CN101817551B - Method for preparing lithium titanate precursor from titanic iron ore - Google Patents

Method for preparing lithium titanate precursor from titanic iron ore Download PDF

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CN101817551B
CN101817551B CN2010101874122A CN201010187412A CN101817551B CN 101817551 B CN101817551 B CN 101817551B CN 2010101874122 A CN2010101874122 A CN 2010101874122A CN 201010187412 A CN201010187412 A CN 201010187412A CN 101817551 B CN101817551 B CN 101817551B
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titanium
lithium titanate
acid
ilmenite
titanate precursor
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CN101817551A (en
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李新海
吴飞翔
王志兴
伍凌
王小娟
郭华军
彭文杰
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Central South University
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Central South University
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Abstract

The invention discloses a method for preparing a lithium titanate precursor from a titanic iron ore. The method comprises the following steps of: leaching the titanic iron ore to obtain titanium slag by using an acid; pulping the titanium slag by using alkali and adjusting the pH of the pulp to be 4 to 14; adding a complexing agent into a stirred reactor at the temperature of 20 to 80 DEG C for leaching and adjusting the pH to be 4 to 14 in a reaction process by using the alkali; heating obtained filtrate to 80 to 110 DEG C, filtering and washing the filtrate to obtain precipitate; and drying the precipitate at the temperature of 50 to 150 DEG C to obtain the precursor of lithium-ion battery cathode material lithium titanate, namely the complex of titanium, or calcining the dried precipitate at the temperature of 400 to 900 DEG C to obtain another precursor of the lithium-ion battery cathode material lithium titanate, namely anatase titanium dioxide (TiO2). The method has the advantages of wide raw material source, simple process flow, high and stable product quality, low energy consumption, low cost and the like.

Description

A kind of method of utilizing ilmenite to prepare lithium titanate precursor
Technical field:
The present invention relates to a kind of industrial method of utilizing ilmenite to prepare the lithium ionic cell cathode material lithium titanate presoma.
Technical background:
Li 4Ti 5O 12It is a kind of spinel structure " zero strain " embedded type electrode materials, cycle performance is highly stable, and its safety performance is better than carbon negative pole material, and big 1 order of magnitude of its chemical diffusion coefficient ratio carbon negative pole material, the speed that discharges and recharges is very fast, and good charge and discharge platform is arranged; Low price, preparation easily.Therefore compare with commercial carbon negative pole material, have better chemical property and security usually; Compare with the alloy type negative material, easier preparation, cost is lower.Therefore, regarded as one of novel negative material of very promising lithium ion battery by people.
At present the titanium source of preparation lithium titanate mostly is chemical pure or analytically pure titanyl compound greatly, mainly contains anatase titanium dioxide and rutile titanium dioxide, and the organism of titanium, as tetrabutyl titanate etc.The raw materials cost height, prospects for commercial application is little.In the energy urgent day by day today, new energy materials has obtained people's attention, and people are seeking cheap raw material always and preparing battery material.
The China's titanium resource is very abundant, first in the reserves row whole world.All there is the titanium ore resource more than 20 provinces and regions, the whole nation, mainly are distributed in Sichuan Pan Xi, Chengde, Yunnan, Hainan, Guangxi and Guangdong Province, about 7.5 hundred million tons of resource reserve.Wherein most important titanium resource is the ilmenite in the Flos Bombacis Malabarici vanadium titano-magnetite of Sichuan, and reserves account for 97% of national primary ilmenite reserves, in the countries first.Nearly 10,000,000,000 tons of the v-ti magnetite ore reserves of Sichuan Panxi Diqu, TiO 2Reserves account for 93% of the whole nation, select titanium factory ilmenite concentrate steady quality 47%, and sulphur is below 0.3%, but impurity Ca, Mg, the Si equal size is higher.The titanium ore grade is lower, the higher present Producing Titanium Dioxide of China that determined of foreign matter content itself can only be used sulfuric acid process.China is except Jinzhou, Liaoning iron alloy titanium powder plant adopts fused salt chlorimation method (1.5 ten thousand tons), and all the other all adopt sulfuric acid process.The fused salt chlorimation method is a kind of method that is adopted at the calcium-magnesium content height, but (contains TiO because the used grade of climbing the ore deposit titanium slag is too low 292%-94%), cause the chlorine consumption big, produce a large amount of chloride waste residue, waste liquid and waste water, and exist equipment capacity low, production poor continuity, equipment are difficult to shortcomings such as maximization, therefore adopt the fused salt chlorimation technology can't satisfy the requirement of carrying forward vigorously China's titanium white chloride industrialization.
Because the natural rutile resource lacks very much, the ilmenite resource more and more is much accounted of, but industrial main employing sulfuric acid process is handled ilmenite and various titanium slag, and leaching process energy consumption and acid consumption are big, and process is tediously long.Solid phase method is all adopted in China's sulfate process titanium dioxide production at present, and the ilmenite and the vitriol oil (85%-92%) react in the acidolysis groove.The acid of industrial general usefulness 95% mixes the heat that produces and comes initiation reaction with water, adding reaction is thermopositive reaction, so top temperature can reach about 200 ℃ in the acidolysis groove.Reaction is fierce, follows reaction to have a large amount of acid waste gas to emit.Because the concentration height of the acid of being adopted, reaction is fierce, not only produces a large amount of acid waste gas, and produces a large amount of spent acid after the hydrolysis, produces 1 ton of titanium dioxide, approximately produces the spent acid of 8-10 ton about 20%.The key issue of sulfuric acid process disposal of waste gas, water and industrial residue is that quantity discharged is big, the processing costs height.The spent acid problem has become a key issue of restriction sulfuric acid process development at present, and along with the enhancing of people's environmental consciousness, if the spent acid problem can not get good solution, sulfate process titanium dioxide will have the danger of closing.
Summary of the invention:
Technical problem to be solved by this invention provides that a kind of raw material sources are wide, technical process is simple, good product quality and stable, that cost is low, environmental a kind of method of utilizing ilmenite to prepare lithium titanate precursor.
In order to solve the problems of the technologies described above, the present invention includes above step:
(1) is that the acidleach of 5%-40% goes out with the ilmenite mass percent, filters, washing obtains iron content acid solution and titanium slag;
(2) with the aqueous solution of alkali titanium slag is pulled an oar, regulate pH=4-14;
(3) in step (2) gained slurry, add the complexing agent agitation leach down at 20-80 ℃, the mol ratio of controlling Ti in complexing agent and the titanium slag in the reaction process is 1-20, the aqueous solution with alkali in the reaction process is regulated pH=4-14, filters the complex solution and the leached mud that obtain titanium;
(4) complex solution with the titanium that obtains is heated to 80-110 ℃ in stirred reactor, filters, and washing obtains throw out; To obtain the presoma of lithium ionic cell cathode material lithium titanate after the drying precipitate---the complex compound of titanium; Perhaps dried throw out is calcined another kind of presoma---the anatase titanium dioxide TiO that obtains lithium ionic cell cathode material lithium titanate down at 400-900 ℃ 2
The present invention adopts a kind of two sections new leaching methods to leach ilmenite, at first is one section and adopts acid leaching ilmenite more than 80 ℃, and filtration washing obtained iron content acid solution and titanium slag when reaction finished.Two sections are adopted a kind of new method, and complexing is at normal temperatures leached the ilmenite acidleach and slagged tap, and reaction removes by filter leached mud when finishing and obtains high-purity titanium liquid.This method is simple, complexing agent is cheap, energy consumption is low and the leaching yield height of Ti, and titanium and iron good separating effect can be prepared the leach liquor of high-purity Ti, thereby prepares high-quality presoma.Again by the superior Li of this presoma processability 4Ti 5O 12Negative material.Realize the process from the refractory ore to the battery material, thereby made resource obtain effective utilization, produced very high economic worth simultaneously.Therefore, the present invention is particularly suitable for providing fine titanium source for the production of lithium ionic cell cathode material lithium titanate, if form large-scale production, will bring huge economic benefit and ecological benefits to society.So far for this reason, do not see about complexing and leach the slag tap report of preparation lithium ionic cell cathode material lithium titanate presoma of ilmenite acidleach.
Described acid is one or more in sulfuric acid, hydrochloric acid and the nitric acid.
Described alkali is a kind of in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, yellow soda ash, sodium bicarbonate, salt of wormwood and the saleratus.
Described complexing agent is a kind of among sodium peroxide, Potassium peroxide, oxalic acid, sodium oxalate, hydrogen peroxide, potassium oxalate, ammonium oxalate, citric acid, tartrate and the EDTA.
Leaching the reaction times in described (3) step can be at 5-720min.
Can be 0.5-8 hour heat-up time in described (4) step.
Drying temperature is preferably 50-150 ℃ in described (4) step.Calcination time can be 1-24h.
The present invention is in order to overcome the raw materials cost height of preparation lithium ionic cell cathode material lithium titanate, the organism of nanometer anatase titania that price is high and titanium particularly, a kind of method of utilizing ilmenite to prepare the lithium ionic cell cathode material lithium titanate presoma that provides, this method is a raw material with cheap natural ilmenite, with acid its leaching is obtained titanium slag earlier, titanium complexing in the titanium slag is leached by control condition with cheap complexing agent again, obtain high-purity titanium liquid.Titanium liquid is heated, filter, washing obtains throw out, is drying to obtain the presoma of lithium titanate.Perhaps dried throw out being calcined and obtained nanometer anatase titania, is the titanium source of preparation lithium titanate material ideal.Raw material sources of the present invention are wide, technical process is simple, energy consumption is little, cost is low, the utilization ratio height of titanium, presoma purity height, are particularly suitable for providing fine titanium source for the scale operation of lithium titanate, also make the ilmenite resource obtain effective utilization simultaneously.
The present invention compares with the method that other prepares lithium titanate precursor, and its advantage fully shows in the following areas:
1) be raw material with natural ilmenite, cost is far below general chemical pure, analytical pure raw material.Efficiently utilized Flos Bombacis Malabarici ilmenite resource, the economic worth height.Go out in the process carrying out acidleach, it is that the acid of 5%-40% is carried out acidleach and gone out that ilmenite only need be used mass percent, significantly reduces the generation of spent acid and acid waste gas.
2) novel method of two sections leaching ilmenites of employing.Iron in one section leaching ilmenite, titanium is not leached.The titanium in the titanium slag is leached in two sections complexings, and other impurity are not leached, and obtain the leach liquor of high purity titanium.
3) adopt cheap complexing agent to leach the ilmenite acidleach and slag tap, the leaching yield height has only micro-beneficial element to enter solution, presoma purity height.
4) the present invention also is provided with the compound that the simple heating prepared goes out nano level Ti especially, does not add any precipitation agent, does not introduce new impurity.Heat-up time, short control easily was the size of may command product (lithium titanate precursor) particle diameter by generated time.
5) compound of the prepared nano level Ti of this technology at high temperature the incinerating product be stable anatase titanium dioxide TiO 2, with synthetic rutile TiO under the high temperature in the traditional technology 2Compare the anatase titanium dioxide TiO that this method is prepared 2Presoma is preparation Li 4Ti 5O 12The titanium source of material ideal.
6) compound of this nano level Ti decomposites a large amount of gases in the incinerating process, at preparation Li 4Ti 5O 12Help the formation of porous nano grade particles in the process of material.The Li for preparing 4Ti 5O 12The chemical property of material is superior.
In sum, the present invention is well-designed by above technical process, has played economizing on resources to greatest extent, reduces cost the effect of environmental protection.Be that a kind of raw material sources are wide, technical process is simple, energy consumption is little, good product quality and stable, that cost is low a kind of method of utilizing ilmenite to prepare lithium titanate precursor.
Description of drawings:
Fig. 1 is the process flow sheet for preparing lithium titanate precursor from ilmenite;
Fig. 2 is the complex compound sem photograph of the titanium among the embodiment 1;
Fig. 3 is the XRD figure spectrum of the anatase titanium dioxide among the embodiment 1;
Fig. 4 is the sem photograph of the complex compound of the titanium among the embodiment 2;
Fig. 5 is the XRD figure spectrum of the anatase titanium dioxide among the embodiment 2.
Embodiment:
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:
At 100 ℃ is that 50% sulfuric acid leaches the 100g ilmenite with mass concentration down, reacts 2h, and filtration washing obtains titanium slag.Sodium hydroxide solution with 0.5mol/L is pulled an oar titanium slag, and regulating pH is 7.Add sodium peroxide solution, the mol ratio of sodium peroxide and titanium is 1, reacts in the stirred reactor under 20 ℃, regulates pH=7 with sodium hydroxide in the reaction process, reacts 5 minutes, filters the leach liquor that obtains titanium.Again reaction in the stirred reactor of leach liquor under 60 ℃ was obtained precipitation in 0.5 hour,, dry presoma---the complex compound of titanium that obtains battery negative pole material of lithium titanate down at 100 ℃ with resulting washing of precipitate, filtration.Yellow mercury oxide after perhaps will drying is calcined another kind of presoma---the nano-scale anatase titanium dioxide that obtained battery negative pole material of lithium titanate in 24 hours down at 400 ℃.
Embodiment 2:
At 100 ℃ is that 5% hydrochloric acid leaches the 100g ilmenite with mass concentration down, reacts 2h, and filtration washing obtains titanium slag.With massfraction is that 5% ammoniacal liquor is pulled an oar titanium slag, and regulating pH is 4.Add superoxol, the mol ratio of hydrogen peroxide and titanium is 6, react in the stirred reactor 80 ℃ under, and in the reaction process be 5% ammoniacal liquor adjusting pH=4 with massfraction, to react 60 minutes, filtration obtains the leach liquor of titanium.Again reaction in the stirred reactor of leach liquor under 90 ℃ was obtained precipitation in 2 hours, with resulting washing of precipitate, filtration.Dry presoma---the complex compound of titanium that obtains battery negative pole material of lithium titanate down at 100 ℃.Throw out after perhaps will drying is calcined another kind of presoma---the nano-scale anatase titanium dioxide that obtained battery negative pole material of lithium titanate in 6 hours down at 700 ℃.
Embodiment 3:
At 100 ℃ is that 20% nitric acid leaches ilmenite with mass concentration down, reacts 2h, and filtration washing obtains titanium slag.Lithium hydroxide with 0.5mol/L is pulled an oar titanium slag, and regulating pH is 14.Add EDTA solution, the mol ratio of EDTA and titanium is 10, reacts in the stirred reactor under 80 ℃, and the lithium hydroxide with 0.5mol/L in the reaction process is regulated pH=14, reacts 720 minutes, filters the leach liquor that obtains titanium.Again reaction in the stirred reactor of leach liquor under 100 ℃ was obtained precipitation in 8 hours,, dry presoma---the complex compound of titanium that obtains battery negative pole material of lithium titanate down at 100 ℃ with resulting washing of precipitate, filtration.Throw out after perhaps will drying is calcined another kind of presoma---the nano-scale anatase titanium dioxide that obtained battery negative pole material of lithium titanate in 2 hours down at 900 ℃.
Embodiment 4:
At 105 ℃ is that 30% hydrochloric acid leaches the 100g ilmenite with mass concentration down, reacts 2h, and filtration washing obtains titanium slag.Potassium hydroxide with 0.5mol/L is pulled an oar titanium slag, and regulating pH is 9.Add hydrogen peroxide solution, the mol ratio of hydrogen peroxide and titanium is 5, react in the stirred reactor 30 ℃ under, and in the reaction process be 30% ammoniacal liquor adjusting pH=9 with massfraction, to react 180 minutes, filtration obtains the leach liquor of titanium.Again reaction in the stirred reactor of leach liquor under 100 ℃ was obtained precipitation in 5 hours,, dry presoma---the complex compound of titanium that obtains battery negative pole material of lithium titanate down at 100 ℃ with resulting washing of precipitate, filtration.Throw out after perhaps will drying is calcined another kind of presoma---the nano-scale anatase titanium dioxide that obtained battery negative pole material of lithium titanate in 4 hours down at 800 ℃.
Embodiment 5:
At 105 ℃ is that 10% nitration mixture (sulfuric acid and hydrochloric acid) leaches the 100g ilmenite with mass concentration down, reacts 2h, and filtration washing obtains titanium slag.Potassium hydroxide with 0.5mol/L is pulled an oar titanium slag, and regulating pH is 9.Add oxalic acid solution, the mol ratio of oxalic acid and titanium is 7, react in the stirred reactor 30 ℃ under, and in the reaction process be 30% ammoniacal liquor adjusting pH=9 with massfraction, to react 150 minutes, filtration obtains the leach liquor of titanium.Again reaction in the stirred reactor of leach liquor under 80 ℃ was obtained precipitation in 4 hours,, dry presoma---the complex compound of titanium that obtains battery negative pole material of lithium titanate down at 100 ℃ with resulting washing of precipitate, filtration.Throw out after perhaps will drying is calcined another kind of presoma---the nano-scale anatase titanium dioxide that obtained battery negative pole material of lithium titanate in 13 hours down at 800 ℃.
Although the present invention is described in each preferred embodiment, but the easy cleavage the present invention of those skilled in the art is not limited to foregoing description, it can be changed by multiple alternate manner or improve, and does not break away from the spirit and scope of illustrating in the claim of the present invention.What wherein acid can also be in nitration mixture (sulfuric acid and nitric acid), nitration mixture (hydrochloric acid and nitric acid), the nitration mixture (sulfuric acid, hydrochloric acid and nitric acid) is several.Alkali can also be in yellow soda ash, sodium bicarbonate, salt of wormwood, the saleratus one or more.Complexing agent can also be in Potassium peroxide, sodium oxalate, potassium oxalate, ammonium oxalate, the citric acid a kind of.

Claims (7)

1. method of utilizing ilmenite to prepare lithium titanate precursor is characterized in that may further comprise the steps:
(1) with mass percent be the acid of 5%-40% at 80-200 ℃ of following agitation leach ilmenite, filtration washing obtains ferruginous acid solution and titanium slag;
(2) titanium slag that step (1) is obtained is pulled an oar with the aqueous solution of alkali, and adjusting pH is 4-14;
(3) adding complexing agent in step (2) the gained slurry carries out complexing and leaches, regulating pH with alkali in the leaching process is 4-14, the mol ratio of controlling Ti in complexing agent and the titanium slag in the reaction process is 1-20, and temperature of reaction is 20-80 ℃, filters the complex solution and the leached mud that obtain titanium;
(4) complex solution with titanium is heated to 80-110 ℃, filters, and washing obtains throw out; Drying precipitate is promptly got the presoma of lithium ionic cell cathode material lithium titanate---the complex compound of titanium; Perhaps will calcine another kind of presoma---the anatase titanium dioxide TiO that obtains lithium ionic cell cathode material lithium titanate down at 400-900 ℃ after the drying precipitate 2
2. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that the acid described in the above-mentioned steps (1) is one or more in sulfuric acid, hydrochloric acid and the nitric acid.
3. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that the alkali described in above-mentioned steps (2) and (3) is a kind of in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor, yellow soda ash, sodium bicarbonate, salt of wormwood and the saleratus.
4. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that the complexing agent described in the above-mentioned steps (3) is a kind of among sodium peroxide, Potassium peroxide, oxalic acid, hydrogen peroxide, sodium oxalate, potassium oxalate, ammonium oxalate, citric acid and the EDTA.
5. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that leaching the reaction times in described (3) step is 5-720min.
6. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that be 0.5-8 hour heat-up time in described (4) step.
7. a kind of method of utilizing ilmenite to prepare lithium titanate precursor according to claim 1 is characterized in that drying temperature is 50-150 ℃ in described (4) step.
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CN101967010B (en) * 2010-11-04 2012-07-25 中南大学 Method for preparing nano-TiO2 serving as cathode material of lithium ion battery
CN102153137B (en) * 2011-05-18 2013-06-05 中南大学 Method for preparing spherical lithium titanate from inorganic titanium sources
CN104805299B (en) * 2015-04-14 2017-02-22 东北大学 Method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag
CN105590756B (en) * 2016-03-21 2017-12-08 王小峰 A kind of preparation method of micro/nano-scale graphene/lithium titanate composite anode material

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WO2007052801A1 (en) * 2005-11-07 2007-05-10 Tohoku University Method for extraction of rutile
CN101709374B (en) * 2009-11-25 2011-05-11 中南大学 Method for preparing precursors of lithium titanate and lithium iron phosphate by comprehensively using ilmenite
CN101704681B (en) * 2009-11-30 2011-12-28 中南大学 Method for preparing lithium titanate with spinel structure

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