CN106868325B - A kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process - Google Patents
A kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process Download PDFInfo
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- CN106868325B CN106868325B CN201710057056.4A CN201710057056A CN106868325B CN 106868325 B CN106868325 B CN 106868325B CN 201710057056 A CN201710057056 A CN 201710057056A CN 106868325 B CN106868325 B CN 106868325B
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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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- 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
- C22B3/20—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
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the methods of scandium-enriched in a kind of hydrochloric acid leaching ilmenite production rich-titanium material process, belong to field of hydrometallurgy.Ferrotianium material obtains leachate through hydrochloric acid leaching, and leachate enters preconcentrator concentration；Leachate after concentration enters cooling bath cooling, separates FeCl using filter2·4H2O crystallization, the cooling medium of cooling bath is the NaOH stripping agent that need to be preheated；Treated, and concentration leachate extractant Sc extraction is stripped with hot NaOH solution with the cleaning solution purification load organic phases of regeneration hydrochloric acid preparation, rich scandium solids is obtained after being separated by solid-liquid separation；Extract lean solution and FeCl2·4H2O crystallization returns to the incinerator in rich-titanium material production procedure；The first grade absorption tower of scrub raffinate return HCl recovery system.The various intermediate products in hydrochloric acid leaching ilmenite production rich-titanium material process are rationally utilized in the present invention, stripping process takes full advantage of the heat of concentration leachate, it extracts lean solution and scrub raffinate returns to rich-titanium material production procedure, there is 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 in a kind of hydrochloric acid leaching ilmenite production rich-titanium material process
The method of scandium.
Background technique
Content of the scandium in the earth's crust is simultaneously many, but only excessively disperses, and Independent Mineral is rare, and reserves are small.Scandium master
It is present in iron-magnesium mineral of basic rock and ultrabasic rock, Sc2O3Content is generally 5 × 10-4-100×10-4%, concentration
With mineral ore acidity increase and reduce, scandium in rock and mineral mostly by oxide, silicate and it is phosphatic in the form of exist, do not have
It is found the scandium mineral of sulfide, arsenide or native metal.Mineral in nature containing scandium have had found more than 800 kinds, in flower
Scandium can be nearly all found in the by-pass product of hilllock pegmatite type, but content is little, be typical rare and scatter element, as scandium
Independent Mineral at present only discovery have scandium yttrium mine, water phosphorus scandium mine, bazzite and the dilute gold mine of titanium silicic acid etc. a few, grade
Sc2O30.05% ore resources of > are more rare, therefore scandium does not have independent resource.Therefore, scandium is only in all kinds of scandium contained minerals of integrated treatment
Whether the recycling of Shi Jinhang synthetical recovery, association scandium is reasonable, adds depending on the content of scandium, the extraction of main mineral constituent in raw material
Work scale, output intermediate products containing scandium or waste material in scandium enrichment degree and the cost of process of enriching etc..In production process
When middle synthetical recovery scandium, distribution concentration of the scandium in major product is extremely important, and the enrichment in waste material (solution, slag, slag mud)
When with extracting scandium, other than enrichment degree of the scandium to be made in waste material improves as far as possible, also to guarantee not destroying the suitable of main flow
Row and balance.
Currently, China mainly mentions scandium from tungsten slag, chlorination flue dust and titanium white waste acid.The vanadium titano-magnetite of Panzhihua Region is
Famous one of the three big mineral intergrowths in China, symbiosis has three kinds of iron, vanadium, titanium main beneficial elements 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 are 0.0009%-0.0015% containing scandium, and ilmenite concentrate is containing scandium
0.0038%-0.0043%, this illustrates that scandium is close titanium elements and is enriched in ilmenite concentrate.Researcher has carried out largely from titanium white
The research work that scandium is directly mentioned in spent acid, blast furnace slag and Tailing of titanium separation is not able to achieve industrialization eventually because cost recovery is higher.
More deep to the enrichment the technique of extracting of scandium at present, the raw material for being suitable for mentioning scandium is mainly titanium white waste acid, chlorine
Slugging and blast furnace slag.The mode that chloride slag uses water or dilute hydrochloric acid (concentration of hydrochloric acid 5%-15%) to leach make scandium be dissolved in hydrochloric acid and with
Scandium ion (Sc3+) form presence, the sulfuric acid or hydrochloric acid (acidity 15%~30%) that blast furnace slag then needs to use higher concentration are specific
At a temperature of carry out leaching and mention scandium, therefore leach scandium from waste residue and not only need acid and water, but also wastewater treatment need to be carried out.Relatively
In recycling scandium from waste residue, the cost that scandium is recycled from titanium white waste acid is then much lower, three kinds of raw materials in the cost recovery of scandium
Sequentially are as follows: blast furnace slag > chloride slag > titanium white waste acid.
When being further enriched with from solution to scandium, existing technique is all using extracting process, extractant formulation phase not to the utmost
Together, but main extraction system to be used is all acid phosphorus oxygen kind of extractants (such as P204, P507), and the extraction system is in washing impurity-removing
The new hydrochloric acid using a large amount of 2~4mol/L is all needed in the process, this part eo-acid cost accounts for 80% or so of Sc extraction cost,
It also needs to be neutralized by lime slurry containing acid waste liquid after washing, this further increases the material cost for mentioning scandium.
In addition mentioning scandium raffinate extracted using above-mentioned three kinds of raw materials is also higher (10%~30%) waste liquid of acid content, needs to carry out
Neutralisation treatment, the 10%~13% of the total material cost of fee of material Zhan of neutralisation treatment.
Chinese patent CN1010579B describes the spent acid with the titanium liquid of ilmenite sulfuric acid decomposition after titanium is analysed in hydrolysis, uses
Acid Phosphorus and neutral phosphorus extractant synergic solvent extraction scandium, organic phase is not washed after extraction is directly stripped with sodium hydroxide, hydrochloric acid
Dissolution, then the extracting resin chromatographic isolation through neutral phosphorus extractant purify scandium, last extracting and refining scandium oxide.Although the patent
To the load organic phases at initial stage without washing, a large amount of detergent cost and subsequent harmless treatment cost can be saved, but
Traditional lime neutralisation treatment mode is still used to raffinate extracted processing.Chinese patent CN1005565B one kind is from artificial
In rutile extract scandium oxide method, by sulfuric acid leaching synthetic rutile, organic solvent extraction, oxalic acid precipitation method from
Scandium in the Ore Leaching mother liquor of the high titanium of peracid, the processing side which also uses lime to neutralize the raffinate containing acid
Method, claim point are then the links of extraction process.Chinese patent application CN102312090A is leaching of pressurizeing from scandium contained mineral
The method for extracting scandium out, the invention with the sulfuric acid solution of 90~120g/L with liquid-solid ratio 4:1,150~300 DEG C of temperature, pressure 2~
Leaching mineral, leaching mother liquor are extracted after filtering with P507 extractant in autoclave under conditions of 3Mpa, load organic phases
Solid primary richness scandium object is obtained after washed, back extraction, then secondary dissolution is carried out to primary rich scandium object with hydrochloric acid, and addition precipitating reagent makes
Scandium precipitating, obtained rich scandium sediment use mode solvent extraction to be enriched with again, and finally calcining obtains thick scandium oxide, this is specially
Though the technique for also taking pressure leaching scandium contained mineral of benefit, the choosing of solvent extraction technology is only laid particular emphasis on to the enrichment process of scandium
It selects, does not all optimize reasonably in terms of the recyclability of economy and various materials to overall flow.
The another kind of different flow and methods that scandium is extracted from mineral, as Chinese patent ZL89109624.8 extracts from ore
The method for taking scandium, this method are the methods of the extracting scandium from zircon, and zircon sand is sent into one about 1000 DEG C of fluidization
It is solid to leach this with acid water to generate a steam phase (mainly zirconium chloride and silicon chloride) and solid residue for bed chlorinator
State residue extracts the leaching mother liquor with the organic matter of the phosphate containing octyl, in the sediment for being stripped out scandium with amine salt solution,
Roasting sediment obtains scandium oxide, which goes back emphasis to fluidised chlorination stream in addition to carrying out claim to extraction process
Cheng Jinhang patent protection.
It is that raw material extracts outside the method for scandium divided by mineral, is to pass through industry of the leaching containing scandium using titanium white waste acid there are also one kind
Waste residue or scandium contained mineral extract the patented method of scandium.It describes to utilize titanium dioxide such as Chinese patent application CN102030355A
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
The pH value of solution is controlled by recycling spent acid and lime slurry, then the precipitation and separation of Lai Shixian different component will contain scandium
It precipitates new sulfuric acid dissolution, after adjustment pH value, sinks scandium with oxalic acid, for sediment containing scandium through dissolving with hydrochloric acid twice, oxalic acid precipitation is last
Calcining obtains scandium oxide.The characteristics of patent is the dissolution and leaching that valuable metal in zinc ore is realized using the control of pH value
Out in liquid scandium precipitating, but due to containing higher iron concentration in titanium white waste acid, the process for adjusting pH also may require that consumption
A large amount of lime slurry, whether this is economically reasonable, which does not have data to compare.Chinese patent application CN102011010A
It is to use titanium dioxide hydrolysis waste acid dip v-bearing steel slag extracting vanadium, the method for gallium and scandium, which leaches v-bearing steel slag with titanium white waste acid,
Vanadium, gallium and scandium in leachate are extracted with acid phosphorus and neutral phosphorus extractant again, then vanadium and gallium are stripped by dilution heat of sulfuric acid,
It is stripped scandium by NaOH+ ethanol solution, makes full use of the CaO in v-bearing steel slag in leaching process consumption titanium white waste acid
H2SO4, in case the neutralisation treatment cost of raffinate, has apparent economic advantages, but the waste residue after acidleach still needs to use lime
It neutralizes to reach waste and stack standard.
The existing description for proposing scandium technique there are three types of different material is illustrated by above-mentioned, even under synthetical recovery mode,
It is also very high that existing technique, which proposes scandium cost,.Scandium work is proposed than what above-mentioned three kinds of modes had more economy the present invention provides a kind of
Skill, i.e., enrichment mentions scandium from the leaching mother liquor of hydrochloric acid leaching ferrotianium material production rich-titanium material process.
In China, with the research of hydrochloric acid leaching ferrotianium material, oneself has more than 30 years history, and direct weighting hydrochloric acid leaching process is
Wherein more mature method has industrial application at present.Mainly using spraying incineration method (or Ruther in the technique
Method) to Cl in leaching mother liquor-Carry out recycling and reusing.It is female to enter leaching for scandium element during hydrochloric acid pressure leaching ferrotianium material
In liquid, so that the mother liquor that leaches containing scandium becomes the material liquid of further rich scandium.Due to the production of general hydrochloric acid method rich-titanium material production line
Gauge mould is all bigger, and the liquid-solid ratio that leaching technology uses in addition is also higher (generally 2.5~4), therefore, in production procedure
A large amount of leaching mother liquor will be generated, the scandium that high value is extracted from leaching mother liquor is also just more meaningful.
In production rich-titanium material process, ilmenite passes through solid-liquid separating machine (such as diaphragm filters pressing after hydrochloric acid pressure leaching
Machine) separate leaching mother liquor with solid material, it leaches mother liquor and enters HCl recovery system, made by spraying incineration system therein
HCl is regenerated, and regenerated acid will be used for the leaching process next time of ilmenite.Its process is in patent application CN102352437A
It is described in detail in " a method of processing hydrochloric acid leachate of ferrotitanium materials ", concrete technology flow process is shown in attached drawing 1.At this
In process, the present invention will leach the extraction original that mother liquor mentions scandium as enrichment into the burning after spraying incineration system preconcentrator
Liquid mentions scandium using extraction enrichment, obtains rich scandium solids.
Summary of the invention
It is rich to provide a kind of hydrochloric acid leaching ilmenite production for deficiency at high cost in existing scandium enrichment process by the present invention
The method of scandium-enriched in titanium stream journey, which is characterized in that include the following steps:
(a) ferrotianium material obtains leaching mother liquor 1 after the pressurization of leaching liquid 12 leaching, separation of solid and liquid, leaches mother liquor 1 and is split into
Mother liquor 2 is leached in circulating leaching mother liquor 3 and burning；
(b) concentration and cooling: burning leaching mother liquor 2 and be concentrated into preconcentrator, the extraction stoste obtained after concentration
7, extraction stoste 7 enters the cooling of coil pipe crystallisation by cooling slot, is separated by solid-liquid separation removal FeCl after crystallisation by cooling2·4H2O crystallization 8, obtains
To extract liquor 13, the cooling medium of the crystallisation by cooling slot is the NaOH solution 14 of 1-3mol/L, which is exchanging heat
It is recycled afterwards as stripping agent；
(c) extract: extract liquor 13 is extracted using extractant, separating load organic phase 16 and extraction lean solution 15, with salt pickling
9 wash load organic phase 16 of agent is washed, load organic phases 17 are purified after washing；Scrub raffinate 10 returns to HCl recovery system one
Grade 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 process
The incinerator of recovery system；The hydrochloric acid detergent 9 is the regeneration hydrochloric acid of HCl recovery system two-level absorption tower；
(d) be stripped: purification load organic phases 17 are stripped with the NaOH solution 14 of 1-3mol/L, and filtering strip liquor obtains
Rich scandium solids, filtered alkaline filtrate return to heat exchanger and are used further to be stripped.
Ferrotianium material described in step (a) is TiO2The ilmenite containing scandium of content 40-50wt% is direct by ferrotianium containing scandium
Restore the titanium slag of 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, leaching process is controlled at 120~150 DEG C, 0.1~0.4Mpa of pressure, 2~6h of leaching time；The leaching is female
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, selects venturi, burns and leaches mother liquor 2 and burn
The high-temperature gas 6 that furnace generates is mixed in venturi, is made to burn moisture in leaching mother liquor 2 and is evaporated 25~30%, venturi air inlet
Temperature is 250~450 DEG C, and venturi delivery temperature is not more than 96 DEG C, and obtained 7 temperature of extraction stoste 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 is cold out
But the temperature of slot is 30~40 DEG C；Sc in the extract liquor 132O3Concentration is 24~31mg/L, 2.2~3.2mol/L of HCl concentration.
The composition of step (c) extractant are as follows: the volumetric concentration of P507 or P402 is 3-12%, sec-octyl alcohol volumetric concentration
For 1.5-3.5%, surplus is sulfonated kerosene；Extraction phase ratio O/A=0.2~0.8, wherein O is organic phase, and A is water phase, extracts grade
1~3 grade of number；9 concentration of hydrochloric acid detergent is 2~4mol/L, and O/A=2~4 are compared in washing, washs 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 invention has the following advantages that
(1) the various intermediate products in hydrochloric acid leaching ilmenite production rich-titanium material process are rationally utilized
Regenerated acid in production rich-titanium material process is used to prepare the hydrochloric acid detergent of 2~4mol/L, is extracted with P507
In extraction process based on agent, 80% or so of the total material cost of material cost Zhan of washing acid, because of method of the invention
It is to depend on the basis of hydrochloric acid leaching ilmenite production rich-titanium material technique, regeneration hydrochloric acid is more low in cost than eo-acid, and washs useless
Liquid is circulated in the production procedure of rich-titanium material by the way that HCl recovery process is again renewable, and therefore, the material cost of washing will be than it
His technique it is low in cost very much, be the 5%~10% of other techniques；
Burning after using concentration leaches mother liquor as the material liquid of extracting and enriching scandium, and mother liquor can be leached than original with higher
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: use burning leaching mother liquor (HCl=1mol/l) for raw material abstraction scandium, single-stage extraction rate 47.4%, and burning with concentration
Burning mother liquor (HCl=2.5mol/l) is raw material abstraction scandium, and single-stage extraction rate is increased to 81.7%.
Relationship between 1 concentration of hydrochloric acid of table and the scandium rate of recovery
| HCl concentration (mol/L) in mother liquor | 1 | 1.5 | 2 | 2.5 |
| Sc extraction yield (%) | 47.4 | 77.6 | 79.3 | 81.7 |
(2) thermal energy is made full use of
Stripping agent NaOH solution is cooled down into extraction stoste as the cooling medium of heat exchanger, can not only make to extract stoste
Temperature reaches the temperature requirement of extraction process, so that the temperature of stripping agent is similarly suitble to the requirement of stripping process, thus saves
It has saved individually to the energy of stripping agent heating.
(3) extraction lean solution, which can return in rich-titanium material production procedure, does not cause secondary pollution
Extractant is acid phosphorus oxygen kind of extractants, the reaction of extraction process are as follows:
Sc3++ 3HL (O)=ScL3(O)+3H+
Reactional equation explanation extraction process extractant will not extracting HCl, H+ ion can be discharged instead, therefore extract lean solution
Acidity will not reduce, in this way extraction lean solution can be directly entered rich-titanium material production line HCl recovery system incinerator carry out
Regeneration treatment, without carrying out neutralization emission treatment.It more or less will cause the damage of organic extractant in extraction process simultaneously
It loses in extraction lean solution, and the present invention burns extraction lean solution return incinerator the dirt to environment for reducing organic extractant
Dye.
Detailed description of the invention
Fig. 1 is conventional ferrotianium material hydrochloric acid leaching and leaching 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 present invention provides the methods of scandium-enriched in a kind of hydrochloric acid leaching ilmenite production rich-titanium material process, below 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 includes the following steps: as shown in attached drawing 2 and attached drawing 3
1, leaching mother liquor preparation process of the ferrotianium material through hydrochloric acid pressurization leaching, separation of solid and liquid
A, the preparation of leaching liquid 12 is formed by the recycling 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；
B, the ratio of mixing ilmenite and leaching liquid 12, ilmenite and leaching liquid 12 is 1g ﹕ 2.5-4ml, and preheating leaches, 12
Enter leaching reactor to 70 DEG C~100 DEG C, then, by Leach reaction by the way of being passed directly into steam or indirect heating
Temperature is controlled at 120 DEG C~150 DEG C, and keeps its reaction temperature 2-6 hours；
C, for reaction paste through being separated by solid-liquid separation, gained liquid is to leach mother liquor 1；
D, it leaches mother liquor 1 and is split into the circulation for burning leaching mother liquor 2 and HCl recovery system according to iron ion equilibrium concentration
Leach mother liquor 3；The high leaching mother liquor of iron concentration enters burning, and the low leaching mother liquor of iron concentration is into HCl recovery system
System keeps the iron that the leaching of ferrotianium material enters the iron of hydrochloric acid system and organic extraction raffinate brings system into be equal to and shunts the row of burning
The iron of desalination acid system, iron concentration boundary are 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+From leaching
Mother liquor 1 is recycled back into out, and concentration of other impurity (calcium, magnesium, aluminium etc.) in leaching liquid 12 depends on handled ilmenite
Impurity content.
Step b needs preheating leaching liquid 12 to 70~100 DEG C before leaching liquid is mixed with ilmenite, and preheating purpose is to use up
Amount shortens heating time, reduces the possibility that is diluted of leaching liquid, and it is closed to react appearance at one that leaching 12 is mixed with ilmenite
It is carried out in device.
It when step c is filtered, needs first for reaction solution to be cooled to 80-90 DEG C and is filtered again, any one can be used in filtering
Form, such as vacuum filtration or filters pressing.
When step d is shunted, resulting leaching mother liquor is female equal to leaching is burned by the total amount that iron in leaching process enters system
The total amount of iron shunts in liquid.
2, it burns the preconcentrator for leaching mother liquor 2 into waste hydrochloric acid recovery system to be concentrated, cooling bath is entered after concentration
It is cooling, FeCl is removed using filter after cooling2·4H2O crystallization
A. 370~450 DEG C of incinerator outlet of gas enters the progress solid gas separation of cyclone clasfficiator, and soild oxide returns
Incinerator is returned, high-temperature gas 6 enters Venturi preconcentrator and mixes with leaching mother liquor 2 is burned, and burns the moisture leached in mother liquor
25~30% are evaporated, Venturi preconcentrator exit gas is no more than 96 DEG C, burns the liquid for leaching mother liquor after pre-concentration
Claim extraction stoste 7, extraction 7 temperature of stoste is 85-91 DEG C；
B. extraction stoste 7 enters coil pipe cooling bath, carries out being cooled to 30~40 DEG C to it, coolant liquid is that back extraction is used
NaOH solution, while NaOH solution is heated to 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 generated2·4H2O crystallization
8, after separation of solid and liquid, solid FeCl2·4H2Incinerator is sent in O crystallization 8 after merging with extraction lean solution 15, filtrate is extract liquor 13,
Sc therein2O3Concentration is 24-31mg/L, HCl concentration 2.2-3.2mol/L.
3, extraction and the isolated rich scandium solids of back extraction；
A. it extracting: extract liquor 13 being mixed with extractant, the formula of extractant are as follows: the volumetric concentration of P507 is 3-7%,
Middle diluent is sec-octyl alcohol and sulfonated kerosene, and volumetric concentration is respectively 1.5-3.5% and 89.5-96.5%, extraction phase ratio O/A
=0.5, extract 2 grades of series；
B. separate: extract liquor is in extraction process, organic load organic phases that match after scandium is migrated into organic phase, through settling
Or load organic phases 16 and extraction lean solution 15 are obtained after centrifuge separation, extract lean solution 15 and FeCl2·4H2O crystallization 8 returns after merging
Incineration system.
C. wash: load organic phases 16 in addition to being loaded with scandium also entrainment of other impurity, with HCl recovery system mat woven of fine bamboo strips second level
The dilute hydrochloric acid of adsorption tower is made into the hydrochloric acid detergent 9 of 2~4mol/L, and wash conditions are to wash series 3 compared to O/A=3:1
Grade, after separation, washing useless 10 return to HCl recovery system mat woven of fine bamboo strips primary adsorption tower, and purification load organic phases 17 enter back extraction and make
Industry.
D. be stripped: purification load organic phases 17 are stripped, and use NaOH solution 4 for stripping agent, and NaOH solution concentration is 1
~3mol/L, back extraction temperature are 50~70 DEG C, and O/A=2:1 is compared in back extraction, is stripped 2 grades of series, and the organic phase after back extraction returns to extraction
It is taken as industry.
E. filter: the strip liquor after back extraction contains scandium and precipitate metal hydroxides and remaining NaOH solution, strip liquor warp
Rich scandium solids and NaOH solution is obtained by filtration.
4, lean solution 15 and FeCl are extracted2·4H28 mixing of O crystallization and regeneration of hydrochloric acid
Extract lean solution 15 and FeCl2·4H2It is made into that burn liquid to enter incinerator main purpose be recycling hydrochloric acid after O crystallization 8 is mixed,
At being 500~820 DEG C in temperature following hydrolysis, decomposition and oxidation occur for burning, burn liquid and are sprayed from the furnace roof of incinerator by sour rifle
Mouth is sprayed into furnace with mist and is burned, and portion is entered in furnace in a furnace with tangential direction for coal gas and air, is burned liquid and is being burnt
Burning furnace 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 on incinerator bottom due to gravity, and arranges from incinerator bottom
Out, fraction solid particle is taken out by blower from furnace roof portion with the exhaust gas generated after hydrogen chloride gas, vapor and gas-fired
Out, solid particle largely returns in furnace after dedusting, and exhaust gas enters Venturi preconcentrator.
The absorption of hydrogen chloride gas is to separate hydrogen chloride from exhaust gas, makes the process of regeneration of hydrochloric acid, whole process
It is completed in second level (or three-level) absorption tower.The exhaust gas containing hydrogen chloride gas come from Venturi preconcentrator initially enters one
The bottom on grade absorption tower (I) rises, then by first grade absorption tower (I) by supporting the screen of filler in the space detour of packing layer
Top discharge, then, into the bottom of two-level absorption tower (II), the hydrogen chloride gas in exhaust gas is made further to be absorbed,
Finally it is discharged by the top of two-level absorption tower (II).The solution of absorbing hydrogen chloride gas is dilute leaching mother liquor 5, is by partially leaching
Mother liquor is the circulating leaching mother liquor 3 obtained after shunting, the washing filtrate 4 of washing procedure and water supplement or dilute hydrochloric acid composition.
Salt sour waste gas is in absorption tower by dilute 5 counter current absorption of leaching mother liquor: dilute leaching mother liquor 5 is first from two-level absorption tower
(II) top is uniformly sprayed to packing layer upper surface, and the bottom of two-level absorption tower (II) is flowed downward to along filler surface
Then portion, then pumps the top to first grade absorption tower (I) after spraying, be collected in the bottom of first grade absorption tower (I), absorbs chlorination
The solution formed after hydrogen is referred to as to recycle dilute leaching mother liquor 11, is solvable containing iron chloride, calcium chloride, magnesium chloride, manganese chloride etc.
Property chlorate hydrochloric acid compound system solution, ferrous ion concentration be 28~100g/L, concentration of hydrochloric acid increase after absorbing to
16~20%.Dilute pump of leaching mother liquor 11 to leaching liquid preparation process will be recycled and realize Recycling.
Embodiment 1
Using scandium-enriched of the present invention: sample is derived from Fu Tai factory, 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 factory, and the ore pulp of leaching passes through solid-liquid separating machine
(such as diaphragm filter press) separates leaching mother liquor with solid material, and mother liquor (burn and leach mother liquor) is leached into waste hydrochloric acid time in part
The preconcentrator of receipts system, the extraction stoste after concentration enters heat exchanger crystallisation by cooling and filter removes FeCl2·4H2O must simultaneously extract
Liquid is taken, the index for extracting extract liquor used is as shown in table 2.
The chemical group analysis of components of the different mother liquors of table 2
| Feed liquid title | Cl-(g/L) | TFe(g/L) | Sc2O3(mg/L) | HCl(g/L) |
| Leach mother liquor | 276.2 | 140.2 | 20 | 41.7 |
| Extract stoste | 369.7 | 185.3 | 26.3 | 88.5 |
| Extract liquor | 326.9 | 145 | 27.3 | 92.1 |
Sc extraction is carried out to extract liquor, using P507 as extractant, extractant formulation is 5%P507+2.5% Zhong Xin
+ 92.5% sulfonated kerosene of alcohol (volume ratio), extraction phase ratio O/A=0.5 extract 2 grades of series；Use 2mol/l HCl solution as washing
Agent, wash load organic phase are washed, O/A=3 is compared in washing, washs 3 grades of series；Use 2.5mol/l NaOH solution as stripping agent,
O/A=2:1 is compared in load organic phases after back extraction washing, back extraction, and 80 DEG C of stripping agent temperature, 2 grades of series of back extraction is used after back extraction
Rich scandium solids is collected in filter, and the yield situation of whole process scandium is as shown in table 3, and the composition analysis of rich scandium solids is as shown in table 4.
3 hydrochloric acid leaching ilmenite of table produces the Sc recovery (%) of scandium-enriched technique in rich-titanium material process
The composition analysis of the rich scandium solids of table 4
| Ingredient | Al(OH)3 | Fe(OH)3 | Ca(OH)2 | Sc(OH)3 |
| Content % (wt) | 6.31 | 13.85 | 55.83 | 24.01 |
Embodiment 2
It is extract liquor with leaching mother liquor, composition index is such as with the leaching mother liquor scandium-enriched (the comparison present invention) not being concentrated
Shown in table 2.
Sc extraction is carried out to mother liquor is leached, using P507 as extractant, extractant formulation is that 5%P507+2.5% is secondary
+ 92.5% sulfonated kerosene of octanol (volume ratio), extraction phase ratio O/A=0.5 extract 2 grades of series；Use 2mol/l HCl solution as
O/A=3 is compared in detergent, wash load organic phase, washing, washs 3 grades of series；Use 2.5mol/l NaOH solution as back extraction
Agent, the load organic phases after back extraction washing, back extraction compare O/A=2:1,80 DEG C of stripping agent temperature, are 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.
The Sc recovery (%) for leaching scandium-enriched technique in mother liquor that table 5 is never concentrated
The composition analysis of the rich scandium solids of table 6
| Ingredient | Al(OH)3 | Fe(OH)3 | Ca(OH)2 | Sc(OH)3 |
| Content % (wt) | 7.17 | 15.75 | 62.47 | 13.62 |
Embodiment 3
With the scandium in P204 extraction extract liquor: being raw material, analysis of components such as table 2 with 1 extract liquor of embodiment.Work as use
For P204 as extractant, extractant formulation is+85% sulfonated kerosene of 12%P204+3% sec-octyl alcohol (volume ratio), extraction phase ratio O/
A=0.5 extracts 2 grades of series；Use 2mol/l HCl solution as detergent, wash load organic phase washs and compares O/A=3,
3 grades of series of washing；Use 2.5mol/l NaOH solution as stripping agent, O/A is compared in the load organic phases after back extraction washing, back extraction
=2:1, is stripped 2 grades of series by 80 DEG C of stripping agent temperature, collects rich scandium solids with flame filter press after back extraction.Extraction process scandium
Yield situation it is as shown in table 7, the composition analysis of rich scandium solids is as shown in table 8.
Table 7 is enriched with the yield (%) for burning scandium technique in mother liquor with P204 extractant
The composition analysis of the rich scandium solids of table 8
| Ingredient | Al(OH)3 | Fe(OH)3 | Ca(OH)2 | Sc(OH)3 |
| Content % (wt) | 6.23 | 15.15 | 54.27 | 24.35 |
Claims (7)
1. a kind of method of scandium-enriched in hydrochloric acid leaching ilmenite production rich-titanium material process, which is characterized in that include the following steps:
(a) ferrotianium material obtains leaching mother liquor (1) after leaching liquid (12) pressurization leaching, separation of solid and liquid, leaches mother liquor (1) and shunts
At circulating leaching mother liquor (3) and burn leaching mother liquor (2)；
(b) concentration and cooling: burning leaching mother liquor (2) enters preconcentrator and is concentrated, the extraction stoste obtained after concentration
(7), extraction stoste (7) is cooling into crystallisation by cooling slot, removes FeCl through being separated by solid-liquid separation after crystallisation by cooling2·4H2O crystallizes (8),
It obtains extract liquor (13), the cooling medium of the crystallisation by cooling slot is the NaOH solution (14) of 1-3mol/L, the NaOH solution
(14) it is recycled after heat exchange as stripping agent；
(c) extract: extract liquor (13) is extracted using extractant, and hydrochloric acid is used in 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 (I)；The FeCl of extraction lean solution (15) and crystallisation by cooling2·4H2It is rich that O crystal (8) returns to production
The incinerator of HCl recovery system in titanium stream journey；The hydrochloric acid detergent (9) is HCl recovery system two-level absorption tower
(II) regeneration hydrochloric acid；
(d) be stripped: purification load organic phases (17) is stripped with the NaOH solution (14) of 1-3mol/L, the organic phase after back extraction
Return step (c) extraction, the strip liquor after back extraction contain scandium and precipitate metal hydroxides and remaining NaOH solution, filtering back extraction
Liquid obtains rich scandium solids, and filtered alkaline filtrate returns to heat exchanger and is used further to be stripped；
Preconcentrator described in step (b) is gas-liquid mixed evaporator, selects venturi, burns and leaches mother liquor (2) and incinerator
The high-temperature gas (6) of generation is mixed in venturi, is made to burn moisture in leaching mother liquor (2) and is evaporated 25 ~ 30%, obtained extraction
Stoste (7)；
The exhaust gas containing hydrogen chloride gas come from venturi initially enters the bottom of first grade absorption tower (I), by supporting filler
Screen, packing layer space detour rise, then by first grade absorption tower (I) top be discharged, subsequently into two-level absorption tower
(II) bottom makes the hydrogen chloride gas in exhaust gas further be absorbed, and is finally discharged by the top of two-level absorption tower (II)；
The solution of absorbing hydrogen chloride gas is dilute leaching mother liquor (5), is that the circulating leaching mother obtained after mother liquor shunts is leached by part
Liquid (3), the washing filtrate (4) of washing procedure and water supplement or dilute hydrochloric acid composition.
2. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process according to claim 1, feature
It is, 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 process according to claim 1, feature
Be, step (a) leaching liquid (12) be hydrochloric acid solution, wherein HCl concentration be 15 ~ 20wt%, leaching solid-to-liquid ratio be 2.5 ~
4g/mL, leaching process is controlled at 120 ~ 150 DEG C, 0.1 ~ 0.4MPa of pressure, 2 ~ 6h of leaching time；In the leaching mother liquor
Sc2O3Concentration 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 process according to claim 1, feature
It is that the venturi intake air temperature is 250 ~ 450 DEG C, venturi delivery temperature is not more than 96 DEG C, obtained extraction stoste (7)
Temperature is 85 ~ 91 DEG C.
5. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process according to claim 1, feature
It is, the temperature that step (b) the cooling medium NaOH solution (14) goes out cooling bath is 50 ~ 70 DEG C, and extraction stoste (13) is cold out
But the temperature of slot is 30 ~ 40 DEG C；Sc in the extract liquor (13)2O3Concentration is 24 ~ 31mg/L, 2.2 ~ 3.2mol/L of HCl concentration.
6. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process according to claim 1, feature
It is, the composition of step (c) extractant are as follows: the volumetric concentration of P507 or P204 is 3-12%, and sec-octyl alcohol volumetric concentration is
1.5-3.5%, surplus are sulfonated kerosene；Extraction phase ratio O/A=0.2 ~ 0.8, wherein O is organic 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, washs 2 ~ 4 grades of series.
7. a kind of method that hydrochloric acid leaching ilmenite produces scandium-enriched in rich-titanium material process according to claim 1, feature
It is, 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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