CN103318925A - Method for producing high-purity lithium carbonate by using lithium concentrate - Google Patents
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Abstract
The invention relates to a method for producing high-purity lithium carbonate by using lithium concentrate. The method is characterized by comprising the following steps of: preparing an acid clinker, preparing a mixing size, preparing a lithium sulfate leaching solution, preparing a lithium sulfate purification liquid, preparing a lithium sulfate finishing solution, preparing a sodium carbonate solution, performing primary lithium deposition reaction, preparing a sodium separating mother liquor, preparing excellent lithium carbonate in a sweating manner, and preparing 99.99% of high-purity lithium carbonate. By adopting the method, the principle of removing calcium and magnesium ions is ingeniously utilized in preparation of common lithium carbonate; a fussy procedure of removing calcium and magnesium by ion exchange resin is avoided when the common lithium carbonate is purified to prepare the high-purity lithium carbonate; a method of recycling after separating out sodium sulfate in a freezing manner is adopted to process the primary lithium settling mother liquor; the high-purity lithium carbonate mother liquor in precipitation of the high-purity lithium carbonate is used as an optimal lithium carbonate washing liquor for primary lithium sedimentation after being recycled for a plurality of times. Thus, the method has the characteristics of simple process, high production efficiency, high recovery rate and low production cost.
Description
Technical field
The present invention relates to a kind of preparation method of pure Lithium Carbonate, relate in particular to a kind of method with lithium concentrate production pure Lithium Carbonate.
Background technology
The preparation method of 99.99% traditional pure Lithium Carbonate has two kinds:
A kind of is to be raw material through being prepared into first the ordinary hydrogen Lithium Oxide 98min after roasting, acidifying, the leaching with lithium concentrate, again the ordinary hydrogen Lithium Oxide 98min being carried out recrystallization purifies, then the lithium hydroxide after purifying is dissolved in and passes into carbonic acid gas in the pure water and carry out carbonization and become pure Lithium Carbonate, the method the ordinary hydrogen Lithium Oxide 98min is carried out recrystallization when purifying in the mother liquor remaining lithium hydroxide amount larger, yield is low.
Another kind is to be raw material with lithium concentrate or salt lake brine, the lithium that extracts obtains sinker mother liquor and common Quilonum Retard with the yellow soda ash reaction first, the sinker mother liquor adopts evaporation process, common Quilonum Retard is put in the pure water logical carbonic acid gas as the raw material of pure Lithium Carbonate and is carried out carbonization and be dissolved into lithium bicarbonate, and then lithia water removed calcium ions and magnesium ions through ion exchange resin, again the solution behind the calcium-magnesium removing is heated up and separate out pure Lithium Carbonate, the method will be used the high ion exchange resin calcium-magnesium removing ion of use cost, and preparation during common Quilonum Retard steam consumption quantity and yellow soda ash consumption all higher, ion exchange resin carries out manipulation of regeneration also can lose the part lithium, and also can produce the large waste water of comparative quantity during the bronsted lowry acids and bases bronsted lowry process resin.
Summary of the invention
The object of the present invention is to provide a kind of produce simple, the rate of recovery is high, energy-conservation produces the method for 99.99% pure Lithium Carbonate with lithium concentrate.
The technical solution used in the present invention is:
A kind of method with lithium concentrate production pure Lithium Carbonate comprises the steps:
(1) the sour grog step of preparation: the lithium concentrate of 2000 mass parts is processed into the roasting material through 1000-1150 ℃ of calcining transformation first in rotary kiln, roasting material is cooled to after 80-145 ℃ through cooler carries out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with the vitriol oil of 500-600 mass parts, and be warming up to 220-280 ℃ of constant temperature 20-30 minute and arrive to get sour grog, the remaining sulfuric acid quality percentage composition of controlling sour grog is 3-6%;
(2) preparation adjusting slurry step: following 1600-2400 mass parts slag washing water and the 1600-800 mass parts sweat mother liquor limit of adding of stirring condition adds 2500 mass parts acid grog and sizes mixing and obtain adjusting slurry in surge tank;
(3) preparation Lithium Sulphate leach liquor step: adjusting slurry is neutralized to pH=5-6 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 6.5-8 again, then filters and washs with filter, obtains Lithium Sulphate leach liquor and slag washing water;
(4) preparation Lithium Sulphate scavenging solution step: in the Lithium Sulphate leach liquor, add the pH to 9.5-11.5 that quality is regulated lithium sulfate solution than yellow soda ash and the sodium hydroxide mixing solutions of yellow soda ash: sodium hydroxide=1:1, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue;
(5) the preparation Lithium Sulphate is finished the liquid step: it is 52-60g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid;
(6) preparation sodium carbonate solution step: yellow soda ash is dissolved in the sweat mother liquor, and obtains after filtering sodium carbonate solution, the concentration of sodium carbonate of sodium carbonate solution is 200-300g/L;
(7) elementary sinker reactions steps: sodium carbonate solution is transferred in the sinker reactor, open and stir, and in reactor, add the additive that accounts for sodium carbonate solution quality 0.02%--0.1%, then sodium carbonate solution is warming up to 80-98 ℃, and keep 80-98 ℃ slowly to add Lithium Sulphate and finish liquid, the excessive 5%-25% of control yellow soda ash, carry out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain calcium contents less than 0.0005%, Mg content is less than 0.0003% top grade Quilonum Retard and elementary sinker mother liquor;
(8) analyse the mother liquid of sodium preparation process: elementary sinker mother liquor is refrigerated to-isolates sodium sulfate behind the 3-5 ℃ to obtain analysing mother liquid of sodium;
(9) sweat prepares top grade Quilonum Retard step: join in the reactor analysing mother liquid of sodium, and be incorporated as the additive of analysing mother liquid of sodium quality 0.002%-0.05% amount, then be warming up to 90 ℃-98 ℃ and separate out precipitation, through solid-liquid separation washing obtain calcium contents less than 0.0005%, Mg content is less than 0.0003% top grade Quilonum Retard, and obtaining the sweat mother liquor, Lithium Oxide 98min concentration remaining in the sweat mother liquor is controlled to be Li
2O≤4g/L; Gained sweat mother liquid recycling is in preparation sodium carbonate solution and a small amount of sour grog leaching Lithium Sulphate of sizing mixing that is used for;
(10) pure Lithium Carbonate preparation process: the top grade Quilonum Retard joined pass into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 14-19g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 90-98 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate; Carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after cooling, and the content of Lithium Oxide 98min is 14-19g/L in the control lithia water, be warming up to after filtering 90-98 ℃ separate out the precipitation and solid-liquid separation, the washing obtain 99.99% pure Lithium Carbonate, obtain equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
Additive in step (7) and the step (9) is at least a in EDTA and the citric acid.
The top grade Quilonum Retard joins and leads to carbon dioxide solubility in the pure water in the step (10), to the purity requirement of pure water is: the Ca in the pure water＜0.00005%, the Mg in the pure water＜0.00005%; Carbonization mother liquor is cooled off, require the carbonization mother liquor temperature be cooled to≤38 ℃.
The present invention has utilized dexterously and just removed calcium ions and magnesium ions when the common Quilonum Retard of preparation, avoided when common Quilonum Retard is carried out the synthesis pure Lithium Carbonate, adopting loaded down with trivial details ion exchange resin calcium-magnesium removing operation, and the processing of elementary sinker mother liquor adopted the freezing method of separating out recycle behind the sodium sulfate, this has not only saved traditional technology is carried out evaporation process to elementary sinker mother liquor steam energy consumption, and elementary mother liquor is separated out and is used for the preparation sodium carbonate solution behind the sodium sulfate and also the excessive remaining yellow soda ash of mother liquor has been recycled, the yellow soda ash consumption is low, and the mother liquor after separating out sodium sulfate is used for heating up before the preparation sodium carbonate solution, the characteristic of utilizing first Quilonum Retard to reduce with temperature rising solubleness, heat up and separate out precipitation analysing behind the sodium sulfate mother liquor, do not consume like this yellow soda ash and just directly obtain a certain amount of top grade Quilonum Retard, and then the sweat mother liquor is used for the preparation sodium carbonate solution while hot, additive decrementation yellow soda ash and steam just do not obtain a certain amount of top grade Quilonum Retard dexterously; And the pure Lithium Carbonate mother liquor of precipitation during pure Lithium Carbonate serve as the usefulness of the top grade Quilonum Retard wash water of elementary sinker after the several recycle, fully guaranteed the rate of recovery of lithium.
The present invention has that technique is simple, production efficiency is high, the rate of recovery is high, various consumption is low, constant product quality, superior product quality, characteristics that production cost is low.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1:
Get 2 tons of Lithium Oxide 98min content and be 6% lithium concentrate and in rotary kiln, be processed into the roasting material through 1000 ℃ of calcining transformations first, roasting material is cooled to after 145 ℃ through cooler carries out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with 500 kilograms of vitriol oils, and be warming up to 220 ℃ of constant temperature and arrived to get sour grog in 30 minutes, the residual sulfur acid content of controlling sour grog is 3%, then whipped state 2.4 tons of slag washing water of following adding and 0.8 ton of sweat mother liquor limit 2500 kilograms of sour grog of adding are sized mixing and are obtained adjusting slurry in surge tank, adjusting slurry is neutralized to pH=5 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 6.5 again, then filter and wash with filter, obtain Lithium Sulphate leach liquor and slag washing water, add mass percent yellow soda ash in the Lithium Sulphate leach liquor: the yellow soda ash of sodium hydroxide=1:1 and sodium hydroxide mixing solutions are regulated the pH to 9.5 of lithium sulfate solution, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue, it is 60g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid 1.9M
3, be mixed with the sodium carbonate solution 2.52M that concentration of sodium carbonate is 200g/L with yellow soda ash and sweat mother liquor again
3, and sodium carbonate solution is transferred to 5M
3The sinker reactor in, open and stir, and in still, add 504 gram EDTA, then sodium carbonate solution is warming up to 80 ℃, and keeps 80 ℃ slowly to add Lithium Sulphate and finish liquid, yellow soda ash is excessive to be 25%, carry out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain top grade Quilonum Retard and elementary sinker mother liquor, isolate sodium sulfate after elementary sinker mother liquor is refrigerated to-3 ℃ and obtain analysing mother liquid of sodium 3.4M
3, analyse mother liquid of sodium and change over to 5M
3The sweat still in, open the sweat still and stir and also add 1700 gram EDTA, then be warming up to 98 ℃ and separate out Quilonum Retard, carry out again centrifugation and washing and obtain the top grade Quilonum Retard, obtain simultaneously the sweat mother liquor; The top grade Quilonum Retard is added to and passes into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 14g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 90 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor is cooled to 37 ℃ of recycles through cooling tower, in the carbonization mother liquor of cooling, adding the top grade Quilonum Retard, then logical carbon dioxide solubility becomes lithia water, control Lithium Oxide 98min content wherein is 19g/L, transfer to after filtering again in high-purity sinker still, open stirring and be warmed up to 90 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after being cooled to 37 ℃, and the content of Lithium Oxide 98min is 14g/L in the control lithia water, be warming up to after filtering 90 ℃ and separate out precipitation and solid-liquid separation, washing obtains 99.99% pure Lithium Carbonate, obtains equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
Embodiment 2:
Get 2 tons of Lithium Oxide 98min content and be 6% lithium concentrate and in rotary kiln, be processed into the roasting material through 1150 ℃ of calcining transformations first, the roasting material when being cooled to 120 ℃, cooler is carried out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with 600 kilograms of vitriol oils, and be warming up to 280 ℃ of constant temperature and arrived to get sour grog in 20 minutes, the residual sulfur acid content of controlling sour grog is 6%, then whipped state 1.6 tons of slag washing water of following adding and 1.6 tons of sweat mother liquor limit 2500 kilograms of sour grogs of adding are sized mixing and are obtained adjusting slurry in surge tank, adjusting slurry is neutralized to pH=6 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 8 again, then filter and wash with filter, obtain Lithium Sulphate leach liquor and slag washing water, add mass percent yellow soda ash in the Lithium Sulphate leach liquor: the yellow soda ash of sodium hydroxide=1:1 and sodium hydroxide mixing solutions are regulated the pH to 11.5 of lithium sulfate solution, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue, it is 52g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid 2.2M
3, be mixed with the sodium carbonate solution 1.41M that concentration of sodium carbonate is 300g/L with yellow soda ash and sweat mother liquor again
3, and sodium carbonate solution is transferred to 5M
3The sinker reactor in, open and stir, and in still, add 1410 gram EDTA, then sodium carbonate solution is warming up to 98 ℃, and keeping 98 ℃ slowly to add Lithium Sulphate and finish liquid, yellow soda ash is excessive to be 5%, carries out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain top grade Quilonum Retard and elementary sinker mother liquor, isolate sodium sulfate after elementary sinker mother liquor is refrigerated to 5 ℃ and obtain analysing mother liquid of sodium 2.4M
3, analyse mother liquid of sodium and change over to 5M
3The sweat still in, open the sweat still and stir and also add 48 gram EDTA, then be warming up to 90 ℃ and separate out Quilonum Retard, carry out again centrifugation and washing and obtain the top grade Quilonum Retard, obtain simultaneously the sweat mother liquor; The top grade Quilonum Retard is added to and passes into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 19g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 98 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor is cooled to 36 ℃ of recycles through cooling tower, in the carbonization mother liquor of cooling, adding the top grade Quilonum Retard, then logical carbon dioxide solubility becomes lithia water, control Lithium Oxide 98min content wherein is 16g/L, transfer to after filtering again in high-purity sinker still, open stirring and be warmed up to 95 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after being cooled to 30 ℃, and the content of Lithium Oxide 98min is 17g/L in the control lithia water, be warming up to after filtering 95 ℃ and separate out precipitation and solid-liquid separation, washing obtains 99.99% pure Lithium Carbonate, obtains equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
Embodiment 3:
Get 2 tons of Lithium Oxide 98min content and be 6% lithium concentrate and in rotary kiln, be processed into the roasting material through 1100 ℃ of calcining transformations first, the roasting material when being cooled to 100 ℃, cooler is carried out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with 550 kilograms of vitriol oils, and be warming up to 250 ℃ of constant temperature and arrived to get sour grog in 25 minutes, the residual sulfur acid content of controlling sour grog is 4%, then following 2 tons of slag washing water and the 1.2 tons of sweat mother liquor limits of adding of whipped state adds 2500 sour grogs and sizes mixing and obtain adjusting slurry in surge tank, adjusting slurry is neutralized to pH=5.5 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 7 again, then filter and wash with filter, obtain Lithium Sulphate leach liquor and slag washing water, add mass percent yellow soda ash in the Lithium Sulphate leach liquor: the yellow soda ash of sodium hydroxide=1:1 and sodium hydroxide mixing solutions are regulated the pH to 10.5 of lithium sulfate solution, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue, it is 55g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid 2.0M
3, be mixed with the sodium carbonate solution 1.71M that concentration of sodium carbonate is 250g/L with yellow soda ash and sweat mother liquor again
3, and sodium carbonate solution is transferred to 5M
3The sinker reactor in, open and stir, and in still, add 1710 gram citric acids, then sodium carbonate solution is warming up to 90 ℃, and keeping 90 ℃ slowly to add Lithium Sulphate and finish liquid, yellow soda ash is excessive to be 10%, carries out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain top grade Quilonum Retard and elementary sinker mother liquor, isolate sodium sulfate after elementary sinker mother liquor is refrigerated to 0 ℃ and obtain analysing mother liquid of sodium 2.6M
3, analyse mother liquid of sodium and change over to 5M
3The sweat still in, open the sweat still and stir and also add 52 gram citric acids, then be warming up to 95 ℃ and separate out Quilonum Retard, carry out again centrifugation and washing and obtain the top grade Quilonum Retard, obtain simultaneously the sweat mother liquor; The top grade Quilonum Retard is added to and passes into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 18g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 95 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor is cooled to 35 ℃ of recycles through cooling tower, in the carbonization mother liquor of cooling, adding the top grade Quilonum Retard, then logical carbon dioxide solubility becomes lithia water, control Lithium Oxide 98min content wherein is 17g/L, transfer to after filtering again in high-purity sinker still, open stirring and be warmed up to 94 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after being cooled to 20 ℃, and the content of Lithium Oxide 98min is 14g/L in the control lithia water, be warming up to after filtering 94 ℃ and separate out precipitation and solid-liquid separation, washing obtains 99.99% pure Lithium Carbonate, obtains equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
Embodiment 4:
Get 2 tons of Lithium Oxide 98min content and be 6% lithium concentrate and in rotary kiln, be processed into the roasting material through 1050 ℃ of calcining transformations first, the roasting material when being cooled to 80 ℃, cooler is carried out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with 560 kilograms of vitriol oils, and be warming up to 260 ℃ of constant temperature and arrived to get sour grog in 20 minutes, the residual sulfur acid content of controlling sour grog is 5%, then whipped state 2.0 tons of slag washing water of following adding and 1.2 tons of sweat mother liquor limit 2500 kilograms of sour grogs of adding are sized mixing and are obtained adjusting slurry in surge tank, adjusting slurry is neutralized to pH=6 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 6.5 again, then filter and wash with filter, obtain Lithium Sulphate leach liquor and slag washing water, add mass percent yellow soda ash in the Lithium Sulphate leach liquor: the yellow soda ash of sodium hydroxide=1:1 and sodium hydroxide mixing solutions are regulated the pH to 10 of lithium sulfate solution, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue, it is 58g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid 1.95M
3, be mixed with the sodium carbonate solution 1.71M that concentration of sodium carbonate is 280g/L with yellow soda ash and sweat mother liquor again
3, and sodium carbonate solution is transferred to 5M
3The sinker reactor in, open and stir, and in still, add 400 gram EDTA and 400 gram citric acids, then sodium carbonate solution is warming up to 92 ℃, and keeping 92 ℃ slowly to add Lithium Sulphate and finish liquid, yellow soda ash is excessive to be 15%, carries out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain top grade Quilonum Retard and elementary sinker mother liquor, isolate sodium sulfate after elementary sinker mother liquor is refrigerated to 2 ℃ and obtain analysing mother liquid of sodium 2.6M
3, analyse mother liquid of sodium and change over to 5M
3The sweat still in, open the sweat still and stir and also add 400 gram EDTA and 200 gram citric acids, then be warming up to 94 ℃ and separate out Quilonum Retard, carry out again centrifugation and washing and obtain the top grade Quilonum Retard, obtain simultaneously the sweat mother liquor; The top grade Quilonum Retard is added to and passes into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 18g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 96 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor is cooled to 34 ℃ of recycles through cooling tower, in the carbonization mother liquor of cooling, adding the top grade Quilonum Retard, then logical carbon dioxide solubility becomes lithia water, control Lithium Oxide 98min content wherein is 16g/L, transfer to after filtering again in high-purity sinker still, open stirring and be warmed up to 93 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate, carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after being cooled to 25 ℃, and the content of Lithium Oxide 98min is 19g/L in the control lithia water, be warming up to after filtering 93 ℃ and separate out precipitation and solid-liquid separation, washing obtains 99.99% pure Lithium Carbonate, obtains equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
Claims (3)
1. the method with lithium concentrate production pure Lithium Carbonate is characterized in that, comprises the steps:
(1) the sour grog step of preparation: the lithium concentrate of 2000 mass parts is processed into the roasting material through 1000-1150 ℃ of calcining transformation first in rotary kiln, roasting material is cooled to after 80-145 ℃ through cooler carries out the grain diameter of ball milling to 95% less than 80 orders with ball mill, and then roasting material mixed through worm conveyor with the vitriol oil of 500-600 mass parts, and be warming up to 220-280 ℃ of constant temperature 20-30 minute and arrive to get sour grog, the remaining sulfuric acid quality percentage composition of controlling sour grog is 3-6%;
(2) preparation adjusting slurry step: following 1600-2400 mass parts slag washing water and the 1600-800 mass parts sweat mother liquor limit of adding of stirring condition adds 2500 mass parts acid grog and sizes mixing and obtain adjusting slurry in surge tank;
(3) preparation Lithium Sulphate leach liquor step: adjusting slurry is neutralized to pH=5-6 with Paris white, with the scavenging solution filter residue slurries pH is transferred to 6.5-8 again, then filters and washs with filter, obtains Lithium Sulphate leach liquor and slag washing water;
(4) preparation Lithium Sulphate scavenging solution step: in the Lithium Sulphate leach liquor, add the pH to 9.5-11.5 that quality is regulated lithium sulfate solution than yellow soda ash and the sodium hydroxide mixing solutions of yellow soda ash: sodium hydroxide=1:1, then it is filtered and obtain Lithium Sulphate scavenging solution and scavenging solution filter residue;
(5) the preparation Lithium Sulphate is finished the liquid step: it is 52-60g/L that the Lithium Sulphate scavenging solution is carried out evaporation concentration to Lithium Oxide 98min content, then filters to obtain Lithium Sulphate and finish liquid;
(6) preparation sodium carbonate solution step: yellow soda ash is dissolved in the sweat mother liquor, and obtains after filtering sodium carbonate solution, the concentration of sodium carbonate of sodium carbonate solution is 200-300g/L;
(7) elementary sinker reactions steps: sodium carbonate solution is transferred in the sinker reactor, open and stir, and in reactor, add the additive that accounts for sodium carbonate solution quality 0.02%--0.1%, then sodium carbonate solution is warming up to 80-98 ℃, and keep 80-98 ℃ slowly to add Lithium Sulphate and finish liquid, the excessive 5%-25% of control yellow soda ash, carry out centrifugation and washing after Lithium Sulphate is finished liquid and added, obtain calcium contents less than 0.0005%, Mg content is less than 0.0003% top grade Quilonum Retard and elementary sinker mother liquor;
(8) analyse the mother liquid of sodium preparation process: elementary sinker mother liquor is refrigerated to-isolates sodium sulfate behind the 3-5 ℃ to obtain analysing mother liquid of sodium;
(9) sweat prepares top grade Quilonum Retard step: join in the reactor analysing mother liquid of sodium, and be incorporated as the additive of analysing mother liquid of sodium quality 0.002%-0.05% amount, then be warming up to 90 ℃-98 ℃ and separate out precipitation, through solid-liquid separation washing obtain calcium contents less than 0.0005%, Mg content is less than 0.0003% top grade Quilonum Retard, and obtaining the sweat mother liquor, Lithium Oxide 98min concentration remaining in the sweat mother liquor is controlled to be Li
2O≤4g/L; Gained sweat mother liquid recycling is in preparation sodium carbonate solution and a small amount of sour grog leaching Lithium Sulphate of sizing mixing that is used for;
(10) pure Lithium Carbonate preparation process: the top grade Quilonum Retard joined pass into carbon dioxide solubility in the pure water and become lithia water, and the content of Lithium Oxide 98min is 14-19g/L in the control lithia water, then filter, filtrate is transferred in high-purity sinker still, open stirring and be warmed up to 90-98 ℃, then carry out centrifugation and washing, obtain carbonization mother liquor and 99.99% pure Lithium Carbonate; Carbonization mother liquor carries out recycle and continues on for carbonization dissolving top grade Quilonum Retard and become lithia water after cooling, and the content of Lithium Oxide 98min is 14-19g/L in the control lithia water, be warming up to after filtering 90-98 ℃ separate out the precipitation and solid-liquid separation, the washing obtain 99.99% pure Lithium Carbonate, obtain equally carbonization mother liquor; Carbonization mother liquor after the several times recycle is as the bath water of top grade Quilonum Retard.
2. a kind of method with lithium concentrate production pure Lithium Carbonate according to claim 1 is characterized in that, the additive in step (7) and the step (9) is at least a in EDTA and the citric acid.
3. a kind of method with lithium concentrate production pure Lithium Carbonate according to claim 1, it is characterized in that, the top grade Quilonum Retard joins and leads to carbon dioxide solubility in the pure water in the step (10), to the purity requirement of pure water is: the Ca in the pure water＜0.00005%, the Mg in the pure water＜0.00005%; Carbonization mother liquor is cooled off, require the carbonization mother liquor temperature be cooled to≤38 ℃.
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