CN101016590A - Method of preparing lithium from spodumene concentrate - Google Patents

Method of preparing lithium from spodumene concentrate Download PDF

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CN101016590A
CN101016590A CNA2007100859015A CN200710085901A CN101016590A CN 101016590 A CN101016590 A CN 101016590A CN A2007100859015 A CNA2007100859015 A CN A2007100859015A CN 200710085901 A CN200710085901 A CN 200710085901A CN 101016590 A CN101016590 A CN 101016590A
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lithium
granularity
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prepared
concentrate
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黄启新
黄颖
黄杰
黄丽
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黄启新
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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
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Abstract

The invention discloses a preparing method of lithium with lithia ore clean ore, which comprises the following steps: (1) allocating mass ratio of lithia ore clean ore (SC) : burnt lime : aluminum oxide : ferrosilicon = formula (3); mixing evenly; (2) pelleting with powder mixture from step one; (3) proceeding reduction reaction under the condition of temperature at 1500-1600 deg.c and vacuum degree P<= 30Pa; generating lithium vapour; (4) condensing to liquid state lithium; (5) leading the liquid state lithium through filter; casting ingot; getting solid lithium. This invention possesses merits of high purity, low cost and less investment.

Description

Method with preparing lithium from spodumene concentrate
Affiliated technical field
The present invention relates to a kind of method of Metal smelting, be meant a kind of method especially with preparing lithium from spodumene concentrate.
Background technology
Metallic lithium is being important raw metal aspect military project, the civilian and new forms of energy, and it is low that existing electrolysis legal system lithium method exists product purity, has only 96-%-98%, also must purify by distillation repeatedly before it uses, so the product cost height.In addition, electrolysis legal system lithium method also exists the serious environmental pollution problem, and promptly the chlorine that produces in the electrolysis system lithium process can cause serious pollution to environment, and the facility investment of electrolysis system lithium method is also bigger.
Summary of the invention
The object of the present invention is to provide a kind of product purity height, cost is low, environmentally safe, facility investment is also less directly makes the method for lithium with the triphane concentrate.This legal system lithium is with following four kinds of starting material: triphane concentrate, unslaked lime, aluminum oxide and ferrosilicon.
The triphane concentrate is by triphane rawore (α triphane Li 2OAl 2O 34SiO 2).After being heated to 950 ℃-1100 ℃ with purified thermal source, the crystal grain efflorescence taking place during cooling become triphane concentrate (beta spodumene), the Lithium Oxide 98min actual content is generally between 2.9--7.6% in the triphane concentrate.
Triphane concentrate major ingredient is: Lithium Oxide 98min (Li 2O), silicon-dioxide (SiO 2), aluminum oxide (Al 2O 3) and a spot of sodium oxide (Na 2O), potassium oxide (K 2O), ferric oxide (Fe 2O 3) etc.The performance requriements of four kinds of reaction material during the system lithium:
The content 2.9-7.6% of Lithium Oxide 98min in the lithium brightness factory concentrate, granularity is less than 100 orders.
Unslaked lime (CaO) purity is more than 96%, and granularity is less than 80 orders.
Aluminum oxide (Al 2O 3) purity is more than 98%, granularity is less than 80 orders.
Ferrosilicon purity is more than 80%, and granularity is less than 120 orders.
The method of calculation of reduction reaction material fiting ratio:
This law adopts electrical conductivity of molten slag vacuum-thermal reduction system lithium principle, and its proportioning is that the change with Lithium Oxide 98min content in the triphane concentrate changes, but is all calculated with the empirical formula of slag component:
Triphane concentrate chemical constitution
Figure A20071008590100041
According to CaO-SiO 2-Al 2O 3The fusibility curve of system shows that it is 1300 ℃ of zones that fusing point is arranged among the figure, considers Al simultaneously 2O 3Dosage must suit, if aluminum oxide deficiency in the slag, will with electrode generation charcoal thermal response, and the consumption of reduction reaction furnace carbon lining is increased.Rule of thumb, the slag components contents should be strict controlled in the following scope: CaO/SiO 2＞2, Al 2O 3/ SiO 2＞0.3 (molecular ratio).
Get 1 #The chemical composition of triphane concentrate, calculate proportioning with 1000 gram concentrate material:
Reduction reaction equation: 2Li 2O+Si==4Li+SiO 2(1)
2Li 2O+2CaO+nAl 2O 3+Si(Fe)＝＝4Li+2CaO·SiO 2·nAl 2O 3+(Fe) (2)
Lithium Oxide 98min content is in the 1000 gram triphane concentrate: 76 grams
Dioxide-containing silica is in the 1000 gram lithium brightness factory concentrate: 645 grams
Alumina content is in the 1000 gram lithium brightness factory concentrate: 269 grams
According to equation one 1., 76 gram Li 2O need generate 35.4 gram Li and 76 gram SiO with 35.4 gram Si reactions 2, SiO in the reaction material then 2Total amount is the 645+76=721 gram.
If: CaO/SiO 2=2.1,
Figure A20071008590100052
Because of unslaked lime CaO content is 96%,
Figure A20071008590100053
If:
Figure A20071008590100054
Figure A20071008590100055
Because of itself containing 269 gram Al in the concentrate 2O 3So, also replenish Al 2O 3=380-269=111 gram
Because of Al 2O 3Purity is 98%, so Al 2O 3Actual amount is 111 0.98 = 113 Gram.
The theoretical reacting weight that calculates Si according to equation (1) is 35.4 grams, is converted into siliceous 80% ferrosilicon consumption to be 35.4 0.8 = 44.25 Gram.In fact Li in whole reduction reaction material 2O content is less, can not add with theoretical reacting weight, and the ferrosilicon that must add overdose just can make Li 2O is fully reacted, and improves the extraction yield of lithium.According to test, the actual amount of ferrosilicon is being adjusted more than 3 times of theoretical reacting weight, thus the ferrosilicon actual amount=more than 44.25 * 3=132.75 gram.The final consumption of four kinds of reaction material is: triphane concentrate 1000 grams, unslaked lime 1472 grams, aluminum oxide 113 grams, 80% ferrosilicon, 133 grams.
The object of the present invention is achieved like this, a kind of method with triphane concentrate system lithium, and it may further comprise the steps:
1. press
Figure A20071008590100062
Figure A20071008590100063
Weight ratio weigh respectively, and mix four.
2. will go up prepared pulverulent mixture of step makes particle diameter n and be: 20mm≤n≤30mm unit weight is 1.8--2g/cm 3Solid particulate.
3. the solid particulate that will go up the step gained is in temperature more than 1350 ℃, optimum control is at 1500 ℃--and (temperature is high again for reduction reaction under 1600 ℃ of temperature, to reduction reaction is favourable, but very unfavorable to the reduction furnace refractory materials) and vacuum degree control at P≤30Pa than carrying out reduction reaction under the appropriate condition, generate lithium vapor.
4. will go up prepared lithium vapor cooling condensation of step becomes liquid lithium to flow in the crucible.
5. will go up prepared liquid lithium of step by the titanium sponge strainer, ingot casting gets solid-state lithium behind nitride in the removing lithium and the oxide compound.
Because the present invention adopts vacuum-thermal method directly to extract lithium from the triphane concentrate, and by starting material are carried out granulation, select for use the method for vacuum electrical conductivity of molten slag heating to smelt, so the lithium purity of producing with method of the present invention can reach more than 99%, most of lithium purity can reach 99.9%, and the rate of recovery of lithium is all more than 90%.Because the lithium purity height made from method of the present invention, repeatedly distill purification process so can save when using.It is lower to add the price of starting material own, so the cost of lithium is lower.In addition, do not produce the objectionable impurities of contaminate environment with this legal system lithium, slag is the good material of building materials industry.Because the present invention does not need the electrolyzer of complex structure costliness, so less to the investment demand of equipment yet.
Description of drawings:
Accompanying drawing is a chemical equation of the present invention:
Embodiment:
Below in conjunction with accompanying drawing the specific embodiment of the present invention is further described, a kind of method with preparing lithium from spodumene concentrate: it may further comprise the steps:
1. press
Figure A20071008590100071
Figure A20071008590100072
Weight ratio weigh granularity respectively less than 100 purpose triphane concentrate powders, purity greater than 96% granularity less than 80 purpose unslaked lime powders, purity greater than 98% granularity less than 80 purpose alumina powders and purity greater than 80% granularity less than 120 purpose ferrosilicon fines, and mix four.
2. will go up prepared pulverulent mixture of step makes particle diameter n and be: 20mm≤n≤30mm, unit weight are 1.8--2g/cm 3Solid particulate, this step purpose that pulverulent mixture is carried out granulation is to reduce in the reaction process dust in the stove and strengthen the contact reacts ability.
3. will go up prepared solid particulate of step at 1500 ℃--carry out reduction reaction under 1600 ℃ and the vacuum tightness P≤30Pa condition, generate lithium vapor and Aluminum calcium silicate, iron is dissolved in the slag.In fact from reaction mechanism, silicon at first reacts with calcium oxide, generates two calcium silicide (CaSi 2), when reducing the system pressure temperature and surpass 1000 ℃, CaSi not only 2Generate, decomposition rate increases, and reduction reaction speed also increases, and has only after Ca content in Ca dilution or the gas phase reduces, and just relies on the more weak Si of reducing power to proceed.Essence entire reaction calcium plays a leading role.Vacuum tightness is high more, and reduction reaction speed is fast more.
According to Ca--SiO 2--Al 2O 3Be fusibility curve, solid particulate is molten state being higher than under 1350 ℃ of temperature, and temperature is high more, and fluidity of molten is good more, and this molten mass has certain resistance simultaneously, can produce enough heats.The contriver adopts vacuum electric furnace to finish the described reduction reaction of this step.The effect of aluminum oxide mainly is the fusing point that reduces whole mixture.
4. will go up prepared lithium vapor cooling condensation of step becomes liquid lithium to flow in the crucible;
5. will go up prepared liquid lithium of step by the titanium sponge strainer, ingot casting gets solid-state lithium behind nitride in the removing lithium and the oxide compound, for nuclear industry, and the Li in the lithium 3N and Li 2O quickens the dirt erosion effect of liquid lithium to titanium components, should remove.
Embodiment 1: get 1 #The triphane concentrate is an example
1. press triphane concentrate (SC): unslaked lime (Cao): aluminum oxide (Al 2O 3): ferrosilicon (FeSi)=1: 1.472: 0.113: 0.133 weight ratio weighs granularity respectively less than 100 purpose triphane concentrate powders, purity greater than 96%, granularity is less than 80 purpose unslaked lime powders, purity greater than 98%, granularity less than 80 purpose alumina powders and purity greater than 80%, granularity is less than 120 purpose ferrosilicon fines, and mix four.
2. will go up prepared pulverulent mixture of step makes particle diameter n and be: n=30mm, unit weight are 1.8g/cm 3Solid particulate.
3. will go up prepared solid particulate of step and under the condition of 1600 ℃ of vacuum electric furnaces and vacuum tightness P≤30Pa, carry out reduction reaction, generate lithium vapor.
4. will go up prepared lithium vapor cooling condensation of step becomes liquid lithium to flow in the crucible;
5. the liquid lithium that will go up the step gained is by the titanium sponge strainer, and ingot casting gets solid-state lithium behind nitride in the removing lithium and the oxide compound.
Embodiment 2: get 2 #The triphane concentrate is an example
1. press triphane concentrate (SC): unslaked lime (Cao): aluminum oxide (Al 2O 3): ferrosilicon (FeSi)=1: 1.451: 0.0984: 0.0919 weight ratio weighs granularity respectively less than 100 purpose triphane concentrate powders, purity greater than 96%, granularity is less than 80 purpose unslaked lime powders, purity greater than 98%, granularity less than 80 purpose alumina powders and purity greater than 80%, granularity is less than 120 purpose ferrosilicon fines, and mix four.
2. will go up prepared pulverulent mixture of step makes particle diameter n and be: n=30mm, unit weight are 1.8g/cm 3Solid particulate.
3. will go up prepared solid particulate of step and under the condition of 1600 ℃ of vacuum electric furnaces and vacuum tightness P≤30Pa, carry out reduction reaction, generate lithium vapor.
4. will go up prepared lithium vapor cooling condensation of step becomes liquid lithium to flow in the crucible;
5. the liquid lithium that will go up the step gained is by the titanium sponge strainer, and ingot casting gets solid-state lithium behind nitride in the removing lithium and the oxide compound.
It is example that embodiment 3 gets 3# triphane concentrate:
1. press triphane concentrate (SC): unslaked lime (Cao): aluminum oxide (Al 2O 3): ferrosilicon (FeSi)=1: 1.406: 0.0644: 0.051 weight ratio weighs granularity respectively less than 100 purpose triphane concentrate powders, purity greater than 96%, granularity is less than 80 purpose unslaked lime powders, purity greater than 98%, granularity, and mixes four greater than 120 purpose ferrosilicon fines less than 80 purpose alumina powders and purity.
2. will go up prepared pulverulent mixture of step makes particle diameter n and be: n=30mm, unit weight are 1.8g/cm 3Solid particulate.
3. will go up prepared solid particulate of step and under the condition of 1600 ℃ of vacuum electric furnaces and vacuum tightness P≤30Pa, carry out reduction reaction, generate lithium vapor.
4. will go up prepared lithium vapor cooling condensation of step becomes liquid lithium to flow in the crucible;
5. will go up prepared liquid lithium of step by the titanium sponge strainer, ingot casting gets solid-state lithium behind nitride in the removing lithium and the oxide compound.

Claims (2)

  1. L, a kind of method with preparing lithium from spodumene concentrate is characterized in that it may further comprise the steps:
    1. press Weight ratio weigh granularity respectively less than 1OO purpose triphane concentrate powder, purity greater than 96%, granularity is less than 8O purpose unslaked lime powder, purity greater than 98%, granularity less than 8O purpose alumina powder and purity greater than 80%, granularity is less than 12O purpose ferrosilicon fines, and mix four.
    2. will going up prepared pulverulent mixture of step, to make particle diameter n be 20mm≤n≤3Omm, and unit weight is 1.8--2g/cm 3Solid particulate.
    3. will go up prepared solid particulate of step and under the condition of vacuum electric furnace 15OO ℃-16OO ℃ and vacuum tightness P≤3OPa, carry out reduction reaction, generate lithium vapor.
    4. will go up prepared lithium vapor cooling of step, and be condensed into liquid lithium and flow in the crucible.
    5. will go up prepared liquid lithium of step by the titanium sponge strainer, ingot casting behind nitride in the removing lithium and the oxide compound gets solid-state lithium.
  2. 2, when the triphane concentrate prepares, used purified thermal source is meant that with natural gas, coal gas, acetylene gas, fuel oil, electricity or alcohol be the thermal source that forms after the fuel combustion.
CNA2007100859015A 2007-02-26 2007-02-26 Method of preparing lithium from spodumene concentrate Pending CN101016590A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101642815A (en) * 2009-09-04 2010-02-10 黄启新 Method for preparing metal lithium at high temperature employing the electrical conductivity of molten slag
CN101818265A (en) * 2010-03-25 2010-09-01 黄启新 Method for preparing metallic lithium by using lithium hydroxide
CN102382991A (en) * 2011-11-02 2012-03-21 昆明理工大学 Method for preparing lithium metal through vacuum hot reduction of iron
CN109437251A (en) * 2018-12-11 2019-03-08 湖南中大联合创新科技发展有限公司 A method of pressure leaching spodumene, which is activated, using white lime mentions lithium salts
CN109811145A (en) * 2019-04-09 2019-05-28 北京欧菲金太科技有限责任公司 A method of lithium metal is prepared containing lithium minerals
CN110129587A (en) * 2019-05-27 2019-08-16 昆明理工大学 A kind of method that spodumene vacuum metling extracts lithium metal and prepares alusil alloy
CN110195159A (en) * 2019-05-28 2019-09-03 昆明理工大学 A kind of method that spodumene prepares alusil alloy and enriching lithium
CN112111660A (en) * 2020-08-10 2020-12-22 昆明理工大学 Method for enriching lithium from lithium ore and preparing ferro-silicon alloy and recycling aluminum oxide
CN112351953A (en) * 2018-06-07 2021-02-09 浦项产业科学研究院 Method and device for preparing lithium chloride
CN113149039A (en) * 2021-04-30 2021-07-23 四川万邦胜辉新能源科技有限公司 Method for preparing lithium oxide by thermally reducing spodumene

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101642815A (en) * 2009-09-04 2010-02-10 黄启新 Method for preparing metal lithium at high temperature employing the electrical conductivity of molten slag
CN101818265A (en) * 2010-03-25 2010-09-01 黄启新 Method for preparing metallic lithium by using lithium hydroxide
CN102382991A (en) * 2011-11-02 2012-03-21 昆明理工大学 Method for preparing lithium metal through vacuum hot reduction of iron
CN112351953A (en) * 2018-06-07 2021-02-09 浦项产业科学研究院 Method and device for preparing lithium chloride
CN112351953B (en) * 2018-06-07 2023-04-18 浦项产业科学研究院 Method and device for preparing lithium chloride
CN109437251A (en) * 2018-12-11 2019-03-08 湖南中大联合创新科技发展有限公司 A method of pressure leaching spodumene, which is activated, using white lime mentions lithium salts
CN109437251B (en) * 2018-12-11 2020-12-08 湖南中大联合创新科技发展有限公司 Method for extracting lithium salt by activating, pressing and immersing spodumene by using hydrated lime
CN109811145A (en) * 2019-04-09 2019-05-28 北京欧菲金太科技有限责任公司 A method of lithium metal is prepared containing lithium minerals
CN110129587A (en) * 2019-05-27 2019-08-16 昆明理工大学 A kind of method that spodumene vacuum metling extracts lithium metal and prepares alusil alloy
CN110195159A (en) * 2019-05-28 2019-09-03 昆明理工大学 A kind of method that spodumene prepares alusil alloy and enriching lithium
CN112111660A (en) * 2020-08-10 2020-12-22 昆明理工大学 Method for enriching lithium from lithium ore and preparing ferro-silicon alloy and recycling aluminum oxide
CN112111660B (en) * 2020-08-10 2021-08-27 昆明理工大学 Method for enriching lithium from lithium ore and preparing ferro-silicon alloy and recycling aluminum oxide
CN113149039A (en) * 2021-04-30 2021-07-23 四川万邦胜辉新能源科技有限公司 Method for preparing lithium oxide by thermally reducing spodumene
CN113149039B (en) * 2021-04-30 2023-03-03 四川万邦胜辉新能源科技有限公司 Method for preparing lithium oxide by thermal reduction of spodumene

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