then by first grade absorption tower (I)
Top discharge, then, into the bottom of two-level absorption tower (II), the hydrogen chloride gas in waste gas is further absorbed,
Discharge at the last top by two-level absorption tower (II).The solution of absorbing hydrogen chloride gas is dilute leaching mother liquor 5, is by partly leaching
Mother liquor is the washing filtrate 4 of the circulating leaching mother liquor 3, washing procedure obtained after shunting and adds water or watery hydrochloric acid composition.
Salt sour waste gas are in absorption tower by dilute leaching counter current absorption of mother liquor 5：Dilute leaching mother liquor 5 is first from two-level absorption tower
(II) uniformly spray arrives packing layer upper surface at top, and the bottom of two-level absorption tower (II) is flowed downward to along filler surface
Portion, then, then pump to the top of first grade absorption tower (I) through spray after, be collected in the bottom of first grade absorption tower (I), absorb chlorination
The solution formed after hydrogen is referred to as to circulate dilute leaching mother liquor 11, is solvable containing iron chloride, calcium chloride, magnesium chloride, manganese chloride etc.
Property chlorate hydrochloric acid compound system solution, its ferrous ion concentration be 28~100g/L, concentration of hydrochloric acid increase after absorption to
16~20%.The dilute leaching pump of mother liquor 11 to leaching liquid preparation process will be circulated and realize Recycling.
Embodiment 1
Using scandium-enriched of the present invention：Sample takes from Fu Tai factories of Panzhihua Xinzhongtai Science ＆ Technology Co., Ltd. HCl recovery system text
Western ilmenite concentrate is climbed using hydrochloric acid pressure leaching by preconcentrator underflow in mound, the Fu Tai factories, and the ore pulp of leaching passes through solid-liquid separating machine
(such as diaphragm filter press) makes leaching mother liquor be separated with solid material, and part is leached mother liquor (burn and leach mother liquor) and returned into waste hydrochloric acid
The preconcentrator of receipts system, the extraction stoste after concentration enters heat exchanger crystallisation by cooling and removes FeCl with filter2·4H2O must simultaneously extract
Liquid is taken, the index for extracting extract used is as shown in table 2.
The chemical group analysis of components of the different mother liquors of table 2
| Feed liquid title | TFe(g/L) | HCl(g/L) | ||
| Leach mother liquor | 276.2 | 140.2 | 20 | 41.7 |
| Extraction stoste | 369.7 | 185.3 | 26.3 | 88.5 |
| Extract | 326.9 | 145 | 27.3 | 92.1 |
Sc extraction is carried out to extract, using P507 as extractant, extractant formulation is 5%P507+2.5% Zhong Xin
The sulfonated kerosene of alcohol+92.5% (volume ratio), extraction phase extracts 2 grades of series than O/A=0.5；With 2mol/l HCl solutions as washing
Agent is washed, O/A=3 is compared in wash load organic phase, washing, washs 3 grades of series；With 2.5mol/l NaOH solutions as back washing agent,
O/A=2 is compared in load organic phases after back extraction washing, back extraction：1,80 DEG C of back washing agent temperature is stripped 2 grades of series, used after back extraction
Rich scandium solids is collected in filter, and as shown in table 3, the composition analysis of rich scandium solids is as shown in table 4 for the yield situation of whole process scandium.
The Sc recovery (%) of scandium-enriched technique in the hydrochloric acid leaching ilmenite of table 3 production rich-titanium material flow
The composition analysis of the rich scandium solids of table 4
| Composition | ||||
| Content % (wt) | 6.31 | 13.85 | 55.83 | 24.01 |
Embodiment 2
It is extract with leaching mother liquor with the leaching mother liquor scandium-enriched (the contrast present invention) not concentrated, its composition index is such as
Shown in table 2.
Sc extraction is carried out to leaching mother liquor, using P507 as extractant, extractant formulation is that 5%P507+2.5% is secondary
The sulfonated kerosene of octanol+92.5% (volume ratio), extraction phase extracts 2 grades of series than O/A=0.5；With 2mol/l HCl solution conducts
O/A=3 is compared in detergent, wash load organic phase, washing, washs 3 grades of series；With 2.5mol/l NaOH solutions as back extraction
O/A=2 is compared in agent, the load organic phases after back extraction washing, back extraction：1,80 DEG C of back washing agent temperature is stripped 2 grades of series, after back extraction
Rich scandium solids is collected with flame filter press.The yield situation of extracting scandium is as shown in table 5, the composition analysis such as table of rich scandium solids
Shown in 6.
What table 5 was never concentrated leaches the Sc recovery (%) of scandium-enriched technique in mother liquor
The composition analysis of the rich scandium solids of table 6
| Composition | ||||
| Content % (wt) | 7.17 | 15.75 | 62.47 | 13.62 |
Embodiment 3
The scandium in extract is extracted with P204：It is raw material with the extract of embodiment 1, its analysis of components such as table 2.Work as use
P204 is the sulfonated kerosene of 12%P204+3% sec-octyl alcohols+85% (volume ratio) as extractant, extractant formulation, and extraction phase compares O/
A=0.5, extracts 2 grades of series；With 2mol/l HCl solutions as detergent, O/A=3 is compared in wash load organic phase, washing,
3 grades of series of washing；With 2.5mol/l NaOH solutions as back washing agent, O/A is compared in the load organic phases after back extraction washing, back extraction
=2：1,80 DEG C of back washing agent temperature is stripped 2 grades of series, and rich scandium solids is collected with flame filter press after back extraction.Extraction process scandium
Yield situation as shown in table 7, the composition analysis of rich scandium solids is as shown in table 8.
The P204 extractants of table 7 are enriched with the yield (%) for burning scandium technique in mother liquor
The composition analysis of the rich scandium solids of table 8
| Composition | ||||
| Content % (wt) | 6.23 | 15.15 | 54.27 | 24.35 |
Claims (7)
1. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow, it is characterised in that comprise the steps：
A () ferrotianium material obtains leaching mother liquor (1) after leaching liquid (12) pressurization leaching, separation of solid and liquid, leach mother liquor (1) shunting
Mother liquor (2) is leached into circulating leaching mother liquor (3) and burning；
B () concentrates and cooling：Burn leaching mother liquor (2) to be concentrated into preconcentrator, the extraction stoste obtained after concentration
(7), extraction stoste (7) enters the cooling of crystallisation by cooling groove, and FeCl is removed through separation of solid and liquid after crystallisation by cooling2·4H2O crystallizes (8),
Extract (13) is obtained, the cooling medium of the crystallisation by cooling groove is the NaOH solution (14) of 1-3mol/L, the NaOH solution
(14) recycled as back washing agent after heat exchange；
C () extracts：Extract (13) uses hydrochloric acid using extractant extraction, separating load organic phase (16) and extraction lean solution (15)
Detergent (9) wash load organic phase (16), is purified load organic phases (17) after washing；Scrub raffinate (10) returns to hydrochloric acid
Recovery system first grade absorption tower；Extraction lean solution (15) and the FeCl of crystallisation by cooling2·4H2O crystal (8) returns to the rich titanium of production
The incinerator of the HCl recovery system in stream journey；The hydrochloric acid detergent (9) for HCl recovery system two-level absorption tower again
Raw hydrochloric acid；
D () is stripped：Purification load organic phases (17) is stripped with the NaOH solution (14) of 1-3mol/L, and filtering strip liquor is obtained
Rich scandium solids, the alkaline filtrate after filtering returns to heat exchanger and is used further to back extraction.
2. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that the ferrotianium material described in step (a) is TiO2The ilmenite containing scandium of content 40-50wt% is reduced directly by ferrotianium containing scandium
The titanium slag of new technological process production.
3. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that step (a) leaching liquid (12) is hydrochloric acid solution, wherein HCl concentration is 15~20wt%, leaching solid-to-liquid ratio is 2.5
~4g/mL, it is 120~150 DEG C, 0.1~0.4Mpa of pressure, 2~6h of leaching time that leaching process controls temperature；It is described to leach mother
Sc in liquid2O3Concentration is 18~25mg/L, and HCl concentration is 0.9~1.6mol/L.
4. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that the preconcentrator described in step (b) is gas-liquid mixed evaporator, from venturi, burns and leach mother liquor (2) and incinerator
The high-temperature gas (6) of generation mixes in venturi, and by evaporation 25~30%, venturi enters moisture in burning is leached mother liquor (2)
Temperature degree is 250~450 DEG C, and venturi delivery temperature is not more than 96 DEG C, and extraction stoste (7) temperature for obtaining is 85~91 DEG C.
5. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that the temperature that step (b) the cooling medium NaOH solution (14) goes out cooling bath is 50~70 DEG C, and extraction stoste (13) goes out cold
But the temperature of groove is 30~40 DEG C；Sc in the extract (13)2O3Concentration is 24~31mg/L, 2.2~3.2mol/ of HCl concentration
L。
6. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that the composition of step (c) extractant is：The volumetric concentration of P507 or P402 is 3-12%, and sec-octyl alcohol volumetric concentration is
1.5-3.5%, balance of sulfonated kerosene；Than O/A=0.2~0.8, wherein O is organic phase to extraction phase, and A is water phase, extracts series
1~3 grade；Hydrochloric acid detergent (9) concentration is 2~4mol/L, and O/A=2~4 are compared in washing, wash 2~4 grades of series.
7. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material flow according to claim 1, its feature
It is that step (d) the back extraction temperature is 50~70 DEG C, and O/A=1~3 are compared in back extraction, is stripped 1~3 grade of series.
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| CN111979413A (en) * | 2019-05-22 | 2020-11-24 | 攀枝花驰瑞矿冶科技有限公司 | Production method of titanium-rich material |
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