WO2019137544A1 - 一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法 - Google Patents

一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法 Download PDF

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WO2019137544A1
WO2019137544A1 PCT/CN2019/071694 CN2019071694W WO2019137544A1 WO 2019137544 A1 WO2019137544 A1 WO 2019137544A1 CN 2019071694 W CN2019071694 W CN 2019071694W WO 2019137544 A1 WO2019137544 A1 WO 2019137544A1
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alkali
vanadium
leaching
acid
titanium
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French (fr)
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张廷安
豆志河
刘燕
张子木
王艳秀
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东北大学
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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
    • 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
    • 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
    • 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
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of non-ferrous metallurgy, and particularly relates to a method for extracting valuable components in vanadium-titanium magnetite by oxygen-rich selective leaching.
  • Vanadium is located in the 4th cycle of the periodic table, VB group, its atomic number is 23, atomic weight is 50.9415, which belongs to the high melting point element in the excessive metal element; vanadium has various oxides, and the industrial vanadium oxide is mainly V.
  • Titanium content accounts for about 0.61% of the crustal mass. It is ranked as the fourth structural metal after aluminum, iron and magnesium according to the abundance of elements in the earth's crust. Its chemical nature is active, and there is no elemental state in nature. Compounds such as acid salts are widely found in seawater, soil, rocks, animals and plants; although there are many minerals containing titanium, the main applications in the industry are ilmenite, vanadium-titanium magnetite and rutile ore; The most widely distributed titanium-containing minerals are ilmenite, accounting for about 80% of titanium ore resources. It is also the main raw material for the preparation of titanium products; currently more than 90% of the world's titanium ore is used to produce titanium dioxide.
  • Titanium dioxide is chemically known as titanium dioxide and is a white inorganic pigment. It is non-toxic, harmless, optimal opacity, best whiteness and brightness. It is considered to be the best white pigment in the world. It is widely used in coatings, plastics, paper and printing. Ink, chemical fiber, rubber, cosmetics and other industries.
  • Vanadium-titanium magnetite is mainly composed of iron (Fe), vanadium (V) and titanium (Ti), accompanied by various valuable elements such as cobalt (Co), nickel (Ni), chromium (Cr), copper ( Multi-symbiotic iron ore of Cu), strontium (Sc), gallium (Ga), etc., due to the close symbiosis of Fe and Ti, V is present in the form of isomorphism in the titanomagnetite. magnetite.
  • Vanadium-titanium magnetite is currently the main resource for the production of vanadium and titanium, and can recycle vanadium, iron and titanium. Vanadium-titanium magnetite deposits are widely distributed in China, with abundant reserves.
  • the reserves and production volume ranks third in the national iron ore mines.
  • the proven reserves are 6.19 billion tons, accounting for 11.6% of the country's proven iron reserves.
  • Such deposits are mainly distributed in Xichang area of Panzhihua, Sichuan, Chengde area of Hebei, Fuyang, Hubei and Fuyang.
  • the main methods for extracting vanadium from vanadium-titanium magnetite are mainly fire method and wet method.
  • the fire method is to smelt vanadium-titanium magnetite in blast furnace or electric furnace to obtain vanadium-containing pig iron, and then selectively oxidize.
  • the method further oxidizes vanadium in the molten iron into the slag, and further extracts vanadium from the obtained vanadium-containing slag;
  • the wet method comprises pre-treating the vanadium-titanium magnetite, and the multivalent vanadium element in the vanadium-titanium magnetite is It is converted into a water-soluble salt of pentavalent vanadium with the aid of sodium salt, calcium salt or oxygen, and then the slag obtained by calcination is subjected to water immersion or acid leaching, and the water-soluble salt of vanadium and a part of impurity metal salt enter the leaching solution.
  • the vanadium acid compound can be precipitated.
  • the crude vanadium pentoxide needs to be subjected to alkali dissolution and impurity removal treatment, and ammonium is carried out.
  • the second precipitation of vanadium salt can obtain the pure ammonium ammonium metavanadate, and the high purity vanadium pentoxide is obtained after calcination; the wet process has the characteristics of high total yield; the patent No. 201010188625.7 proposes the ore or concentrate.
  • vanadium and chromium After being crushed, it is mixed with sodium salt, oxidized and calcined, and vanadium and chromium are converted into water-soluble sodium vanadate and sodium chromate. The water is immersed in the solution, and vanadium chromium is separated from the solution to obtain vanadium pentoxide and trioxide.
  • Chromium product; residue after leaching can be blended into pulverized coal pelletizing, reduction, magnetic separation of iron and titanium, magnetic iron powder can be used as raw material for powder metallurgy or steelmaking, and non-magnetic products containing TiO 2 greater than 50%
  • the raw material for titanium extraction; the calcination process of the method consumes a large amount of energy, and the vanadium pentoxide, iron and titanium oxide prepared by the method contain more impurities, which are primary industrial raw materials, and the added value of the product is low; application number 201310183580.8
  • the washing water and the washing residue are filtered, and the washing residue is subjected to a molten salt reaction to obtain a molten salt reaction material; the molten salt reaction material is washed with water and filtered to obtain a water washing material; the water washing material is pickled to obtain a slurry, and the mixture is filtered to obtain pickling.
  • Acid The washing material is acid-dissolved with sulfuric acid solution to obtain an acid-soluble material; the acid-dissolved material is added to the sulfuric acid solution for leaching, and the obtained leaching liquid is titanium liquid; the method ignores the vanadium-titanium magnetite Contains a large amount of iron-containing compounds, and a variety of high value-added metal elements, low resource utilization.
  • the invention provides a method for extracting valuable components in vanadium-titanium magnetite by oxygen-rich selective leaching, using vanadium-titanium magnetite as raw material to oxidize Sodium and hydrochloric acid are used as solvents, and the vanadium-titanium magnetite is subjected to high-pressure oxygen-enriched alkali leaching and high-pressure acid leaching to prepare titanium dioxide by mechanical activation, oxygen enrichment and high pressure, and is prepared by subsequent purification and crystal transformation.
  • High purity TiO 2 is obtained ; the vanadium element in the leachate is subjected to ammonium salt precipitation recovery and calcination to obtain high-purity vanadium oxide, thereby enriching vanadium elements, reducing energy consumption, and effectively reducing the acid-base concentration in the leaching process, and Recycling to achieve recycling of resources, while improving equipment working conditions and extending equipment life.
  • the vanadium-titanium magnetite is crushed to a particle size of ⁇ 0.125 mm to obtain a vanadium-titanium magnetite powder; the vanadium-titanium magnetite powder and the sodium hydroxide solution are placed in an autoclave for caustic soaking, wherein the sodium hydroxide solution
  • the mass concentration is 20-40%, the ratio of sodium hydroxide solution to vanadium-titanium magnetite powder is (5-15):1; oxygen is introduced into the autoclave for alkali leaching, and then the temperature is raised to 200 ⁇ At 300 °C, the mixture is kept under stirring for 1 to 3 hours to complete the alkali leaching; 2.
  • the alkali leached material is separated by filtration to obtain the alkali decomposition product and the alkali immersion liquid; the alkali decomposition product is washed with water until the filtrate is neutral, and the alkali is formed into a base. Decompose slag;
  • the alkali decomposition slag and hydrochloric acid in the acid leaching autoclave wherein the concentration of hydrochloric acid is 14 to 20%, the ratio of hydrochloric acid to alkali decomposition slag according to liquid-solid ratio (4 ⁇ 10): 1;
  • the seed crystal is added to the autoclave for acid leaching to facilitate the growth of the titanium oxide nucleation formed by the alkali decomposition slag during the hydrolysis of hydrochloric acid, and then the temperature is raised to 120-150 ° C, and the mixture is kept under stirring for 1 to 3 hours to complete the acid.
  • the acid leached and hydrolyzed material is separated by filtration to obtain a hydrolyzate and an acid leaching solution; the hydrolyzed product is washed with water until the filtrate is neutral, and then dried to remove water, and finally calcined at 800 to 900 ° C for 30 to 60 minutes to be oxidized. titanium.
  • the liquid phase obtained in the step 3 is used to remove SiO 2 by using CaO as a precipitating agent, and the calcium silicate by-product is recovered.
  • the weight percentage of SiO 2 in the liquid phase is ⁇ 0.05%, it is returned to the step 1 as a sodium hydroxide solution.
  • the above seed crystal is titanium dioxide and/or metatitanic acid in an amount of 0.2 to 0.5% by weight based on the total weight of the alkali decomposition slag.
  • the excess hydrogen chloride in the acid immersion liquid is volatilized, and the hydrochloric acid prepared by absorption is concentrated to a weight concentration of 14 to 20%, and is returned to the step 4.
  • the above vanadium oxide purity is ⁇ 95%.
  • the above titanium oxide has a purity of ⁇ 98.5% and a particle size of 0.1 to 13 ⁇ m.
  • the material remaining after the above-mentioned acid immersion liquid is heated and evaporated is separated into a single metal salt solution by extraction, and the metal salt solution is electrolyzed by an electrolytic cell to prepare a high-purity hydroxide precipitate; for example, Fe is used as a Fe 3+ ion concentration.
  • Fe is used as a Fe 3+ ion concentration.
  • a small amount of iron red is added before iron removal, and the cathode area of the electrolytic cell is mechanically stirred, and the electrolyte and hydroxide in the cathode area are directed to flow, and then filtered by a filtering device to achieve solidification.
  • the liquid is separated, and the filtrate is recycled to the cathode region to obtain ultrafine high-purity iron red.
  • the impurity metal ions are separately removed; since the metal salt solution contains impurities, the metal ions have their activities after H + , and the leaching solution is in the electrolysis process. Containing a large amount of Cl - , so there will be hydrogen and chlorine gas between the two stages of the electrolysis cell; collecting anode and cathode gases to obtain by-product hydrogen and chlorine; drying and filtering the electrolysis product to obtain impurity hydroxide products, or calcining the electrolysis products Metal oxide products.
  • Oxygen is introduced during the leaching process to oxidize titanium, iron, and vanadium oxides in the vanadium-titanium magnetite, destroying the stable magnetite ore phase, and dispersing the impurity elements in the solid solution. Combining into a compound which can be fused to an acid and a base, is separated and removed in a subsequent washing and filtering stage;
  • Alkali leaching of vanadium-titanium magnetite will have a certain destructive effect on the surface of the slag particles, which is conducive to the precipitation of impurity phases, enhance the effect of subsequent acid leaching, and simultaneously use acid-base distribution leaching, which is simpler than acid leaching.
  • the impurity removal rate of oxides such as Si and Al is greatly increased, the dedusting pressure of the subsequent production process is greatly reduced, and high-performance materials are easily prepared, and the oxygen-rich acid leaching oxidizes Fe 2+ in the leachate. Will improve the efficiency of post-electrical transformation of iron sink process;
  • the alkali used is sodium hydroxide.
  • the waste alkali liquor produced during the alkali leaching process can be added with a small amount of ammonium salt, and the vanadate ion can be precipitated as a precipitate, filtered to obtain enrichment; then a small amount of CaO is added.
  • the calcium silicate is formed to effectively remove the Si impurities, thereby achieving the purpose of enriching and removing vanadium oxide, and the lye after filtration can be further used for alkali leaching of vanadium-titanium magnetite to achieve resource recycling; acid leaching The process uses hydrochloric acid, the generated waste acid is heated, and the HCl gas volatilized by heating is absorbed by water atomization, and the formed hydrochloric acid solution is concentrated and returned to the leaching process to realize recycling of resources, and almost no industrial waste water or waste residue is realized to realize green. produce;
  • the impurity ions can be separated and electrically converted by using the extraction principle, and the obtained metal oxide or hydroxide has high purity, and ultra-fine high-purity oxide can be obtained by drying and calcining, and electrolysis can be produced.
  • the valuable by-product hydrogen and chlorine gas can be recycled back to the process through the impurity-free acidic leachate to achieve green recycling and energy saving.
  • CaO is used as a precipitating agent and a silicate ion in a lye is formed to form a calcium silicate precipitate for preparing cement.
  • the autoclave for caustic soak used in the embodiment of the present invention is a ZRYK 1L stainless steel nickel-plated autoclave of Weihai Zhengwei Machinery Equipment Co., Ltd.
  • the autoclave for acid leaching used in the examples of the present invention is a KCFD1-10 type zirconium autoclave of Yantai Keli Chemical Equipment Co., Ltd.
  • the titanium concentrate crushing device in the embodiment of the present invention is a pulverisette 5/4 classic line type planetary high energy ball mill of FRITSCH.
  • the liquid-solid ratio in the embodiment of the present invention is the weight ratio of the volume of the liquid material (sodium hydroxide solution or hydrochloric acid) to the solid material (vanadium-titanium magnetite powder or alkali-decomposed slag), and the unit is L/kg.
  • the stirring speed in the alkali immersion was 500 r/min, and the stirring speed in the acid leaching hydrolysis was 300 rpm.
  • titanium dioxide and metatitanic acid used in the examples of the present invention are commercially available analytically pure reagents.
  • the material remaining after heating and evaporation of the acid immersion liquid is separated into a single metal salt solution by an extraction method, and the metal salt solution is electrolyzed by an electrolytic cell (temperature: 20 ° C, cell voltage: 20 V) to prepare a high-purity hydroxide precipitate;
  • an electrolytic cell temperature: 20 ° C, cell voltage: 20 V
  • a small amount of iron red is added before the iron removal, and the cathode region of the electrolytic cell is mechanically stirred, and the electrolyte and hydroxide in the cathode region are directed to flow.
  • the impurity metal ions are separately removed; since the metal salt solution contains impurity metal ions thereof After the activity is located at H + , the leaching solution contains a large amount of Cl ⁇ during the electrolysis process, so hydrogen and chlorine gas are formed between the two stages of the electrolysis cell; the anode and cathode gases are collected to obtain by-product hydrogen and chlorine gas; and the electrolysis product is dried to obtain impurity hydrogen.
  • the oxygen product, or the metal oxide product obtained after calcination of the electrolytic product has a purity of ⁇ 95%.
  • the vanadium titano-magnetite used in the specific embodiment of the present invention contains 12.8% by weight of TiO 2 , 3.8 % of SiO 2 , 1.1% of CaO, 3.22% of MgO, 53.7% of TFe, 0.24% of MnO, and 2.86% of Al 2 O 3 . , V 2 O 5 0.53%.
  • the vanadium-titanium magnetite is crushed to a particle size of ⁇ 0.125 mm to obtain a vanadium-titanium magnetite powder; the vanadium-titanium magnetite powder and the sodium hydroxide solution are placed in an autoclave for caustic soaking, wherein the mass concentration of the sodium hydroxide solution 20%, the ratio of sodium hydroxide solution to vanadium-titanium magnetite powder is 5:1 according to liquid-solid ratio; oxygen is introduced into the autoclave for alkali leaching, then the temperature is raised to 200 ° C, and the mixture is kept under stirring for 3 hours.
  • the alkali leaching is completed; the alkali leached material is separated by filtration to obtain an alkali decomposition product and an alkali immersion liquid; the alkali decomposition product is washed with water until the filtrate is neutral to be an alkali decomposition slag;
  • the ammonium salt is added to the alkali immersion liquid in an amount of 1:3 in a molar ratio of VO 4 3+ in the alkali immersion liquid to NH 4 + in the ammonium salt, and is allowed to stand until the precipitate is completely precipitated, and the solid phase is obtained by filtration and separation.
  • Liquid phase the solid phase is dried to remove water, and then calcined at 850 ⁇ 5 ° C for 30 min to prepare vanadium oxide, the purity is 96.5%; wherein the washing liquid formed after washing is collected, added to the alkali immersion liquid; CaO is used as a precipitating agent to remove SiO 2 , and when the weight percentage of SiO 2 in the liquid phase is ⁇ 0.05%, it is recycled as a sodium hydroxide solution;
  • the alkali decomposition slag and hydrochloric acid are placed in an autoclave for acid leaching, wherein the weight concentration of hydrochloric acid is 14%, the ratio of hydrochloric acid to alkali decomposition slag is 10:1, and the liquid-solid ratio is added to the autoclave for acid leaching.
  • the acid leached and hydrolyzed material is separated by filtration to obtain a hydrolyzate and an acid immersion liquid; the hydrolyzed product is washed with water until the filtrate is neutral, and then dried to remove water, and finally calcined at 900 ° C for 30 min to prepare titanium oxide; the acid immersion liquid is heated After evaporation, the evaporated hydrogen chloride gas is atomized and absorbed by water, and the prepared hydrochloric acid is concentrated to a mass concentration of 14% and recycled; the purity of the titanium oxide is 98.5%, and the mass percentage includes SiO 2 0.31%, CaO 0.07%, MgO. 0.96%, TFe 3.6%, Mn 0.18%; particle size 0.16 to 4.29 microns.
  • the weight concentration of sodium hydroxide solution is 30%, the ratio of sodium hydroxide solution to vanadium-titanium magnetite powder is 10:1 according to liquid-solid ratio; the alkali immersion temperature is 250 °C, time 2h; (2) solid phase After drying, it is calcined for 40 minutes to prepare vanadium oxide with a purity of 97.2%;
  • the concentration of hydrochloric acid is 18%, the ratio of hydrochloric acid to alkali decomposition slag is 8:1; the temperature of alkali leaching is 130 °C, time 2h; the seed crystal is metatitanic acid, the amount is alkali Decompose 0.3% of the total weight of the slag;
  • the mass concentration of sodium hydroxide solution is 40%, the ratio of sodium hydroxide solution to vanadium-titanium magnetite powder is 15:1 according to liquid-solid ratio; the alkali immersion temperature is 300 °C, time 1h; (2) solid phase After drying, it is calcined for 60 minutes to prepare vanadium oxide with a purity of 96.7%;
  • the mass concentration of hydrochloric acid is 20%, the ratio of hydrochloric acid to alkali decomposition slag is 4:1; the temperature of alkali leaching is 150 ° C, time 1 h; the seed crystal is the quality of titanium dioxide and metatitanic acid.
  • the mixture is added in an amount of 0.2% by weight based on the total weight of the alkali decomposition slag;

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Abstract

一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，按以下步骤进行：(1)将钒钛磁铁矿破碎后与氢氧化钠溶液置于高压釜中，通入氧气，升温搅拌并保温完成碱浸；(2)将碱浸后物料过滤分离，碱分解产物水洗制成碱分解渣料；(3)向碱浸液中加入铵盐，静置析出，固相烘干煅烧制成氧化钒；(4)碱分解渣料与盐酸高压釜，添加晶种升温搅拌并保温完成酸浸水解；(5)过滤分离，水解产物水洗烘干后煅烧制成氧化钛。所述方法实现资源的循环利用，不产生工业废水、废渣实现绿色生产；实现了绿色循环，节能减排。

Description

一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法 技术领域
本发明属于有色冶金技术领域，具体涉及一种一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法。
背景技术
钒在元素周期表中位于第4周期、VB族，其原子序数为23，原子量为50.9415，属于过度金属元素中的高熔点元素；钒具有多种氧化物，工业上钒的氧化物主要以V 2O 2、V 2O 3、V 2O 4，特别是V 2O 5的形式存在，进入20世纪，英国首次制造出含钒的合金钢，在钒的应用领域首先取得突破；随后应用于电池行业，作为目前最有前途的新能量贮蓄***之一，同时钒钛组成的重要金属合金Ti-6A1-4V广泛应用于军事、航空、超导、核反应堆等领域；钒在地壳中的总含量排在金属的第22位，含量虽然不少，但是很分散，至今没有发现单独的钒矿；其主要和一些金属矿共生,我国的钒储量丰富，主要以钒钛磁铁矿和碳质页岩作为工业生产的原料。
钛含量约占地壳质量的0.61％，按地壳中元素丰度排列，是继铝、铁、镁之后的第四位结构金属；其化学性质活泼，在自然界无单质状态，均以氧化物、钛酸盐等化合物形式广泛存在于海水、土壤、岩石、动植物体内；虽然含钛的矿物众多，但目前在工业上得到应用的主要是钛铁矿、钒钛磁铁矿和金红石矿；地壳中的含钛矿物中分布最广，储量最大的是钛铁矿，占钛矿资源的80％左右，也是制备钛产品的主要原料；目前世界上90％以上的钛矿用于生产钛白粉，约4～5％的钛矿用于生产金属钛，其余钛铁矿用于制造电焊条、合金、碳化物、陶瓷、玻璃和化学品等；钛白粉化学名为二氧化钛，是一种白色无机颜料，具有无毒、无害、最佳的不透明性、最佳的白度和光亮度，被认为是目前世界上性能最好的一种白色颜料，广泛应用于涂料，塑料、造纸、印刷油墨、化纤、橡胶、化妆品等工业。
钒钛磁铁矿是一种以铁(Fe)、钒(V)、钛(Ti)为主，伴生多种有价元素如钴(Co)、镍(Ni)、铬(Cr)、铜(Cu)、钪(Sc)、镓(Ga)等的多元共生铁矿，由于Fe、Ti紧密共生，V以类质同象的形式赋存于钛磁铁矿中，因此，通常称为钒钛磁铁矿。钒钛磁铁矿是目前生产钒、钛冶炼的主要资源，可以回收利用其中的钒、铁、钛。钒钛磁铁矿床在中国分布广泛，储量丰富，储量和开采量居全国铁矿的第三位，已探明储量61.9亿吨，站全国探明铁储量的11.6％。此类矿床主要分布在四川攀枝花西昌地区、河北承德地区、湖北郧阳、襄阳等地区。
目前利用钒钛磁铁矿提钒的主要方主要有火法和湿法两种方法，火法工艺是将钒钛磁铁 矿在高炉或电炉中冶炼得到含钒生铁，再用选择性氧化的方法使铁水中的钒氧化进入炉渣，用得到的含钒炉渣进一步提钒；湿法是将钒钛磁铁矿进行焙烧预处理，将钒钛磁铁矿中的中的多价态钒元素在钠盐、钙盐或氧气的辅助下转化为五价钒元素的水溶性盐，然后对经过焙烧处理的得到的矿渣进行水浸或酸浸，钒的水溶性盐和部分杂质金属盐进入了浸出液中，将浸出液净化后加入铵盐，或钙盐沉淀法的处理可以得到钒酸化合物的沉淀，为得到较纯净的产品，需要对粗五氧化二钒进行碱溶和除杂处理，并且进行铵盐二次沉钒，可得到较纯净的偏钒酸铵，经过焙烧后得到高纯度的五氧化二钒；湿法工艺具有总收率高的特点；申请号201010188625.7的专利提出将矿石或精矿破碎后配入钠盐、氧化焙烧，将钒和铬转化为可溶于水的钒酸钠和铬酸钠，水浸到溶液中，从溶液中分离钒铬得到五氧化二钒和三氧化二铬产品；浸出后残渣可配入煤粉造球，经还原，磁选分离铁和钛，得到磁性铁粉可作为粉末冶金或炼钢的原料，和含TiO 2大于50％的非磁性产品作为提钛的原料；该方法的焙烧工艺将消耗大量能量，经该方法制得的五氧化二钒、铁、钛氧化物所含杂质较多，为初级工业原料，产品附加值低；申请号201310183580.8的专利提到湿法处理钒钛磁铁精矿制备钛液的方法，将钒钛磁铁精矿与盐酸混合，浸取，得到中间浆料，将中间浆料过滤得到浸出液和浸出渣随后进行水洗，过滤得洗水和洗渣，将洗渣进行熔盐反应，得到熔盐反应料；将熔盐反应料进行水洗、过滤，得到水洗料；将水洗料进行酸洗获得浆料，过滤得到酸洗料；将酸洗料用硫酸溶液进行酸溶，得到酸溶后物料；将酸溶后物料加入硫酸溶液中进行浸取，过滤获得的浸取液即为钛液；该方法忽略了钒钛磁铁矿中所含有的大量含铁化合物，及多种高附加值金属元素，资源利用率较低。
发明内容
根据对现有钒钛磁铁矿生产工艺的研究，本发明提出一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，以钒钛磁铁矿为原料，以氢氧化钠、盐酸为溶剂，利用机械活化、富氧、高压等强化浸出手段，对钒钛磁铁矿进行高压富氧碱浸， 高压酸浸，制备出钛白粉，经后续的提纯及晶型转化制备出高纯度的TiO 2；对浸出液中有价钒元素进行铵盐沉淀回收、焙烧制得高纯氧化钒，实现钒元素的富集，减少能源消耗，有效的降低浸出过程的酸碱浓度，并加以回收实现资源的循环利用，同时改善设备工作条件，延长设备使用寿命。
本发明的方法按以下步骤进行：
1、将钒钛磁铁矿破碎至粒度≤0.125mm，获得钒钛磁铁矿粉；将钒钛磁铁矿粉与氢氧化钠溶液置于碱浸用高压釜中，其中氢氧化钠溶液的质量浓度为20～40％，氢氧化钠溶液与钒钛磁铁矿粉的比例按液固比为(5～15):1；向碱浸用高压釜内通入氧气，然后升温至200～300 ℃，在搅拌条件下保温1～3h，完成碱浸；2、将碱浸后的物料过滤分离，获得碱分解产物和碱浸液；将碱分解产物水洗至滤液为中性，制成碱分解渣料；
3、向碱浸液中加入铵盐，加入量按碱浸液中的VO 4 3+与铵盐中的NH 4 +的摩尔比为1:3，静置至沉淀完全析出，过滤分离获得固相和液相；将固相烘干去除水分，再在850±5℃煅烧30～60min，制成氧化钒；
4、将碱分解渣料与盐酸置于酸浸用高压釜中，其中盐酸的质量浓度为14～20％，盐酸与碱分解渣料的比例按液固比为(4～10):1；向酸浸用高压釜中添加晶种，便于碱分解渣料在盐酸水解过程中形成的钛氧化物形核长大，然后升温至120～150℃，在搅拌条件下保温1～3h，完成酸浸水解；
5、将酸浸水解后的物料过滤分离，获得水解产物和酸浸液；将水解产物水洗至滤液为中性，再烘干去除水分，最后在800～900℃煅烧30～60min，制成氧化钛。
上述方法中，步骤3获得的液相用CaO作为沉淀剂去除SiO 2，回收硅酸钙副产品，当液相中SiO 2重量百分比≤0.05％时，作为氢氧化钠溶液返回步骤1使用。
上述的晶种为二氧化钛和/或偏钛酸，加入量为碱分解渣料总重量的0.2～0.5％。
上述方法中，获得的酸浸液加热蒸发后，将酸浸液中多余的氯化氢挥发出来经吸收制成的盐酸浓缩至重量浓度为14～20％，返回步骤4使用。
上述的氧化钒纯度≥95％。
上述的氧化钛纯度≥98.5％，粒度在0.1～13微米。
上述的酸浸液加热蒸发后剩余的物料采用萃取的方法分离成单一金属盐溶液，将金属盐溶液采用电解槽电解，分别制成高纯氢氧化物沉淀；以Fe为例，由于Fe 3+离子浓度较高，为防止氢氧化铁团聚，在除铁之前加入少量铁红，同时对电解槽阴极区进行机械搅拌，阴极区电解液和氢氧化物定向流动，此时通过过滤装置进行过滤，实现固液分离，滤液循环返回阴极区，制得超细高纯铁红；依据相同的原理，分别除去所含杂质金属离子；由于金属盐溶液所含杂质金属离子其活性位于H +之后，电解过程中浸出液中含有大量Cl -，所以电解槽两级之间会有氢气和氯气生成；收集阳极和阴极气体，获得副产品氢气和氯气；烘干过滤电解产物获得杂质氢氧物产品，或将电解产物煅烧后获得金属氧化物产品。
电转化直接分离氢氧化沉淀的方法涉及的主要反应如下：
阳极反应：2Cl --2e＝Cl 2↑，
阴极反应：2H ++2e＝H 2↑，
总反应：MeCl 2+2H 2O＝Me(OH) 2+H 2+Cl 2，
煅烧反应：Me(OH)＝MeO+H 2O↑。
本发明的原理及有益效果是：
(1)在浸出过程中通入氧气，会对钒钛磁铁矿中低价的钛、铁、钒氧化物进行氧化，破坏稳定的磁铁矿矿相，使该固溶体中弥散分布的杂质元素结合成可融于酸碱的化合物，在随后的洗涤过滤阶段分离除去；
(2)在浸出过程中保证体系的密闭性，随着氧气的通入或温度的持续升高，釜内产生较大的气压，很大程度的优化浸出过程的动力学条件，对钒钛磁铁矿氧化、杂质析出，矿相的破坏都有促进作用，将其作为强化浸出的一种手段在与其他浸出工艺参数共同作用的过程中，可以适当降低温度，酸碱度，浸出时间等工艺条件，达到环保节能目的；
(3)对钒钛磁铁矿先进行碱浸，会对渣粒表面有一定破坏作用，有利于杂质相的析出，增强后续酸浸的效果，同时采用酸碱分布浸出，较单纯的酸浸，Si，Al等氧化物的杂质去除率会大大增加，对后续的生产工艺的除杂压力大大减小，易于制备出高性能材料，同时富氧酸浸会把浸出液中的Fe 2+氧化，会提高后期电转化沉铁过程效率；
(4)采用的碱为氢氧化钠，碱浸过程中产生的废碱液可添加少量铵盐，即可将其中的钒酸根离子以沉淀形式析出，过滤使其得到富集；后加入少量CaO生成硅酸钙将Si杂质有效除去，实现钒氧化物富集和除杂的目的，同时过滤后的碱液经浓缩可以继续用于钒钛磁铁矿碱浸，实现资源的循环利用；酸浸过程用盐酸，产生的废酸经加热，同时利用水雾化吸收加热挥发出的HCl气体，形成的盐酸溶液经浓缩返回到浸出工艺，实现资源的循环利用，几乎不产生工业废水、废渣实现绿色生产；
(5)可以利用萃取原理将各杂质离子分离并进行电转化，制得的金属氧化物或氢氧化物纯度较高，经干燥、煅烧可制得超细的高纯氧化物，同时电解会产生有价值的副产品氢气、氯气，经除杂的酸性浸出液可循环回工艺流程中，实现绿色循环，节能减排。
具体实施方式：
本发明实施例中用CaO作为沉淀剂与碱液中硅酸根离子生成硅酸钙沉淀用于制备水泥。
本发明实施例中采用的碱浸用高压釜为威海市正威机械设备有限公司的ZRYK 1L型不锈钢镀镍高压釜。
本发明实施例中采用的酸浸用高压釜为烟台科立化工设备有限公司的KCFD1-10型锆质高压釜。
本发明实施例中钛精矿破碎设备为FRITSCH的pulverisette 5/4classic line型行星式高能球磨机。
本发明实施例中的液固比是液体物料(氢氧化钠溶液或盐酸)的体积与固体物料(钒钛磁铁矿粉或碱分解渣料)的重量比，单位为L/kg。
本发明实施例中碱浸时的搅拌速度为500r/min，酸浸水解时的搅拌速度为300r/min。
本发明实施例中采用的二氧化钛和偏钛酸为市购分析纯试剂。
本发明实施例中酸浸液加热蒸发后剩余的物料采用萃取方法分离成单一金属盐溶液，将金属盐溶液采用电解槽电解(温度20℃，槽电压20V)，分别制成高纯氢氧化物沉淀；以Fe为例，由于Fe 3+离子浓度较高，为防止氢氧化铁团聚，在除铁之前加入少量铁红，同时对电解槽阴极区进行机械搅拌，阴极区电解液和氢氧化物定向流动，此时通过过滤装置进行过滤，实现固液分离，滤液循环返回阴极区，制得超细高纯铁红；依据相同的原理，分别除去所含杂质金属离子；由于金属盐溶液所含杂质金属离子其活性位于H +之后，电解过程中浸出液中含有大量Cl -，所以电解槽两级之间会有氢气和氯气生成；收集阳极和阴极气体，获得副产品氢气和氯气；烘干过滤电解产物获得杂质氢氧物产品，或将电解产物煅烧后获得金属氧化物产品，纯度≥95％。
下面结合实施例对本发明作进一步的详细说明。
本发明具体实施例中采用的钒钛磁铁矿按重量百分比含TiO 2 12.8％，SiO 2 3.83％，CaO1.16％，MgO 3.22％，TFe 53.7％，MnO 0.24％，Al 2O 3 2.86％，V 2O 5 0.53％。
实施例1
将钒钛磁铁矿破碎至粒度≤0.125mm，获得钒钛磁铁矿粉；将钒钛磁铁矿粉与氢氧化钠溶液置于碱浸用高压釜中，其中氢氧化钠溶液的质量浓度为20％，氢氧化钠溶液与钒钛磁铁矿粉的比例按液固比为5:1；向碱浸用高压釜内通入氧气，然后升温至200℃，在搅拌条件下保温3h，完成碱浸；将碱浸后的物料过滤分离，获得碱分解产物和碱浸液；将碱分解产物水洗至滤液为中性制成碱分解渣料；
向碱浸液中加入铵盐，加入量按碱浸液中的VO 4 3+与铵盐中的NH 4 +的摩尔比为1:3，静置至沉淀完全析出，过滤分离获得固相和液相；将固相烘干去除水分，再在850±5℃煅烧30min，制成氧化钒，纯度96.5％；其中水洗后生成的洗液经收集后，加入到碱浸液中；液相用CaO作为沉淀剂去除SiO 2，当液相中SiO 2重量百分比≤0.05％时，作为氢氧化钠溶液循环使用；
将碱分解渣料与盐酸置于酸浸用高压釜中，其中盐酸的重量浓度为14％，盐酸与碱分解渣料的比例按液固比为10:1；向酸浸用高压釜中添加晶种，便于碱分解渣料在盐酸水解过程中形成的钛氧化物形核长大，升温至120℃，在搅拌条件下保温3h，完成酸浸水解；晶种为 二氧化钛，晶种的加入量为碱分解渣料总重量的0.5％；
将酸浸水解后的物料过滤分离，获得水解产物和酸浸液；将水解产物水洗至滤液为中性，再烘干去除水分，最后在900℃煅烧30min，制成氧化钛；酸浸液加热蒸发后，将挥发出来的氯化氢气体用水雾化吸收，制成的盐酸浓缩至质量浓度为14％，循环使用；氧化钛纯度为98.5％，按质量百分比含SiO 2 0.31％，CaO 0.07％，MgO 0.96％，TFe 3.6％，Mn 0.18％；粒度为0.16～4.29微米。
实施例2
方法同实施例1，不同点在于：
(1)氢氧化钠溶液的重量浓度为30％，氢氧化钠溶液与钒钛磁铁矿粉的比例按液固比为10:1；碱浸温度250℃，时间2h；(2)固相烘干后煅烧40min，制成氧化钒，纯度97.2％；
(3)盐酸的质量浓度为18％，盐酸与碱分解渣料的比例按液固比为8:1；碱浸水解的温度130℃，时间2h；晶种为偏钛酸，加入量为碱分解渣料总重量的0.3％；
(4)将水解产物水洗烘干后，在850℃煅烧40min；氯化氢气体吸收制成的盐酸浓缩至重量浓度为18％；氧化钛纯度为98.7％，按质量百分比含SiO 2 0.22％，CaO 0.07％，MgO 0.64％，TFe 2.1％，Mn 0.16％；粒度为0.5～12微米。
实施例3
方法同实施例1，不同点在于：
(1)氢氧化钠溶液的质量浓度为40％，氢氧化钠溶液与钒钛磁铁矿粉的比例按液固比为15:1；碱浸温度300℃，时间1h；(2)固相烘干后煅烧60min，制成氧化钒，纯度96.7％；
(3)盐酸的质量浓度为20％，盐酸与碱分解渣料的比例按液固比为4:1；碱浸水解的温度150℃，时间1h；晶种为二氧化钛和偏钛酸的等质量混合物，加入量为碱分解渣料总重量的0.2％；
(4)水解产物水洗烘干后，在800℃煅烧60min；氯化氢气体吸收制成的盐酸浓缩至质量浓度为20％，循环使用；氧化钛纯度为98.9％，按质量百分比含SiO 2 0.18％，CaO 0.07％，MgO 0.32％，TFe 1.5％，Mn<0.05％；粒度为0.8～13微米。

Claims (6)

  1. 一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于按以下步骤进行：
    (1)将钒钛磁铁矿破碎至粒度≤0.125mm，获得钒钛磁铁矿粉；将钒钛磁铁矿粉与氢氧化钠溶液置于碱浸用高压釜中，其中氢氧化钠溶液的质量浓度为20～40％，氢氧化钠溶液与钒钛磁铁矿粉的比例按液固比为(5～15):1；向碱浸用高压釜内通入氧气，然后升温至200～300℃，在搅拌条件下保温1～3h，完成碱浸；(2)将碱浸后的物料过滤分离，获得碱分解产物和碱浸液；将碱分解产物水洗至滤液为中性，制成碱分解渣料；
    (3)向碱浸液中加入铵盐，加入量按碱浸液中的VO 4 3+与铵盐中的NH 4 +的摩尔比为1:3，静置至沉淀完全析出，过滤分离获得固相和液相；将固相烘干去除水分，再在850±5℃煅烧30～60min，制成氧化钒；
    (4)将碱分解渣料与盐酸置于酸浸用高压釜中，其中盐酸的质量浓度为14～20％，盐酸与碱分解渣料的比例按液固比为(4～10):1；向酸浸用高压釜中添加晶种，便于碱分解渣料在盐酸水解过程中形成的钛氧化物形核长大，升温至120～150℃，在搅拌条件下保温1～3h，完成酸浸水解；
    (5)将酸浸水解后的物料过滤分离，获得水解产物和酸浸液；将水解产物水洗至滤液为中性，再烘干去除水分，最后在800～900℃煅烧30～60min，制成氧化钛。
  2. 根据权利要求1所述的一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于步骤(3)获得的液相用CaO作为沉淀剂去除SiO 2，回收硅酸钙副产品；当液相中SiO 2质量百分比≤0.05％时，作为氢氧化钠溶液返回步骤(1)使用。
  3. 根据权利要求1所述的一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于所述的晶种为二氧化钛和/或偏钛酸，加入量为碱分解渣料总重量的0.2～0.5％。
  4. 根据权利要求1所述的一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于步骤(5)获得的酸浸液加热蒸发后，将多余氯化氢挥发出来用水雾化吸收制成的盐酸浓缩至重量浓度为14～20％，返回步骤4使用。
  5. 根据权利要求1所述的一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于所述的氧化钒纯度≥95％。
  6. 根据权利要求1所述的一种富氧选择性浸出提取钒钛磁铁矿中有价组元的方法，其特征在于所述的氧化钛纯度≥98.5％，粒度在0.1～13微米。
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