WO2019015011A1 - 一种酸化法从锂磷铝石中提取碳酸锂的工艺 - Google Patents

一种酸化法从锂磷铝石中提取碳酸锂的工艺 Download PDF

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WO2019015011A1
WO2019015011A1 PCT/CN2017/098775 CN2017098775W WO2019015011A1 WO 2019015011 A1 WO2019015011 A1 WO 2019015011A1 CN 2017098775 W CN2017098775 W CN 2017098775W WO 2019015011 A1 WO2019015011 A1 WO 2019015011A1
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lithium
solution
lithium carbonate
reaction
carbonate
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PCT/CN2017/098775
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French (fr)
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范兵
彭秋华
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汕头市泛世矿产资源股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • the invention relates to the technical field of lithium extraction research and development of lithium phosphestite, in particular to a process for extracting lithium carbonate from lithium phosphite by an acidification method.
  • spodumene is the most famous, because the spodumene is large in scale and simple in composition.
  • the lithium process is mature and is currently the most used lithium mineral.
  • lithium mica is also a relatively large scale of mineralization, due to its complex composition and complex lithium extraction process, it is used for less lithium, mainly used in the glass ceramic industry.
  • Iron-lithium mica, lithium-phosphorite and lithium feldspar are sparsely distributed, and the metallogenic scale is small. So far, there have been no reports on industrial applications, and there is no public report on the lithium extraction process for these three minerals.
  • the lithium-aluminite that we want to study is a lithium mineral with the highest lithium content. Its pure mineral contains 10.1% of lithium oxide, but it is not common in nature. It is occasionally found to be small scale and not used as industrial mining. the value of. But the lithium phosphite mine discovered in Africa now has a certain scale and has the value of industrial mining.
  • Lithium phosphite is often irregular and nearly equiaxed, and its color is gray, yellow, white, green and white. Due to a certain amount of other symbiotic minerals, it actually contains Li 2 O8-9.5%, which is the highest industrial mineral containing lithium. It is produced in granitic pegmatites and is sometimes found in Yunyingyan and high-temperature quartz veins. Lithium phosphite is a lithium- and aluminum-containing fluorophosphate produced in granitic pegmatite and symbiotic with spodumene, tourmaline, lithium mica and apatite, and is mainly used as a resource for extracting lithium.
  • composition of lithium phosphite is as follows: %
  • One of the objects of the present invention is to provide a process for extracting lithium carbonate from lithium phosphite by an acidification method, and more particularly to a process for extracting lithium carbonate from lithium phosphite by a pioneering acidification method.
  • the present invention adopts the following technical scheme: a process for extracting lithium carbonate from lithium phosphite by an acidification method, which comprises the following steps:
  • Raw material grinding grinding the raw materials in the lithium phosphite
  • step (3) roasting: the material after mixing in step (2) is calcined to obtain clinker;
  • step (3) clinker is placed in the reaction vessel, water is added and heated and stirred to obtain a lithium-containing leachate;
  • the concentrated lithium sulfate solution in the step (6) and the lithium carbonate solution are subjected to a stirring reaction; after the reaction is completed, the filtration is separated, and after suction filtration, a crude lithium carbonate and a lithium negative mother liquor are obtained;
  • the lithium carbonate obtained in the step (7) is stirred and washed with water, and subjected to suction filtration to obtain a washing lithium carbonate and a mother liquor;
  • the lithium phosphite raw material is ground to 100 to 200 mesh in the step (1).
  • the ground lithium phosgene and concentrated sulfuric acid are mixed at a weight ratio of 1:0.25 to 0.37.
  • the temperature is controlled to be calcined at 500 ° C to 800 ° C, and the calcination time is 10 to 60 minutes.
  • the clinker calcined in the step (4) is ground to 100 to 200 mesh.
  • the liquid-solid ratio is 3 to 5:1
  • the leaching temperature is 20 to 150 ° C
  • the constant temperature leaching time is 0.5 to 2 hours.
  • the lithium sulfate concentrated solution and the sodium carbonate solution in the step (6) are respectively placed in an injection bottle, and the flow rate is controlled by a bottle syringe, and the two solutions are added.
  • a slurry is prepared at a liquid-solid ratio of 3:1, heating and stirring are turned on, separation by filtration, and suction washing to obtain a washed lithium carbonate and a mother liquor.
  • the temperature is gradually increased to about 80 ° C during the stirring, the time is 30 to 40 minutes, and then the temperature is raised to 95 ° C, and then separated by filtration, and then separated after separation. Filter, filter dry, rinse with water, and filter.
  • the leachate obtained in the step (4) is adjusted to a pH of 7 to 8 with solid sodium hydroxide, and the solution is heated to 80 to 90 ° C and reacted at a constant temperature for 10 to 15 minutes; After the aluminum reaction is completed, the solution is filtered; then, the pH is adjusted to 14 by adding sodium hydroxide, and then a saturated sodium carbonate solution of 10% of the calculated amount or a lithium mother liquor in the production is added, and the solution is heated to 80-90 ° C and constant temperature during the reaction. The reaction is carried out for 10 to 15 minutes, and after the reaction is completed, it is filtered, and the filtered supernatant is adjusted to pH 6.5 to 7.5 with sulfuric acid.
  • the ratio of the materials provided by the present invention, the reaction time, etc. can be economically extracted and utilized to meet the commercial value of the development of the raw materials, so as to further improve the market competitiveness of the products;
  • the experimental scheme is reliable, the impurities are few, the process route is simple, and the mother liquor in the processing process can be further utilized;
  • the process route is: lithium phosphite has been ground and mixed with concentrated sulfuric acid ⁇ roasting ⁇ clinker grinding and leaching ⁇ purification and impurity removal ⁇ evaporation concentration ⁇ sinking lithium ⁇ once irrigating ⁇ secondary rinsing ⁇ drying package;
  • lithium can be extracted from lithium phosphite to become a standard battery-grade lithium carbonate product.
  • 1 is a flow chart showing the process of extracting lithium sulfate from lithium phosgene from the acidification method of the embodiment.
  • Example 1 A process for extracting lithium carbonate from lithium phosphite by an acidification method, which is characterized Lie in: including the following steps:
  • Raw material grinding grinding the lithium phosphite raw material
  • step (3) roasting: the material after mixing in step (2) is calcined to obtain clinker;
  • step (3) clinker is placed in the reaction vessel, water is added and heated and stirred to obtain a lithium-containing leachate;
  • the lithium sulfate solution in the step (6) and the lithium carbonate solution are subjected to a stirring reaction; after the reaction is completed, the filtration is separated, and after suction filtration, a crude lithium carbonate and a lithium hydride mother liquor are obtained;
  • the lithium carbonate obtained in the step (7) is stirred and washed with water, and subjected to suction filtration to obtain a washing lithium carbonate and a mother liquor;
  • the step (4), the step (8), and the step (9) may be stirred by using a power agitator.
  • distilled water may be used, and the reaction vessel may preferably be a high pressure reactor or a stainless steel reaction vessel. After the reaction, a lithium-containing leachate was obtained.
  • the raw material in the lithium phosgene is ground to 100 to 200 mesh in the step (1).
  • the temperature is controlled to be calcined at 500 ° C to 800 ° C, and the calcination time is 20 to 60 minutes.
  • the clinker calcined in the step (4) is ground to 100 to 200 mesh.
  • the liquid-solid ratio is 3 to 5:1
  • the leaching temperature is room temperature (about 20 ° C) to 150 ° C
  • the constant temperature leaching time is 0.5 to 2 hours.
  • the lithium sulfate concentrated solution and the sodium carbonate solution in the step (6) are respectively placed in an injection bottle, and the flow rate is controlled by a bottle syringe, and the two solutions are added.
  • the slurry is prepared at a liquid-solid ratio of 3:1, the heating and stirring are turned on, the filtration is separated, and the mixture is filtered to obtain a lithium carbonate and a mother liquor, and two are obtained. Wash the lithium carbonate and the second mother liquor.
  • the temperature is gradually increased to about 80 ° C during the stirring, the time is 30 to 40 minutes, and then the temperature is raised to 95 ° C, followed by filtration, and dried after filtration. The water is rinsed once and then drained.
  • the leachate obtained in the step (4) is adjusted to a pH of 7 to 8 with solid sodium hydroxide, the solution is heated to 80 to 90 ° C and the reaction is kept at a constant temperature for 10 to 15 minutes; After filtration; then add sodium hydroxide to adjust the pH to 14, and then add a calculated amount of excess 10% sodium carbonate saturated solution or the production of sinking lithium mother liquor, heat soluble during the reaction The solution is heated to 80-90 ° C and reacted at a constant temperature for 10-15 minutes. After the reaction is completed, it is filtered, and the filtered supernatant is adjusted to pH 6.5-7.5 with sulfuric acid.
  • Embodiment 2 The main process routes and technical features of the present invention are detailed as follows:
  • the ingredients are added to react with the lithium mayenite ore and convert the lithium to the water-soluble lithium compound to the maximum extent, thereby facilitating the subsequent The process extracts lithium.
  • the lithium aluminite is ground to 180 mesh, then weighed and placed in a porcelain crucible.
  • the concentrated sulfuric acid is then added in proportions and then mixed by hand until the mixture is homogeneous.
  • the water-insoluble lithium in the material is converted into a water-soluble lithium compound.
  • the prepared material is placed in a muffle furnace for heating and calcination, the baking temperature is controlled at 500 to 700 ° C (each sample is set to a different baking temperature), and the constant temperature baking time is controlled to 30 minutes.
  • the calcination temperature is determined by experiments, and the constant temperature roasting time is based on the passage time of the high temperature section of the general roasting kiln in industrial production for about half an hour. Taking the four formulations in the table as an example, the lithium conversion rates at different calcination temperatures are as follows:
  • the calcination temperature is determined by experiments, and the constant temperature roasting time is based on the passage time of the high temperature section of the general roasting kiln in industrial production for about half an hour. Taking the four recipes in the table as an example, the lithium conversion rates at different calcination temperatures and at different constant temperature times are as follows:
  • the calcined clinker is ground to 180 mesh, and then a certain amount (generally 2.5 to 10 g) is weighed into the reaction vessel, and then 100 ml of distilled water is added to the reaction vessel, and the reaction vessel is packed. Turn on heating and stirring, set the reaction temperature to 95-150 ° C, reaction time 1 ⁇ 2 hours, turn off the heating after the reaction is finished, continue stirring and cool down, then filter, the filtrate is sampled and analyzed, and the leaching residue is added with 50 ml of water to heat and stir. Filtration, slag and 50 ml of water were rinsed twice. After filtration, it was placed in an oven for drying. After cooling, it was weighed and sampled to analyze the amount of lithium oxide contained in the slag. The slag water is returned for leaching (no leaching due to measurement and analysis reasons during the test).
  • the leachate obtained in the third step is adjusted to pH 7-8 with solid sodium hydroxide, and the solution is heated to 80 to 90 ° C and reacted at a constant temperature for 10 to 15 minutes to neutralize the acid in the solution and remove impurities such as aluminum in the solution. After the reaction was completed, it was filtered. Then, solid sodium hydroxide was added to adjust the pH to 14 to remove impurities such as magnesium and part of calcium in the solution. In order to remove the calcium in depth, a saturated sodium carbonate solution with a calculated excess of 10% is added (in the production, the lithium hydroxide mother liquor can be used instead of the carbonate). During the reaction, the solution should be heated to 80-90 ° C and reacted at a constant temperature for 10-15 minutes. After the reaction is completed, it is filtered. The filtered supernatant was adjusted to pH 6.5-7.5 with sulfuric acid.
  • the main chemical reactions for purifying impurities are as follows:
  • the solution obtained after the completion of the fourth step is added into a beaker or a stainless steel reaction pot, placed on an electric furnace and heated to be concentrated by evaporation, and then concentrated to a concentration of 45 g/l of lithium oxide in the solution.
  • the heating is stopped, and some impurities (mainly super-saturated precipitated calcium and magnesium) precipitated during the evaporation process are removed by suction filtration to obtain a clear lithium sulfate concentrate, and the solution components are as follows: (g/l)
  • the sodium carbonate was dissolved in distilled water or purified water, and it was made into a solution having a concentration of about 300 g/l, and filtered.
  • the lithium carbonate solution (lithium sulfate concentrated solution 1#) obtained after the completion of the fifth step and the sodium carbonate solution obtained in the sixth step are respectively placed in an injection bottle, and the flow rate is controlled by a bottle syringe, and the two solutions are added.
  • the reaction is carried out in a 1000 ml glass beaker, stirred with an electric mixer, and the heating and electric stirring are turned on during the reaction, and the reaction temperature is controlled at 85 ⁇ At 95 ° C, not more than 95 ° C, after the completion of the reaction, the temperature was kept at 95 ° C for 10 minutes and then separated by filtration.
  • the filtration separation was filtered by a filter flask. After suction filtration, crude lithium carbonate and lithium hydride mother liquor are obtained. The crude lithium carbonate must be washed to remove impurities in the liquid, and the lithium sulphate is used to recover the remaining lithium and its Sodium sulfate, recovered sodium sulfate can be sold as a by-product.
  • the lithium carbonate obtained in the seventh step is stirred and washed with distilled water or purified water.
  • the slurry is prepared by a liquid-solid ratio of 3:1, and is carried out in a high-pressure reaction kettle. Electric stirring is applied, heating and electric stirring are started, and the temperature is gradually raised to about 80 ° C for 30 to 40 minutes, and then the temperature is raised to 95 ° C. Filtration separation was carried out, and the separation was filtered by a filter flask. After suction filtration, a washed lithium carbonate and a mother liquor were obtained.
  • the lithium carbonate obtained after the completion of the eighth step is distilled and washed again with distilled water or purified water. Still in a liquid-solid ratio of 3:1 to form a slurry, in a high-pressure reactor, add electric stirring, turn on heating and electric stirring, gradually increase the temperature to about 80 ° C, the time is 30 ⁇ ⁇ 40 minutes, and then warmed to 95 ° C, The mixture was immediately separated by filtration, separated by a filter flask, filtered, and then rinsed with water, and then filtered. After suction filtration, two washed lithium carbonate and two washed mother liquors were obtained.
  • the two washed lithium carbonate obtained after the completion of the step 9 is dried.
  • the two washed lithium carbonate was placed in a porcelain dish, baked in an oven at 120 ° C for two hours, then taken out and placed in a desiccator to cool to room temperature to obtain a lithium carbonate product, which was weighed and sampled for analysis.
  • the analysis results are as follows:
  • the following is a preferred embodiment of the invention.
  • the above quality battery grade lithium carbonate product and the best recovery rate are obtained by the following steps.
  • the leach residue is heated and stirred and washed at a liquid-solid ratio of about 3:1, and then rinsed.
  • the wet slag weighs 427 grams, and the measuring cylinder is used to measure 1000 ml of distilled water into a stainless steel reaction pot.
  • the reaction pot is placed on an electric furnace, equipped with electric stirring, then turned on for heating and stirring, and stirred at 70-80 ° C for 15 minutes, then vacuum-filtered with a suction filter bottle, and rinsed twice with water, 100 ml of water each time.
  • the dried slag is washed in an enamel pan, placed in an oven, dried at 105 ° C, weighed after cooling, and sampled and analyzed.
  • the analysis results are as follows: (%)
  • the second step of the milled clinker is ground to 100 mesh, 400 g is weighed into a stainless steel reaction pot, and 1600 ml of distilled water is weighed into a stainless steel reaction pot according to a ratio of liquid to solid ratio of 4:1. Place the pot on the electric stove, install the electric stirring, cover the lid, turn on the heating and stirring, and react at a constant temperature of about 95 °C for 1 hour. After the reaction is completed, the hot solution is filtered. Here, a suction filter was used for suction filtration to obtain 1455 ml of the filtrate, which was sampled and analyzed. The analysis results were as follows: (g/l)
  • the leach residue is heated and stirred and washed at a liquid-solid ratio of about 3:1, and then rinsed.
  • the wet slag weighs 410 grams, and the measuring cylinder is used to measure 1000 ml of distilled water into a stainless steel reaction pot.
  • the reaction pot is placed on an electric furnace, equipped with electric stirring, then turned on for heating and stirring, and stirred at 70-80 ° C for 15 minutes, then vacuum-filtered with a suction filter bottle, and rinsed twice with water, 100 ml of water each time.
  • the dried slag is washed in an enamel pan, placed in an oven, dried at 105 ° C, weighed after cooling, and sampled and analyzed.
  • the analysis results are as follows: (%)
  • the second step of the milled clinker is ground to 200 mesh, 400 g is weighed into a stainless steel reaction pot, and 1200 ml of distilled water is weighed into a stainless steel reaction pot according to a ratio of liquid to solid ratio of 3:1, and the reaction is carried out. Place the pot on the electric stove, install the electric stirring, cover the lid, turn on the heating and stirring, and react at a constant temperature of about 95 °C for 1 hour. After the reaction is completed, the hot solution is filtered. Here, a suction filter was used for suction filtration to obtain 1056 ml of filtrate, which was sampled and analyzed. The analysis results were as follows: (g/l)
  • the leach residue is heated and stirred and washed at a liquid-solid ratio of about 3:1, and then rinsed.
  • the wet slag weighs 413 grams, and the measuring cylinder is used to measure 1000 ml of distilled water into a stainless steel reaction pot.
  • the reaction pot is placed on an electric furnace, equipped with electric stirring, then turned on for heating and stirring, and stirred at 70-80 ° C for 15 minutes, then vacuum-filtered with a suction filter bottle, and rinsed twice with water, 100 ml of water each time.
  • the dried slag is washed in an enamel pan, placed in an oven, dried at 105 ° C, weighed after cooling, and sampled and analyzed.
  • the analysis results are as follows: (%)
  • the leaching solution obtained in the step 3-1 is adjusted to pH 7-8 with solid sodium hydroxide, and the solution is heated to 80 to 90 ° C and reacted at a constant temperature for 10 to 15 minutes to neutralize the acid in the solution and remove the aluminum in the solution. Impurities, filtered after completion of the reaction. Then, solid sodium hydroxide was added to adjust the pH to 14 to remove impurities such as magnesium and part of calcium in the solution. In order to remove the calcium in depth, a saturated sodium carbonate solution with a calculated excess of 10% is added (in the production, the lithium hydroxide mother liquor can be used instead of the carbonate). During the reaction, the solution should be heated to 80-90 ° C and reacted at a constant temperature for 10-15 minutes. After the reaction is completed, it is filtered. The filtered supernatant was adjusted to pH 6.5-7.5 with sulfuric acid.
  • Evaporation and concentration 1794ml of the solution obtained after the completion of the fourth step is added to the beaker, placed on an electric furnace and heated to evaporate and concentrate. When it is concentrated to about 550 ml of the solution, the heating is stopped, the cooling is allowed to stand, and then some filtration is carried out to remove some impurities precipitated during the evaporation process ( Mainly super-saturated precipitated calcium and magnesium impurities, etc., to obtain a clear lithium sulphate concentrate 541ml, the composition of the solution is as follows: (g / l)
  • the sodium carbonate was dissolved in distilled water or purified water, and it was made into a solution having a concentration of about 300 g/l, and filtered.
  • the lithium carbonate solution obtained after the completion of the fifth step and the sodium carbonate solution obtained in the sixth step are respectively placed in the hanging bottle for injection, and the flow rate is controlled by the bottle syringe, and the two solutions are added, and the ratio of the addition time is lithium sulfate.
  • Solution: sodium carbonate solution 1: 0.15
  • the reaction is carried out in a 1000 ml glass beaker, stirred with an electric mixer, and the heating and electric stirring are turned on during the reaction, and the reaction temperature is controlled within 85 to 95 ° C, not exceeding 95 ° C.
  • the mixture was centrifuged at 95 ° C for 10 minutes and then separated by filtration. The filtration separation was filtered by a filter flask. After suction filtration, crude lithium carbonate and lithium cation mother liquor are obtained, and the crude lithium carbonate must be washed to remove impurities in the liquid solution.
  • the lithium carbonate obtained in the seventh step is stirred and washed with distilled water or purified water.
  • the slurry is prepared by a liquid-solid ratio of 3:1, and is carried out in a high-pressure reaction kettle, and electric stirring is applied to turn on the heating. With electric stirring, gradually increase the temperature to about 80 ° C for 30 minutes, then raise the temperature to 95 ° C, immediately filter and separate, and use a filter bottle to filter. After suction filtration, a washed lithium carbonate and a mother liquor were obtained.
  • the lithium carbonate obtained after the completion of the eighth step is distilled and washed again with distilled water or purified water. Still in a liquid-solid ratio of 3:1 to form a slurry, in a high pressure reactor, add electric stirring, turn on heating and electric stirring, gradually warm to 80 ° C, time is 30 minutes, then warm to 95 ° C, immediately filter Separation and separation were filtered by a filter flask, filtered, washed with water, and then filtered. After suction filtration, two washed lithium carbonate and two washed mother liquors were obtained.
  • the two washed lithium carbonate obtained after the completion of the step 9 is dried.
  • the two washed lithium carbonate was placed in a porcelain dish, baked in an oven at 120 ° C for two hours, then taken out and placed in a desiccator to cool to room temperature to obtain a lithium carbonate product, which was weighed and sampled for analysis.
  • the analysis results of lithium carbonate products are shown in Table 9, which meets the battery-grade lithium carbonate standard.
  • the lithium recovery rate of the entire process can reach 88%.

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Abstract

提供一种酸化法从锂磷铝石中提取碳酸锂的工艺，包括以下步骤：原料磨细-配料-磨细后的锂磷铝石以及浓硫酸进行混合-焙烧-调浆浸出-净化除杂-除去铝或钙等杂质-蒸发浓缩-一次沉锂-一次搅洗-二次搅洗-烘干得到碳酸锂产品。该方法的可靠性以及经济性高。

Description

一种酸化法从锂磷铝石中提取碳酸锂的工艺 技术领域：
本发明涉及锂磷铝石的锂提取研发技术领域，尤其涉及一种酸化法从锂磷铝石中提取碳酸锂的工艺。
背景技术：地球上锂的工业矿物主要有以下几种：
表1 锂的工业矿物
Figure PCTCN2017098775-appb-000001
其中以锂辉石最为著名，因为锂辉石成矿规模大，成分简单，提 锂工艺成熟，是目前使用最多的锂矿物。而锂云母虽然也是成矿规模比较大，但由于其成分复杂，提锂工艺也复杂，因而用于提锂较少，主要用于玻璃陶瓷行业。铁锂云母、锂磷铝石和透锂长石则由于分布稀少，成矿规模小，至今未有工业应用的报道，而关于对此三种矿物的提锂工艺方法则更未见公开报道。
我们要研究的锂磷铝石是一种含锂量最高的锂矿物，其纯矿物含氧化锂量为10.1％，但其在自然界中不常见，偶有发现也是很小规模，没有作为工业开采的价值。但现在在非洲发现的这个锂磷铝石矿则有一定的规模，具备工业开采的价值。
锂磷铝石常为不规则块状和近等轴状，颜色为灰色、黄白、绿白等，由于有一定量的其它共生矿物，实际含Li2O8～9.5％，是含锂最高的工业矿物，产于花岗伟晶岩中，有时也见于云英岩和高温石英脉中。锂磷铝石是一种含锂、铝的氟磷酸盐，产于花岗伟晶岩，与锂辉石、电气石、锂云母及磷灰石共生，主要用作提取锂的资源。
锂磷铝石的组成如下：％
表2
Figure PCTCN2017098775-appb-000002
发明内容：
本发明的目的之一在于提供一种酸化法从锂磷铝石中提取碳酸锂的工艺，尤其是一种开创性的酸化法从锂磷铝石中提取碳酸锂的工艺。
为达到上述目的，本发明采用如下技术方案：一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：包括以下步骤：
(1)原料磨细：对锂磷铝石中的原料进行磨细；
(2)配料：将步骤(1)磨细后的锂磷铝石以及浓硫酸以重量比为1∶0.25～0.37进行混合；
(3)焙烧：对步骤(2)混合后的物料进行焙烧，得到熟料；
(4)调浆浸出：对步骤(3)熟料置于反应釜中加入水进行加热搅拌，得到含锂的浸出液；
(5)净化除杂：对步骤(4)中浸出的溶液中除去铝或钙等杂质；
(6)蒸发浓缩：在步骤(5)中反应完成后的溶液进行蒸发浓缩，得到硫酸锂浓溶液。
(7)一次沉锂：将步骤(6)中的浓硫酸锂溶液与碳酸锂溶液进行在搅拌反应；在反应完成后进行过滤分离，在抽滤后得到粗品碳酸锂和沉锂母液；
(8)一次搅洗：将步骤(7)完成得到的碳酸锂加水搅拌洗涤，并进行抽滤得到一洗碳酸锂和一洗母液；
(9)二次搅洗：将步骤(8)完成得到的碳酸锂加水搅拌洗涤；抽滤后得到二洗碳酸锂和二洗母液；
(10)烘干：将第9步完成后得到的二洗碳酸锂置于烘箱内进行烘干，烘干完成后取出冷却至室温，得到碳酸锂产品。
作为优选的，在步骤(1)中对锂磷铝石原料磨细至100～200目。
作为优选的，在步骤(2)中将磨细后的锂磷铝石以及浓硫酸以重量比为1∶0.25～0.37进行混合。
作为优选的，在步骤(3)中温度控制在500℃～800℃进行焙烧，焙烧时间为10～60分钟。
作为优选的，在步骤(4)焙烧后的熟料磨细至100～200目。
作为优选的，在步骤(4))中浸出液固比3～5∶1，浸出温度20～150℃，恒温浸出时间0.5～2小时。
作为优选的，在步骤(7)中，将步骤(6)中的硫酸锂浓溶液与碳酸钠溶液分别装入注射用吊瓶内，用吊瓶注射器控制流量，两种溶液对加。
进一步的，在步骤(7)中对加时的比例为硫酸锂溶液∶碳酸钠溶液＝1∶0.15，控制反应温度在85～95℃。
进一步的，在步骤(8)和\或步骤(9)中以液固比3∶1配成浆液，开启加热以及搅拌，过滤分离，抽滤后得到一洗碳酸锂和一洗母液。
作为优选的，在步骤(8)和\或步骤(9)中，在搅拌过程中逐步升温至80℃左右，时间为30～40分钟，然后升温至95℃后进行过滤分离，分离后进行抽滤，滤干后加水淋洗一遍，再滤干。
作为优选的，在步骤(5)中，将步骤(4)得到的浸出液用固体氢氧化钠调PH至7～8，加热溶液至80～90℃并恒温反应10～15分钟； 将铝反应完成后过滤；然后再加氢氧化钠调PH至14，再加入计算量过量10％的碳酸钠饱和溶液或生产中的沉锂母液，反应过程中加热溶液至80～90℃并恒温反应10～15分钟，待反应完成后过滤，过滤后的清液再用硫酸调PH至6.5～7.5。
本发明的优点在于：
1，提供了一种开创性的锂磷铝石提取碳酸锂的工艺；其通过原料磨细、配料、焙烧、调浆浸出、净化除杂、一次沉锂、一次搅洗、二次搅洗、等步骤提取碳酸锂产品；
2，在本发明提供的物料的配比、反应的时间等可以经济性的提取利用其原料，以符合对该原料的开发的商业价值，以进一步的提高其产品的市场竞争力；
3，实验的方案可靠，杂质少，工艺路线简单，且可以对加工过程中的母液进一步的利用；
4，工艺路线为：锂磷铝石经过磨细并与浓硫酸一起配料→焙烧→熟料磨细并浸出→净化除杂→蒸发浓缩→沉锂→一次搅洗→二次搅洗→烘干包装；
5，应用本发明的工艺技术，可以从锂磷铝石中将锂提取出来，变成符合标准的电池级碳酸锂产品，
附图说明：
附图1为实施例的酸化法从锂磷铝石中提取硫酸锂的工艺流程图。
具体实施方式：
实施例1：一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征 在于：包括以下步骤：
(1)原料磨细：对锂磷铝石原料进行磨细；
(2)配料：将步骤(1)磨细后的锂磷铝石以及浓硫酸以重量比为1∶0.25～0.37进行混合；
(3)焙烧：对步骤(2)混合后的物料进行焙烧，得到熟料；
(4)调浆浸出：对步骤(3)熟料置于反应釜中加入水进行加热搅拌，得到含锂的浸出液；
(5)净化除杂：对步骤(4)中浸出的溶液中除去铝或钙等杂质；
(6)蒸发浓缩：在步骤(5)中反应完成后的溶液进行蒸发浓缩，得到硫酸锂浓溶液。
(7)一次沉锂：将步骤(6)中的硫酸锂溶液与碳酸锂溶液进行在搅拌反应；在反应完成后进行过滤分离，在抽滤后得到粗品碳酸锂和沉锂母液；
(8)一次搅洗：将步骤(7)完成得到的碳酸锂加水搅拌洗涤，并进行抽滤得到一洗碳酸锂和一洗母液；
(9)二次搅洗：将步骤(8)完成得到的碳酸锂加水搅拌洗涤；抽滤后得到二洗碳酸锂和二洗母液；
作为优选的，步骤(4)、步骤(8)、步骤(9)可以采用电动搅拌器进行搅拌，其较佳的可以采用蒸馏水，其反应釜较佳的可以采用高压反应釜或不锈钢反应锅，反应后得到含锂的浸出液。
(10)烘干：将第9步完成后得到的二洗碳酸锂置于烘箱内进行烘干，烘干完成后取出冷却至室温，得到碳酸锂产品。
作为优选的，在步骤(1)中对锂磷铝石中的原料磨细至100～200目。
作为优选的，在步骤(3)中温度控制在500℃～800℃进行焙烧，焙烧时间为20～60分钟。
作为优选的，在步骤(4)焙烧后的熟料磨细至100～200目。
作为优选的，在步骤(4))中浸出液固比3～5∶1，浸出温度室温(约20℃)～150℃，恒温浸出时间0.5～2小时。
作为优选的，在步骤(7)中，将步骤(6)中的硫酸锂浓溶液与碳酸钠溶液分别装入注射用吊瓶内，用吊瓶注射器控制流量，两种溶液对加。
进一步的，在步骤(7)中对加时的比例为硫酸锂溶液∶碳酸钠溶液＝1∶0.15，控制反应温度在85～95℃。
进一步的，在步骤(8)和\或步骤(9)中以液固比3∶1配成浆液，开启加热以及搅拌，过滤分离，抽滤后得到一洗碳酸锂和一洗母液以及得到二洗碳酸锂和二洗母液。
作为优选的，在步骤(8)和\或步骤(9)中，在搅拌过程中逐步升温至80℃左右，时间为30～40分钟，然后升温至95℃后进行过滤分离，滤干后加热水淋洗一遍，再滤干。
作为优选的，在步骤(5)中，将步骤(4)得到的浸出液用固体氢氧化钠调PH至7～8，加热溶液至80～90℃并恒温反应10～15分钟；将铝反应完成后过滤；然后再加氢氧化钠调PH至14，再加入计算量过量10％的碳酸钠饱和溶液或生产中的沉锂母液，反应过程中加热溶 液至80～90℃并恒温反应10～15分钟，待反应完成后过滤，过滤后的清液再用硫酸调PH至6.5～7.5。
实施例2：本发明的主要工艺路线及技术特征详述如下：
1、原料磨细与配料
将原料磨细并在配料时混匀有利于固相反应的顺利进行，配料是为了加入能与锂磷铝石矿反应并将锂最大程度转化为可溶于水的锂化合物，从而有利于后续工序提取锂。
1.1、将锂磷铝石矿磨细至180目，然后称重，放入一瓷坩埚中。然后按比例加入浓硫酸，再进行手工混合，直至混合均匀为止。
锂磷铝石与硫酸的配比为：锂磷铝石∶硫酸＝1∶0.25～～0.37
配方经过了预选后，将几组主要配方列出。
具体试验配方如下表3：
编号 1 2 3 4
配方 1∶0.25 1∶0.30 1∶0.35 1∶0.37
2、焙烧
通过焙烧，物料中不溶于水的锂转化为可溶于水的锂化合物。
将配好的料放入马弗炉内升温焙烧，焙烧温度控制在500～700℃(每个样品设定不同的焙烧温度)，恒温焙烧时间控制为30分钟。
焙烧温度通过试验确定，而恒温焙烧时间则是以工业生产上一般的焙烧窑高温段通过时间约半小时为依据。以表中的4个配方为例，其不同焙烧温度下的锂转化率如下表：
表4
焙烧温度 500℃ 600℃ 650℃ 700℃ 800℃
1∶0.25 51.26％ 55.31％ 58.45％ 59.68％ 59.98％
1∶0.30 71.84％ 77.19％ 82.56％ 83.95％ 84.12％
1∶0.35 76.34％ 86.13％ 94.36％ 95.20 95.52
1∶0.37 79.65％ 86.96％ 95.11％ 97.48％ 97.58％
焙烧温度通过试验确定，而恒温焙烧时间则是以工业生产上一般的焙烧窑高温段通过时间约半小时为依据。以表中的4个配方为例，其不同焙烧温度下及不同恒温时间的锂转化率如下表：
表4-1(以锂磷铝石∶硫酸＝1∶0.37配比的焙烧为例)
Figure PCTCN2017098775-appb-000003
表4-2(以锂磷铝石∶硫酸＝1∶0.37配比且30分钟恒温焙烧为例)
磨细精细度(目) 500℃ 600℃ 650℃ 700℃ 800℃
100 32.49％ 35.26％ 45.25％ 56.28％ 63.63％
180 79.65％ 86.96％ 95.11％ 97.48％ 97.69％
200 81.52％ 87.32％ 95.45％ 97.62％ 97.96％
3、调浆浸出
将焙烧好的熟料磨细至180目，然后称取一定的量(一般2.5～～10克)加入反应釜中，再量取100ml蒸馏水加入反应釜，将反应釜装好， 开启加热和搅拌，设定反应温度为95～150℃，反应时间1～～2小时，反应结束后关闭加热，继续搅拌并冷却降温，然后过滤，滤液取样分析，浸出渣加50ml水加热搅拌洗涤，过滤，渣再加50ml水淋洗两次，过滤后放入烘箱内烘干，冷却后称重并取样分析渣含氧化锂量。洗渣水返回用于浸出(由于试验时计量及分析原因没有返回浸出)。
为了得到较高浓度及较大体积的锂溶液，每次称取200～400克焙烧熟料以液固比3～5∶1的比例在不锈钢反应锅内进行浸出，加热则用电炉，并用电动搅拌。同样反应温度为95～150℃，反应时间1～～2小时。反应完成后自然冷却，然后过滤，采用瓷漏斗和滤瓶以及真空泵进行真空抽滤，滤干后取出浸出渣以液固比3∶1加水并加热搅拌洗涤，加热时间10～20分钟，加热温度80℃左右，然后再次抽滤，待抽干后加水淋洗两次，每次淋洗液固比为0.5∶1，抽滤干后取出放入烘箱内烘干，冷却后称重并取样分析渣含氧化锂量，洗渣水可以返回用于浸出(由于试验时计量及分析原因没有返回浸出)。浸出液分析结果(1#、2#对应的配方分别是1∶0.35和1∶0.37)
表5(mg/l)
Figure PCTCN2017098775-appb-000004
Figure PCTCN2017098775-appb-000005
注：1#2#是用反应釜在高液固比时的结果，3#是用反应锅在低液固比时的结果。
不同浸出温度及不同浸出时间对浸出率的影响如下
表6
Figure PCTCN2017098775-appb-000006
浸出渣分析结果如下：
表7(％)
Figure PCTCN2017098775-appb-000007
Figure PCTCN2017098775-appb-000008
4、净化除杂
将第3步得到的浸出液用固体氢氧化钠调PH至7～8，加热溶液至80～90℃并恒温反应10～15分钟，以中和溶液中的酸并除去溶液中的铝等杂质，反应完成后过滤。然后再加固体氢氧化钠调PH至14，以除去溶液中的镁和部分的钙等杂质。为了深度去除其中的钙，还要加入计算量过量10％的碳酸钠饱和溶液(生产中可以用沉锂母液代替，利用其中的碳酸根)。反应过程中应加热溶液至80～90℃并恒温反应10～15分钟，待反应完成后过滤。过滤后的清液再用硫酸调PH至6.5～7.5。
净化除杂的主要化学反应如下：
Al3++OH-→Al(OH)3↓
Mg2++OH-→Mg(OH)2↓
Ca2++OH→Ca(OH)2↓
Ca2++CO3 2-→CaCO3↓
5、蒸发浓缩
将第4步完成后得到的溶液加入烧杯或不锈钢反应锅内，置于电炉上加热进行蒸发浓缩，等到浓缩到溶液中氧化锂浓度为45g/l 左右时，停止加热，抽滤去除蒸发过程中析出的一些杂质(主要是过饱和析出的钙镁等杂质)，得到清亮的硫酸锂浓缩液，溶液成分如下：(g/l)
表8
Figure PCTCN2017098775-appb-000009
6、溶解碳酸钠
用蒸馏水或纯净水溶解碳酸钠，将其配制成浓度约300g/l的溶液，过滤。
7、一次沉锂
将第5步完成后得到的碳酸锂溶液(硫酸锂浓溶液1#)与第6步得到的碳酸钠溶液分别装入注射用吊瓶内，用吊瓶注射器控制流量，两种溶液对加，对加时的比例为硫酸锂溶液∶碳酸钠溶液＝1∶0.15，反应在1000ml玻璃烧杯内进行，用电动搅拌机进行搅拌，在反应进行时开启加热和电动搅拌，并控制反应温度在85～～95℃内，不超过95℃，反应完成后，在95℃恒温10分钟再进行过滤分离。过滤分离采用滤瓶抽滤。抽滤后得到粗品碳酸锂和沉锂母液，粗品碳酸锂必须经过洗涤去除附液中的杂质，沉锂母液则用于回收剩余的锂和其中的 硫酸钠，回收的硫酸钠可以作为副产品销售。
8、一次搅洗
将第7步完成得到的碳酸锂加蒸馏水或纯净水搅拌洗涤。以液固比3∶1配成浆液，在高压反应釜内进行，加电动搅拌，开启加热和电动搅拌，逐步升温至80℃左右，时间为30～～40分钟，然后升温至95℃，马上进行过滤分离，分离采用滤瓶抽滤。抽滤后得到一洗碳酸锂和一洗母液。
9、二次搅洗
将第8步完成后得到的碳酸锂加蒸馏水或纯净水再次搅拌洗涤。仍以液固比3∶1配成浆液，在高压反应釜内进行，加电动搅拌，开启加热和电动搅拌，逐步升温至80℃左右，时间为30～～40分钟，然后升温至95℃，马上进行过滤分离，分离采用滤瓶抽滤，滤干后加水淋洗一遍，再滤干。抽滤后得到二洗碳酸锂和二洗母液。
10、烘干
将第9步完成后得到的二洗碳酸锂进行烘干。将二洗碳酸锂装在瓷盘中，放入烘箱内在120℃下烘两个小时，然后取出并放入干燥器内冷却至室温，得到碳酸锂产品，将其称重，取样分析。分析结果如下：
表9
Figure PCTCN2017098775-appb-000010
实施例3：
以下为本发明的最佳实施例。通过以下各步骤得到上述质量的电池级碳酸锂产品和最好的回收率。
(1)原料磨细与配料：
先将锂磷铝石矿磨细至180目。取一瓷坩埚，洗净烘干，称重， 然后将磨细的锂磷铝石粉加入瓷坩埚中称重，称取重量为400克，再用一塑料烧杯称取140克浓硫酸，将称好的浓硫酸加入瓷坩埚中与锂磷铝石混合，手工混合均匀。此时的配方及配比为：锂磷铝石∶硫酸＝1∶0.35。
(2)焙烧：
将第1步配好的料用两个瓷坩埚装好，放入马弗炉内，开启加热，设置最高温度为700℃。待马弗炉内温度升到700℃后，恒温焙烧30分钟，到时间后关闭开关停止加热。然后待炉温降下来后取出置干燥器中，冷却至室温，称重。然后将其磨细至过180目筛。
(3-1)浸出：
将第2步经磨细至180目后的熟料称取400克加入不锈钢反应锅中，按照液固比5∶1的比例用量筒量取2000ml蒸馏水加入不锈钢反应锅中，将反应锅置于电炉上，装上电动搅拌，盖好盖子，开启加热和搅拌，在95℃左右恒温反应1小时。
反应完成后，将热溶液过滤。此处采用抽滤瓶进行抽滤，得滤液1827ml，取样分析，分析结果如下：(g/l)
Figure PCTCN2017098775-appb-000011
浸出渣以液固比约3∶1的比例加水加热搅拌洗涤，然后再淋洗。
湿渣重427克，用量筒量取1000ml蒸馏水加入不锈钢反应锅中， 反应锅置于电炉上，装上电动搅拌，然后开启加热和搅拌，在70～80℃温度下搅洗15分钟，然后用抽滤瓶真空抽滤，并加水淋洗两次，每次加水100ml，滤干，洗过的湿渣用搪瓷盘装好放入烘箱中，在105℃温度下烘干，冷却后称重，并取样分析，分析结果如下：(％)
Figure PCTCN2017098775-appb-000012
(3-2)浸出：
将第2步经磨细后的熟料磨细至100目，称取400克加入不锈钢反应锅中，按照液固比4∶1的比例用量筒量取1600ml蒸馏水加入不锈钢反应锅中，将反应锅置于电炉上，装上电动搅拌，盖好盖子，开启加热和搅拌，在95℃左右恒温反应1小时。反应完成后，将热溶液过滤。此处采用抽滤瓶进行抽滤，得滤液1455ml，取样分析，分析结果如下：(g/l)
Figure PCTCN2017098775-appb-000013
浸出渣以液固比约3∶1的比例加水加热搅拌洗涤，然后再淋洗。
湿渣重410克，用量筒量取1000ml蒸馏水加入不锈钢反应锅中， 反应锅置于电炉上，装上电动搅拌，然后开启加热和搅拌，在70～80℃温度下搅洗15分钟，然后用抽滤瓶真空抽滤，并加水淋洗两次，每次加水100ml，滤干，洗过的湿渣用搪瓷盘装好放入烘箱中，在105℃温度下烘干，冷却后称重，并取样分析，分析结果如下：(％)
Figure PCTCN2017098775-appb-000014
(3-3)浸出：
将第2步经磨细后的熟料磨细至200目，称取400克加入不锈钢反应锅中，按照液固比3∶1的比例用量筒量取1200ml蒸馏水加入不锈钢反应锅中，将反应锅置于电炉上，装上电动搅拌，盖好盖子，开启加热和搅拌，在95℃左右恒温反应1小时。反应完成后，将热溶液过滤。此处采用抽滤瓶进行抽滤，得滤液1056ml，取样分析，分析结果如下：(g/l)
Figure PCTCN2017098775-appb-000015
浸出渣以液固比约3∶1的比例加水加热搅拌洗涤，然后再淋洗。
湿渣重413克，用量筒量取1000ml蒸馏水加入不锈钢反应锅中， 反应锅置于电炉上，装上电动搅拌，然后开启加热和搅拌，在70～80℃温度下搅洗15分钟，然后用抽滤瓶真空抽滤，并加水淋洗两次，每次加水100ml，滤干，洗过的湿渣用搪瓷盘装好放入烘箱中，在105℃温度下烘干，冷却后称重，并取样分析，分析结果如下：(％)
Figure PCTCN2017098775-appb-000016
(4)净化除杂
将第3-1步得到的浸出液用固体氢氧化钠调PH至7～8，加热溶液至80～90℃并恒温反应10～15分钟，以中和溶液中的酸并除去溶液中的铝等杂质，反应完成后过滤。然后再加固体氢氧化钠调PH至14，以除去溶液中的镁和部分的钙等杂质。为了深度去除其中的钙，还要加入计算量过量10％的碳酸钠饱和溶液(生产中可以用沉锂母液代替，利用其中的碳酸根)。反应过程中应加热溶液至80～90℃并恒温反应10～15分钟，待反应完成后过滤。过滤后的清液再用硫酸调PH至6.5～7.5。
蒸发浓缩： 将第4步完成后得到的溶液1794ml加入烧杯内，置于电炉上加热进行蒸发浓缩，等到浓缩到溶液约550ml时，停止加热，静置冷却，然后抽滤去除蒸发过程中析出的一些杂质(主要是过饱和析出的钙镁等杂质)，得到清亮的硫酸锂浓缩液541ml，溶液成分如下：(g/l)
溶液成分 Li2O Na K Ca Mg Fe SO4
检测结果 46.74 9.63 0.54 0.055 0.003 0.003 169.26
6、溶解碳酸钠
用蒸馏水或纯净水溶解碳酸钠，将其配制成浓度约300g/l的溶液，过滤。
7、一次沉锂
将第5步完成后得到的碳酸锂溶液与第6步得到的碳酸钠溶液分别装入注射用吊瓶内，用吊瓶注射器控制流量，两种溶液对加，对加时的比例为硫酸锂溶液∶碳酸钠溶液＝1∶0.15，反应在1000ml玻璃烧杯内进行，用电动搅拌机进行搅拌，在反应进行时开启加热和电动搅拌，并控制反应温度在85～～95℃内，不超过95℃，反应完成后，在95℃恒温10分钟再进行过滤分离。过滤分离采用滤瓶抽滤。抽滤后得到粗品碳酸锂和沉锂母液，粗品碳酸锂必须经过洗涤去除附液中的杂质。
8、一次搅洗
将第7步完成得到的碳酸锂加蒸馏水或纯净水搅拌洗涤。以液固比3∶1配成浆液，在高压反应釜内进行，加电动搅拌，开启加热 和电动搅拌，逐步升温至80℃左右，时间为30分钟，然后升温至95℃，马上进行过滤分离，分离采用滤瓶抽滤。抽滤后得到一洗碳酸锂和一洗母液。
9、二次搅洗
将第8步完成后得到的碳酸锂加蒸馏水或纯净水再次搅拌洗涤。仍以液固比3∶1配成浆液，在高压反应釜内进行，加电动搅拌，开启加热和电动搅拌，逐步升温至80℃左右，时间为30分钟，然后升温至95℃，马上进行过滤分离，分离采用滤瓶抽滤，滤干后加水淋洗一遍，再滤干。抽滤后得到二洗碳酸锂和二洗母液。
10、烘干
将第9步完成后得到的二洗碳酸锂进行烘干。将二洗碳酸锂装在瓷盘中，放入烘箱内在120℃下烘两个小时，然后取出并放入干燥器内冷却至室温，得到碳酸锂产品，将其称重，取样分析。碳酸锂产品分析结果见表9，符合电池级碳酸锂标准。
整个工艺过程的锂回收率可以达到88％。
当然，以上仅为本发明较佳实施方式，并非以此限定本发明的使用范围，故，凡是在本发明原理上做等效改变均应包含在本发明的保护范围内。

Claims (10)

  1. 一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：包括以下步骤：
    (1)原料磨细：对锂磷铝石原料进行磨细；
    (2)配料：将步骤(1)磨细后的锂磷铝石以及浓硫酸以重量比为1∶0.25～0.37进行混合；
    (3)焙烧：对步骤(2)混合后的物料进行焙烧，得到熟料；
    (4)调浆浸出：对步骤(3)熟料置于反应釜中加入水进行加热搅拌，得到含锂的浸出液；
    (5)净化除杂：对步骤(4)中浸出的溶液中除去铝或钙等杂质；
    (6)蒸发浓缩：在步骤(5)中反应完成后的溶液进行蒸发浓缩，得到硫酸锂浓溶液。
    (7)一次沉锂：将步骤(6)中的硫酸锂溶液与碳酸锂溶液进行在搅拌反应；在反应完成后进行过滤分离，在抽滤后得到粗品碳酸锂和沉锂母液；
    (8)一次搅洗：将步骤(7)完成得到的碳酸锂加水搅拌洗涤，并进行抽滤得到一洗碳酸锂和一洗母液；
    (9)二次搅洗：将步骤(8)完成得到的碳酸锂加水搅拌洗涤；抽滤后得到二洗碳酸锂和二洗母液；
    (10)烘干：将第9步完成后得到的二洗碳酸锂置于烘箱内进行烘干，烘干完成后取出冷却至室温，得到碳酸锂产品。
  2. 根据权利要求1所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(1)或在步骤(4)中对应的锂磷铝石原料或焙烧后的熟料磨细至100～200目。
  3. 根据权利要求1所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(2)中将磨细后的锂磷铝石以及浓硫酸以重量比为1∶0.25～0.37进行混合；
  4. 根据权利要求1所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(3)中温度控制在500℃～800℃进行焙烧，焙烧时间为20～60分钟。
  5. 根据权利要求1所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(4))中浸出液固比3～5∶1，浸出温度20～150℃，恒温浸出时间0.5～2小时。
  6. 根据权利要求1所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(7)中，将步骤(6)中的硫酸锂浓溶液与碳酸钠溶液分别装入注射用吊瓶内，用吊瓶注射器控制流量，两种溶液对加。
  7. 根据权利要求6所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(7)中对加时的比例为硫酸锂溶液∶碳酸钠溶液＝1∶0.15，控制反应温度在85～95℃。
  8. 根据权利要求1-7任一项所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(8)和\或步骤(9)中以液固比3∶1配成浆液，开启加热以及搅拌，过滤分离，抽滤后得到一洗碳酸锂和 一洗母液。
  9. 根据权利要求8所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(8)和\或步骤(9)中，在搅拌过程中逐步升温至80℃左右，时间为30～40分钟，然后升温至95℃后进行过滤分离，分离后进行抽滤，滤干后加水淋洗一遍，再滤干。
  10. 根据权利要求1-7任一项所述的一种酸化法从锂磷铝石中提取碳酸锂的工艺，其特征在于：在步骤(5)中，将步骤(4)得到的浸出液用固体氢氧化钠调PH至7～8，加热溶液至80～90℃并恒温反应10～15分钟；将铝反应完成后过滤；然后再加氢氧化钠调PH至14，再加入计算量过量10％的碳酸钠饱和溶液或生产中的沉锂母液，反应过程中加热溶液至80～90℃并恒温反应10～15分钟，待反应完成后过滤，过滤后的清液再用硫酸调PH至6.5～7.5。
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