CN108149015A - A kind of method of valuable constituent element in oxygen-enriched Selectively leaching extraction vanadium titano-magnetite - Google Patents
A kind of method of valuable constituent element in oxygen-enriched Selectively leaching extraction vanadium titano-magnetite Download PDFInfo
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- CN108149015A CN108149015A CN201810035224.4A CN201810035224A CN108149015A CN 108149015 A CN108149015 A CN 108149015A CN 201810035224 A CN201810035224 A CN 201810035224A CN 108149015 A CN108149015 A CN 108149015A
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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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- 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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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The method of valuable constituent element, carries out according to the following steps in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite：(1) it is placed in autoclave with sodium hydroxide solution after vanadium titano-magnetite is crushed, is passed through oxygen, heating, which is stirred and kept the temperature, completes alkali leaching；(2) material filtering detaches after alkali is soaked, and caustic digestion slag charge is made in the washing of caustic digestion product；(3) ammonium salt is added in into alkali immersion liquid, stands and is precipitated, vanadium oxide is made in solid phase drying calcining；(4) caustic digestion slag charge and hydrochloric acid autoclave, addition crystal seed heating, which is stirred and kept the temperature, completes acidleach hydrolysis；(5) it is separated by filtration, is calcined after hydrolysate washing drying and titanium oxide is made.The method of the present invention realizes recycling for resource, does not generate industrial wastewater, waste residue realizes green production；Realize green circulatory, energy-saving and emission-reduction.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, and in particular to a kind of oxygen-enriched Selectively leaching extraction v-ti magnetite
The method of valuable constituent element in ore deposit.
Background technology
Vanadium is located at the 4th period, VB races, atomic number 23 in the periodic table of elements, and atomic weight 50.9415 belongs to
High-melting-point element in transition metals；Vanadium has many oxide, and the oxide of industrial vanadium is mainly with V2O2、V2O3、
V2O4, particularly V2O5Form exist, into 20th century, Britain produces the steel alloy containing vanadium for the first time, in the application field of vanadium
It makes a breakthrough first；Battery industry is subsequently applied to, as one of most promising new energy storage or saving system, while vanadium titanium at present
The important meals alloy Ti-6A1-4V of composition is widely used in the fields such as military affairs, aviation, superconduction, nuclear reactor；Vanadium is in the earth's crust
Total content come the 22nd of metal, although content is many, disperse very much, so far without finding individual navajoite；It is led
Will with some metallic ore symbiosis, the vanadium rich reserves in China, mainly using vanadium titano-magnetite and culm as industrial
Raw material.
Ti content accounts for about the 0.61% of earth crustal mass, is arranged by elemental abundance in the earth's crust, is after aluminium, iron, magnesium
Four bit architecture metals；Its chemical property is active, in nature without elemental stage, with compound forms such as oxide, titanates
Be widely present in seawater, soil, rock, in animal and plant body；Although the mineral of titaniferous are numerous, industrially it is applied at present
Mainly ilmenite, vanadium titano-magnetite and rutile ore；It is distributed in titaniferous ore in the earth's crust most extensively, reserves maximum is titanium
Iron ore accounts for 80% or so of titanium ore resource and prepares the primary raw material of titanium products；More than 90% titanium ore is used in the world at present
In production titanium dioxide, for producing Titanium, remaining ilmenite is used to manufacture welding rod, alloy, carbonization about 4~5% titanium ore
Object, ceramics, glass and chemicals etc.；The entitled titanium dioxide of titanium dioxide chemistry, is a kind of white inorganic pigment, has nontoxic, nothing
Harmful, best opacity, best whiteness and brightness, it is considered to be a kind of best white face of current performance in the world
Material is widely used in coating, the industry such as plastics, papermaking, printing ink, chemical fibre, rubber, cosmetics.
Vanadium titano-magnetite is a kind of based on iron (Fe), vanadium (V), titanium (Ti), a variety of valuable elements of association such as cobalt (Co), nickel
(Ni), the Pluralistic and semiotiC iron ore of chromium (Cr), copper (Cu), scandium (Sc), gallium (Ga) etc., due to the close symbiosis of Fe, Ti, V is same with class matter
The form preservation of elephant is in titanomagnetite, therefore, commonly referred to as vanadium titano-magnetite.Vanadium titano-magnetite is current production vanadium, titanium smelting
The main resource of refining can recycle vanadium therein, iron, titanium.V-ti magnetite mineral deposit is extensive in distribution in China, rich reserves,
Reserves and yield occupy the third position of national iron ore, 61.9 hundred million tons of proven reserve, and the whole nation of standing verifies the 11.6% of iron reserves.This
Class mineral deposit is mainly distributed on the areas such as Sichuan Xichang Region, Chengde area, Hubei Yun county sun, Xiangyang.
Mainly there are two methods of pyrogenic process and wet method currently with the main side of vanadium titano-magnetite vanadium extraction, thermal process is by vanadium
Titanomagnetite is smelted in blast furnace or electric furnace obtains pig iron containing vanadium, then made with the method for selective oxidation the vanadium in molten iron aoxidize into
Enter clinker, with the further vanadium extraction of obtained vanadium containing slag；Wet method is that vanadium titano-magnetite is carried out roasting pretreatment, by v-ti magnetite
Multivalent state v element in ore deposit is converted into the water soluble salt of pentavalent v element under the auxiliary of sodium salt, calcium salt or oxygen, so
Water logging is carried out to the obtained slag by calcination process afterwards or acidleach, the water soluble salt and partial impurities metal salt of vanadium enter
In leachate, the processing that ammonium salt or calcium salt precipitation method are added in after purification of leaching liquor can be obtained to the precipitation of vanadic acid compound, be
Purer product is obtained, needs to carry out thick vanadic anhydride alkali soluble and removal of impurities processing, and carry out the secondary precipitation of ammonium salt, it can
Purer ammonium metavanadate is obtained, the vanadic anhydride of high-purity is obtained after roasting；Wet processing is high with total recovery
Feature；Supplying sodium salt, oxidizing roasting after the patent proposition of application number 201010188625.7 crushes ore or concentrate, by vanadium and
Chromium is converted into water-soluble sodium vanadate and sodium chromate, and in water logging to solution, separation vanadium chromium obtains vanadic anhydride from solution
With chrome green product；Residue can be incorporated coal dust pelletizing after leaching, and through reduction, magnetic separation separation iron and titanium obtain magnetic powder
It can be as the raw material of powder metallurgy or steel-making and containing TiO2Non-magnetic product more than 50% is as the raw material for carrying titanium；This method
Roasting technique will consume big energy, it is more through vanadic anhydride made from this method, iron, titanium oxide impurities, be
Primary industry raw material, added value of product are low；The patent of application number 201310183580.8 mentions wet-treating v-ti magnetite concentrate
The method for preparing titanium liquid, by v-ti magnetite concentrate and mixed in hydrochloric acid, leaching obtains intermediate pulp, intermediate pulp is obtained by filtration
Leachate and leached mud are then washed, and filter to obtain wash water and washery slag, and washery slag is carried out fused salt reaction, obtain fused salt reaction
Material；Fused salt reaction material is washed, is filtered, obtains washing material；Washing is expected that carrying out pickling obtains slurry, is obtained by filtration pickling
Material；By pickling material with sulfuric acid solution carry out acid it is molten, obtain acid it is molten after material；The molten rear material of acid is added in sulfuric acid solution and is soaked
It takes, the leaching liquid for filtering acquisition is titanium liquid；This method have ignored in vanadium titano-magnetite contained a large amount of iron containing compounds and
A variety of high added value metallic elements, resource utilization are relatively low.
Invention content
According to the research to existing v-ti magnetite ore production technology, the present invention proposes a kind of oxygen-enriched Selectively leaching extraction vanadium
The method of valuable constituent element in titanomagnetite, it is living using machinery using sodium hydroxide, hydrochloric acid as solvent using vanadium titano-magnetite as raw material
The enhanced leachings means such as change, oxygen-enriched, high pressure carry out high-pressure oxygen-enriched alkali leaching to vanadium titano-magnetite,High pressure acidleach, prepare titanium white
Powder prepares the TiO of high-purity through subsequent purification and transformation of crystal2；Ammonium salt precipitation is carried out to v element valuable in leachate
High-purity vanadium oxide is made in recycling, roasting, realizes the enrichment of v element, reduces energy consumption, effectively reduces the acid of leaching process
Alkali concn, and recycled and realize recycling, while improve equipment operating condition for resource, extend service life of equipment.
The method of the present invention carries out according to the following steps：
1st, vanadium titano-magnetite is crushed to granularity≤0.125mm, obtains v-ti magnetite miberal powder；By v-ti magnetite miberal powder and hydrogen
Sodium hydroxide solution is placed in alkali leaching autoclave, and wherein the mass concentration of sodium hydroxide solution is 20~40%, and sodium hydroxide is molten
The ratio of liquid and v-ti magnetite miberal powder is (5~15) by liquid-solid ratio:1；Oxygen is passed through into alkali leaching autoclave, is then heated to
200~300 DEG C, 1~3h is kept the temperature under agitation, completes alkali leaching；2nd, the material filtering separation after alkali is soaked, obtains caustic digestion
Product and alkali immersion liquid；Caustic digestion product is washed to filtrate as neutrality, caustic digestion slag charge is made；
3rd, ammonium salt is added in into alkali immersion liquid, addition presses the VO in alkali immersion liquid4 3+With the NH in ammonium salt4 +Molar ratio be 1:
3, it stands to precipitation completely is precipitated, is separated by filtration and obtains solid phase and liquid phase；Solid phase drying is removed into moisture removal, then forge at 850 ± 5 DEG C
30~60min is burnt, vanadium oxide is made；
4th, caustic digestion slag charge and hydrochloric acid are placed in acidleach autoclave, wherein the mass concentration of hydrochloric acid is 14~20%,
The ratio of hydrochloric acid and caustic digestion slag charge is (4~10) by liquid-solid ratio:1；To acidleach with crystal seed is added in autoclave, convenient for caustic digestion
The titanium oxide forming core that slag charge is formed in hydrochloric acid hydrolytic process is grown up, and then heats to 120~150 DEG C, under agitation
1~3h is kept the temperature, completes acidleach hydrolysis；
5th, the material filtering separation after acidleach is hydrolyzed, obtains hydrolysate and pickle liquor；Hydrolysate is washed to filter
Liquid is neutrality, then dries moisture removal, finally calcines 30~60min at 800~900 DEG C, titanium oxide is made.
In the above method, the liquid phase that step 3 obtains removes SiO by the use of CaO as precipitating reagent2, calcium silicates byproduct is recycled, when
SiO in liquid phase2During weight percent≤0.05%, used as sodium hydroxide solution return to step 1.
Above-mentioned crystal seed is titanium dioxide and/or metatitanic acid, and addition is the 0.2~0.5% of caustic digestion slag charge total weight.
In the above method, after the pickle liquor heating evaporation of acquisition, by volatile hydrogen chloride extra in pickle liquor out through inhaling
It is 14~20% that hydrochloric acid made of receipts, which is concentrated into weight concentration, and return to step 4 uses.
Above-mentioned vanadium oxide purity >=95%.
Above-mentioned titanium oxide purity >=98.5%, granularity is at 0.1~13 micron.
Remaining material is separated into individual metal salt solution using the method for extraction after above-mentioned pickle liquor heating evaporation, will
Metal salt solution uses electrolytic tank electrolysis, and High Purity Hydrogen oxide precipitation is respectively prepared；By taking Fe as an example, due to Fe3+Ion concentration compared with
Height to prevent iron hydroxide from reuniting, adds in a small amount of iron oxide red, while carry out mechanical agitation to electric tank cathode area before except iron,
Cathodic region electrolyte and hydroxide directed flow, are filtered at this time by filter device, realize separation of solid and liquid, filtrate cycle
Cathodic region is returned to, superfine high-purity iron oxide red is made；According to identical principle, impurities metal ion is removed respectively；Due to metal
Its activity of salting liquid impurities metal ion is located at H+Later, contain a large amount of Cl in electrolytic process in leachate-, so electrolysis
Hydrogen and chlorine generation are had between slot two-stage；Anode and cathode gas are collected, obtains byproduct hydrogen and chlorine；Drying filtering
Electrolysate obtains impurity hydrogen-oxygen produce product or obtains metal oxide products after electrolysate is calcined.
The key reaction that the method that electricity conversion is directly separated hydroxide precipitation is related to is as follows：
Anode reaction：2Cl-- 2e=Cl2↑,
Cathode reaction：2H++ 2e=H2↑,
Overall reaction：MeCl2+2H2O=Me (OH)2+H2+Cl2,
Calcination reaction：Me (OH)=MeO+H2O↑。
The principle of the present invention and advantageous effect are：
(1) oxygen is passed through in leaching process, the titanium, iron, barium oxide of vanadium titano-magnetite middle or low price can be aoxidized,
Stable magnetic iron ore ore deposit phase is destroyed, the impurity element of Dispersed precipitate in the solid solution is made to be combined into the compound that can be melted into soda acid,
It is separated off in subsequent washing filtration stage；
(2) in leaching process guarantee system seal, with oxygen be passed through or the lasting raising of temperature, produce in kettle
Raw larger air pressure significantly optimizes the dynamic conditions of leaching process, vanadium titano-magnetite oxidation, impurity is precipitated, ore deposit
The destruction of phase has facilitation, as enhanced leaching a kind of means coefficient with other extract technology parameters
In the process, the process conditions such as temperature, acid-base value, extraction time can be suitably reduced, reach environmental protection and energy saving purpose；
(3) alkali leaching is first carried out to vanadium titano-magnetite, there can be certain destruction to slag particle surface, be conducive to the analysis of impurity phase
Go out, enhance the effect of follow-up acidleach, while leach using soda acid distribution, more simple acidleach, the impurity of the oxides such as Si, Al is gone
Except rate can greatly increase, the removal of impurities pressure of subsequent production technology is greatly reduced, it is easily prepared go out high performance material, it is while rich
Oxygen acidleach can be the Fe in leachate2+Oxidation can improve the heavy iron process efficiency of later stage electricity conversion；
(4) for the alkali used for sodium hydroxide, the spent lye that alkali leaching generates in the process can add a small amount of ammonium salt, you can will wherein
Vanadic acid radical ion be precipitated with precipitation form, filtering be enriched with it；After add in a small amount of CaO generation calcium silicates and have Si impurity
Effect removes, and realizes the purpose of barium oxide enrichment and removal of impurities, while the lye after filtering concentrated can continue on for vanadium titanium magnetic
Iron ore alkali soaks, and realizes recycling for resource；Acidleach process hydrochloric acid, the spent acid of generation is heated, while is inhaled using water atomization
The HCl gases that heating volatilizes are received, the hydrochloric acid solution of formation is concentrated to return to extract technology, realizes recycling for resource,
It is nearly free from industrial wastewater, waste residue realizes green production；
(5) each foreign ion can be detached using principle is extracted and carries out electric conversion, metal oxide or hydrogen obtained
Oxide purity is higher, and ultra-fine high pure oxide can be made, while be electrolysed and can generate valuable byproduct through drying, calcining
Hydrogen, chlorine, the acid leaching solution through removal of impurities are recycled into technological process, realize green circulatory, energy-saving and emission-reduction.
Specific embodiment：
It is used to prepare in the embodiment of the present invention by the use of CaO as precipitating reagent and silicate ion generation precipitated calcium silicate in lye
Cement.
The alkali leaching autoclave used in the embodiment of the present invention is the ZRYK 1L of Zheng Wei mechanical equipments Co., Ltd of Weihai City
Type stainless steel nickel plating autoclave.
The acidleach autoclave used in the embodiment of the present invention is the KCFD1-10 of Yantai Ke Li Chemical Equipment Co., Ltd.s
Type zirconium matter autoclave.
Ilmenite concentrate crushing plant is the 5/4 classic line of pulverisette of FRITSCH in the embodiment of the present invention
Type planetary high-energy ball mill.
Liquid-solid ratio in the embodiment of the present invention is the volume and solid material of liquid material (sodium hydroxide solution or hydrochloric acid)
The weight ratio of (v-ti magnetite miberal powder or caustic digestion slag charge), unit L/kg.
Mixing speed when alkali soaks in the embodiment of the present invention is 500r/min, and mixing speed when acidleach hydrolyzes is 300r/
min。
The titanium dioxide and metatitanic acid used in the embodiment of the present invention is analytical reagents purchased in market.
Remaining material is separated into individual metal salt using extracting process after pickle liquor heating evaporation in the embodiment of the present invention
By metal salt solution using electrolytic tank electrolysis (20 DEG C of temperature, tank voltage 20V), High Purity Hydrogen oxide precipitation is respectively prepared in solution；
By taking Fe as an example, due to Fe3+Ion concentration is higher, to prevent iron hydroxide from reuniting, a small amount of iron oxide red is added in before except iron, while right
Electric tank cathode area carries out mechanical agitation, cathodic region electrolyte and hydroxide directed flow, is carried out at this time by filter device
Separation of solid and liquid is realized in filtering, and filtrate cycle returns to cathodic region, and superfine high-purity iron oxide red is made；According to identical principle, remove respectively
Impurities metal ion；Due to metal salt solution impurities metal ion, its activity is located at H+Later, it is soaked in electrolytic process
Go out and contain a large amount of Cl in liquid-, so having hydrogen and chlorine generation between electrolytic cell two-stage；Anode and cathode gas are collected, is obtained
Obtain byproduct hydrogen and chlorine；Drying filtering electrolysate obtains impurity hydrogen-oxygen produce product or is obtained after electrolysate is calcined
Metal oxide products, purity >=95%.
With reference to embodiment, the present invention is described in further detail.
The vanadium titano-magnetite used in the specific embodiment of the invention contains TiO by weight percentage212.8%, SiO2
3.83%, CaO 1.16%, MgO 3.22%, TFe 53.7%, MnO 0.24%, Al2O32.86%, V2O50.53%.
Embodiment 1
Vanadium titano-magnetite is crushed to granularity≤0.125mm, obtains v-ti magnetite miberal powder；By v-ti magnetite miberal powder and hydrogen-oxygen
Change sodium solution to be placed in alkali leaching autoclave, wherein the mass concentration of sodium hydroxide solution is 20%, sodium hydroxide solution and vanadium
The ratio of titanomagnetite powder is 5 by liquid-solid ratio:1；Oxygen is passed through into alkali leaching autoclave, then heats to 200 DEG C, is being stirred
Under the conditions of keep the temperature 3h, complete alkali leaching；Material filtering separation after alkali is soaked, obtains caustic digestion product and alkali immersion liquid；By caustic digestion
Product is washed to filtrate and caustic digestion slag charge is made for neutrality；
Ammonium salt is added in into alkali immersion liquid, addition presses the VO in alkali immersion liquid4 3+With the NH in ammonium salt4 +Molar ratio be 1:3,
It stands to precipitation completely is precipitated, is separated by filtration and obtains solid phase and liquid phase；Solid phase drying is removed into moisture removal, then in 850 ± 5 DEG C of calcinings
Vanadium oxide, purity 96.5% is made in 30min；The washing lotion generated after wherein washing is added to after collection in alkali immersion liquid；Liquid phase
SiO is removed by the use of CaO as precipitating reagent2, as SiO in liquid phase2During weight percent≤0.05%, recycled as sodium hydroxide solution
It uses；
Caustic digestion slag charge and hydrochloric acid are placed in acidleach autoclave, wherein the weight concentration of hydrochloric acid is 14%, hydrochloric acid with
The ratio of caustic digestion slag charge is 10 by liquid-solid ratio:1；To acidleach with crystal seed is added in autoclave, convenient for caustic digestion slag charge in hydrochloric acid
The titanium oxide forming core formed in hydrolytic process is grown up, and is warming up to 120 DEG C, keeps the temperature 3h under agitation, completes acidleach hydrolysis；
Crystal seed is titanium dioxide, and the addition of crystal seed is the 0.5% of caustic digestion slag charge total weight；
Material filtering separation after acidleach is hydrolyzed, obtains hydrolysate and pickle liquor；Hydrolysate is washed to filtrate
For neutrality, then moisture removal is dried, finally calcine 30min at 900 DEG C, titanium oxide is made；After pickle liquor heating evaporation, it will volatilize
Hydrogen chloride gas out is absorbed with water atomization, and it is 14% that manufactured hydrochloric acid, which is concentrated into mass concentration, is recycled；Titanium oxide is pure
It is 98.5% to spend, by mass percentage containing SiO20.31%, CaO 0.07%, MgO 0.96%, TFe 3.6%, Mn
0.18%；Granularity is 0.16~4.29 micron.
Embodiment 2
With embodiment 1, difference is method：
(1) weight concentration of sodium hydroxide solution is 30%, and the ratio of sodium hydroxide solution and v-ti magnetite miberal powder presses liquid
Gu than being 10:1；Alkali soaks 250 DEG C of temperature, time 2h；(2) 40min is calcined after solid phase drying, vanadium oxide, purity 97.2% is made；
(3) mass concentration of hydrochloric acid is 18%, and it is 8 that the ratio of hydrochloric acid and caustic digestion slag charge, which presses liquid-solid ratio,:1；Alkali immersion solution
130 DEG C of temperature, time 2h；Crystal seed is metatitanic acid, and addition is the 0.3% of caustic digestion slag charge total weight；
(4) by after hydrolysate washing drying, 40min is calcined at 850 DEG C；Hydrochloric acid made of absorbing hydrogen chloride gas concentrates
It is 18% to weight concentration；Titanium oxide purity is 98.7%, by mass percentage containing SiO20.22%, CaO 0.07%, MgO
0.64%, TFe 2.1%, Mn 0.16%；Granularity is 0.5~12 micron.
Embodiment 3
With embodiment 1, difference is method：
(1) mass concentration of sodium hydroxide solution is 40%, and the ratio of sodium hydroxide solution and v-ti magnetite miberal powder presses liquid
Gu than being 15:1；Alkali soaks 300 DEG C of temperature, time 1h；(2) 60min is calcined after solid phase drying, vanadium oxide, purity 96.7% is made；
(3) mass concentration of hydrochloric acid is 20%, and it is 4 that the ratio of hydrochloric acid and caustic digestion slag charge, which presses liquid-solid ratio,:1；Alkali immersion solution
150 DEG C of temperature, time 1h；Crystal seed is titanium dioxide and the grade mass mixings object of metatitanic acid, and addition is total for caustic digestion slag charge
The 0.2% of weight；
(4) after hydrolysate washing drying, 60min is calcined at 800 DEG C；Hydrochloric acid is concentrated into made of absorbing hydrogen chloride gas
Mass concentration is 20%, is recycled；Titanium oxide purity is 98.9%, by mass percentage containing SiO20.18%, CaO
0.07%, MgO 0.32%, TFe 1.5%, Mn<0.05%；Granularity is 0.8~13 micron.
Claims (6)
1. a kind of method of valuable constituent element in oxygen-enriched Selectively leaching extraction vanadium titano-magnetite, it is characterised in that according to the following steps into
Row：
(1) vanadium titano-magnetite is crushed to granularity≤0.125mm, obtains v-ti magnetite miberal powder；By v-ti magnetite miberal powder and hydrogen-oxygen
Change sodium solution to be placed in alkali leaching autoclave, wherein the mass concentration of sodium hydroxide solution is 20~40%, sodium hydroxide solution
It is (5~15) to press liquid-solid ratio with the ratio of v-ti magnetite miberal powder:1；Oxygen is passed through into alkali leaching autoclave, is then heated to
200~300 DEG C, 1~3h is kept the temperature under agitation, completes alkali leaching；(2) the material filtering separation after alkali is soaked, obtains alkali point
Solve product and alkali immersion liquid；Caustic digestion product is washed to filtrate as neutrality, caustic digestion slag charge is made；
(3) ammonium salt is added in into alkali immersion liquid, addition presses the VO in alkali immersion liquid4 3+With the NH in ammonium salt4 +Molar ratio be 1:3, it is quiet
It puts to precipitation and is precipitated completely, be separated by filtration and obtain solid phase and liquid phase；Solid phase drying is removed into moisture removal, then calcine 30 at 850 ± 5 DEG C
~60min, is made vanadium oxide；
(4) caustic digestion slag charge and hydrochloric acid are placed in acidleach autoclave, wherein the mass concentration of hydrochloric acid is 14~20%, hydrochloric acid
It is (4~10) to press liquid-solid ratio with the ratio of caustic digestion slag charge:1；To acidleach with crystal seed is added in autoclave, convenient for caustic digestion slag charge
The titanium oxide forming core formed in hydrochloric acid hydrolytic process is grown up, and is warming up to 120~150 DEG C, under agitation keep the temperature 1~
3h completes acidleach hydrolysis；
(5) the material filtering separation after acidleach is hydrolyzed, obtains hydrolysate and pickle liquor；Hydrolysate is washed to filtrate is
Neutrality, then moisture removal is dried, 30~60min finally is calcined at 800~900 DEG C, titanium oxide is made.
2. the method for valuable constituent element in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite according to claim 1,
It is characterized in that the liquid phase that step (3) obtains removes SiO by the use of CaO as precipitating reagent2, recycle calcium silicates byproduct；As SiO in liquid phase2
During mass percent≤0.05%, used as sodium hydroxide solution return to step (1).
3. the method for valuable constituent element in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite according to claim 1,
It is titanium dioxide and/or metatitanic acid to be characterized in that the crystal seed, and addition is the 0.2~0.5% of caustic digestion slag charge total weight.
4. the method for valuable constituent element in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite according to claim 1,
After being characterized in that the pickle liquor heating evaporation that step (5) obtains, by extra volatile hydrogen chloride out made of water atomization absorbs
It is 14~20% that hydrochloric acid, which is concentrated into weight concentration, and return to step 4 uses.
5. the method for valuable constituent element in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite according to claim 1,
It is characterized in that vanadium oxide purity >=95%.
6. the method for valuable constituent element in a kind of oxygen-enriched Selectively leaching extraction vanadium titano-magnetite according to claim 1,
It is characterized in that titanium oxide purity >=98.5%, granularity is at 0.1~13 micron.
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| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
| WO2019137542A1 (en) * | 2018-01-15 | 2019-07-18 | 东北大学 | Method for selectively leaching and upgrading high-titanium slag |
| WO2019137544A1 (en) * | 2018-01-15 | 2019-07-18 | 东北大学 | Method for extracting valent component in vanadium titanium magnetite by means of oxygen-rich selective leaching |
| CN113355511A (en) * | 2021-06-01 | 2021-09-07 | 四川省有色矿冶科技有限公司 | Method for selectively reducing vanadium and titanium content in vanadium-titanium magnetite concentrate through ammonium-ammonia oxidation leaching system |
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| CN114480881A (en) * | 2022-01-18 | 2022-05-13 | 龙佰集团股份有限公司 | Method for extracting valuable elements in iron ore concentrate by wet-fire combined process |
| CN114480881B (en) * | 2022-01-18 | 2023-12-12 | 龙佰集团股份有限公司 | Method for extracting valuable elements from iron concentrate by wet-fire combined process |
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