CN116395720A - Carbonization method for purifying industrial Li 2 CO 3 Preparation of pure Li by continuous flow carbonization in process 2 CO 3 Is a process and device for the production of a metal product - Google Patents
Carbonization method for purifying industrial Li 2 CO 3 Preparation of pure Li by continuous flow carbonization in process 2 CO 3 Is a process and device for the production of a metal product Download PDFInfo
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- 238000003763 carbonization Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 50
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000002184 metal Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract 2
- 238000003860 storage Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
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- 238000007664 blowing Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 3
- 239000010959 steel Substances 0.000 claims 3
- 238000002156 mixing Methods 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 2
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- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 description 14
- 238000012546 transfer Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
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- 238000005265 energy consumption Methods 0.000 description 3
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- 238000005243 fluidization Methods 0.000 description 2
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
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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
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- 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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Abstract
Description
技术领域technical field
本发明涉及一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的工艺及装置。The invention relates to a process and a device for preparing pure Li2CO3 by continuous flow carbonization reaction in the process of purifying industrial Li2CO3 by a carbonization method .
背景技术Background technique
Li2CO3是锂的基础性化合物，有多种工业用途，可转化成其他多种锂化合物，广泛应用于锂电池正极材料、医药、航空航天、冶金、焊接、陶瓷、锂合金等领域。随着新能源汽车的发展，电池级Li2CO3的需求和价格仍将不断攀升。Li 2 CO 3 is a basic compound of lithium. It has many industrial uses and can be converted into other lithium compounds. It is widely used in lithium battery cathode materials, medicine, aerospace, metallurgy, welding, ceramics, lithium alloys and other fields. With the development of new energy vehicles, the demand and price of battery-grade Li2CO3 will continue to rise.
目前，工业Li2CO3的制备分为矿石提锂和盐湖卤水提锂两种方式，所得Li2CO3纯度低于高纯电池级Li2CO3(99.5％-99.9％)的标准。对工业级Li2CO3的进一步提纯可得到电池级Li2CO3，目前常用的技术有重结晶法、碳化分解法、碳化沉淀法、苛化法。At present, the preparation of industrial Li 2 CO 3 is divided into two methods: extraction of lithium from ore and extraction of lithium from salt lake brine. The purity of Li 2 CO 3 obtained is lower than the standard of high-purity battery-grade Li 2 CO 3 (99.5%-99.9%). Further purification of industrial-grade Li 2 CO 3 can produce battery-grade Li 2 CO 3 . Currently, commonly used techniques include recrystallization, carbonization decomposition, carbonization precipitation, and causticization.
在现有公开的碳酸锂提纯方法中，碳化分解法因其工艺流程短、母液循环利用、回收率高、操作简单而在工业生产中被广泛应用。具体反应方程如下：Among the existing disclosed lithium carbonate purification methods, the carbonization decomposition method is widely used in industrial production because of its short process flow, mother liquor recycling, high recovery rate, and simple operation. The specific reaction equation is as follows:
碳化反应：Li2CO3(s)+CO2(g)+H2O(l)→2LiHCO3(aq)；Carbonization reaction: Li 2 CO 3 (s)+CO 2 (g)+H 2 O(l)→2LiHCO 3 (aq);
热分解反应：2LiHCO3(aq)→Li2CO3(↓)+CO2(g)+H2O(l)。Thermal decomposition reaction: 2LiHCO 3 (aq)→Li 2 CO 3 (↓)+CO 2 (g)+H 2 O(l).
昆明理工大学赵泉峰、江西理工大学温皓、武汉工程大学龚翰章等人的硕士论文研究中均使用了常压碳化分解法来提纯Li2CO3。其常压碳化反应的时间分别为30min、45min、60min，其CO2的消耗量巨大，分别为30eq、88eq、146eq；专利CN110357129A和专利CN115072750A也采用了相同的方式进行碳化反应，其缺点是反应效率低下，能耗过大。Quanfeng Zhao from Kunming University of Science and Technology, Hao Wen from Jiangxi University of Science and Technology, and Gong Hanzhang from Wuhan University of Technology all used carbonization decomposition at atmospheric pressure to purify Li 2 CO 3 . The time of its normal pressure carbonization reaction is 30min, 45min, 60min respectively, and its CO consumption is huge, respectively 30eq, 88eq, 146eq; Low efficiency and excessive energy consumption.
J MATER RES TECHNOL.2020；9(5):9498-9505报道了在反应釜内采用CO2加压微泡辅助碳化反应。该工艺虽然采用了加压的方式进行碳化反应，仍然未能改变反应时间过长(2.0h)和二氧化碳消耗过高的缺点；专利CN209338136U中提出了一种连续的Li2CO3提纯反应釜组。在0.1～0.2MPa的低压下，通过连续五个反应釜(内有布气管道)进行碳化反应，因釜组传质传热性能差的缺点，反应效果并不理想。综合以上研究，在气液固三相的碳化反应中，传统釜式反应器存在比表面积小热交换效率低、气液传质效率有限等缺点，导致了大量CO2无法有效利用而使能耗过高不利于工业化应用。J MATER RES TECHNOL.2020;9(5):9498-9505 reported the use of CO 2 pressurized microbubbles to assist carbonization reactions in reactors. Although this process adopts a pressurized method for carbonization reaction, it still fails to change the shortcoming of too long reaction time (2.0h) and high carbon dioxide consumption; a continuous Li2CO3 purification reactor group is proposed in the patent CN209338136U . Under the low pressure of 0.1-0.2MPa, the carbonization reaction is carried out through five consecutive reaction kettles (with gas distribution pipes inside), but the reaction effect is not ideal due to the shortcomings of the poor mass and heat transfer performance of the kettle group. Based on the above studies, in the gas-liquid-solid three-phase carbonization reaction, the traditional tank reactor has the disadvantages of small specific surface area, low heat exchange efficiency, and limited gas-liquid mass transfer efficiency, which lead to a large amount of CO2 that cannot be effectively used and energy consumption Too high is not conducive to industrial applications.
在采用碳化分解法提纯Li2CO3时，优化碳化反应是一个关键步骤。Li2CO3和CO2在水中的溶解度随温度的降低而降低，但碳化反应属于放热反应(绝热温升在10-13℃之间)，受限于传统釜式反应器的缺点，使得反应过程的传质传热性能不足。本发明所提出的装置—微泡立式反应器，利用管式反应器优良的传质传热性能，通过鼓CO2微泡增大相接触面积，加压提高CO2溶解度，在本质上缩短反应时间，降低CO2用量，安全高效地实现LiHCO3溶液的连续化生产。对比釜式生产技术，碳化反应的连续流管式工艺生产能耗小，速率快，效率高。Optimizing the carbonation reaction is a key step in the purification of Li2CO3 by carbonation decomposition. The solubility of Li 2 CO 3 and CO 2 in water decreases with the decrease of temperature, but the carbonization reaction is an exothermic reaction (adiabatic temperature rise between 10-13 ° C), limited by the shortcomings of traditional tank reactors, making The mass and heat transfer performance of the reaction process is insufficient. The device proposed in the present invention—the microbubble vertical reactor, utilizes the excellent mass and heat transfer performance of the tubular reactor, increases the phase contact area by blowing CO2 microbubbles, increases the solubility of CO2 under pressure, and shortens the process in essence. The reaction time is shortened, the amount of CO2 is reduced, and the continuous production of LiHCO3 solution is realized safely and efficiently. Compared with the kettle-type production technology, the continuous-flow tube-type process of carbonization reaction has low energy consumption, fast speed and high efficiency.
发明内容Contents of the invention
为解决现有Li2CO3碳化法提纯工艺存在的缺陷，本发明的目的在于提供一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的工艺及装置，适合大规模开发应用。本发明采用连续流立式反应器对Li2CO3碳化法提纯中的碳化反应进行反应过程强化，提供了一条更加绿色高效的生产途径，克服了现有碳化反应工艺的不足。In order to solve the defects existing in the existing Li2CO3 carbonization purification process, the object of the present invention is to provide a technology and device for preparing pure Li2CO3 by continuous flow carbonization reaction in the process of carbonization purification of industrial Li2CO3 , suitable for Develop applications at scale. The invention adopts a continuous flow vertical reactor to intensify the reaction process of the carbonization reaction in the Li2CO3 carbonization method purification, provides a greener and more efficient production approach, and overcomes the shortcomings of the existing carbonization reaction process.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
所述的一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的工艺，包括以下步骤：The process of preparing pure Li 2 CO 3 by continuous flow carbonization reaction in the process of purifying industrial Li 2 CO 3 by carbonization method comprises the following steps:
1)将工业级Li2CO3与去离子水在配料罐中混合充分搅拌配制浆料a，通过计量泵控制浆料a的流量，将浆料a以连续化进料的方式输送至微泡立式反应器的底部内；通过气体流量计分别控制CO2和空气的流量，CO2和空气经气体混合器混合后鼓入至微泡立式反应器的底部内，通过调节反应器内部压力，CO2微泡与浆料a在反应器内充分接触发生碳化反应；1) Mix industrial-grade Li 2 CO 3 and deionized water in the batching tank to fully stir to prepare slurry a, control the flow rate of slurry a through a metering pump, and deliver slurry a to the microbubble in a continuous feeding mode In the bottom of the vertical reactor; through the gas flow meter to control the flow of CO 2 and air respectively, CO 2 and air are blown into the bottom of the microbubble vertical reactor after being mixed by the gas mixer, by adjusting the internal pressure of the reactor , the CO microbubbles and the slurry a are fully contacted in the reactor to undergo a carbonization reaction;
2)反应后的反应液经反应器顶部排出并收集于反应液储罐中，即得到LiHCO3溶液，经精密滤膜过滤后，通过计量泵注入填有阳离子树脂的交换柱中，接收料液，获得LiHCO3纯化液；2) After the reaction, the reaction liquid is discharged from the top of the reactor and collected in the reaction liquid storage tank to obtain the LiHCO3 solution. After being filtered through a precision membrane, it is injected into the exchange column filled with cationic resin through a metering pump, and the feed liquid is received. , to obtain LiHCO Purified solution;
3)然后将LiHCO3纯化液加热分解脱去CO2气体，所得Li2CO3沉淀经离心、洗涤、烘干破碎后得电池级Li2CO3产品。3) The purified LiHCO 3 liquid is then heated and decomposed to remove CO 2 gas, and the resulting Li 2 CO 3 precipitate is centrifuged, washed, dried and crushed to obtain a battery-grade Li 2 CO 3 product.
进一步地，步骤1)中所用工业级Li2CO3的粒径大小范围为1.0μm-25.0μm，工业级Li2CO3与去离子水的质量比为1:20-25。Further, the particle size range of industrial grade Li 2 CO 3 used in step 1) is 1.0 μm-25.0 μm, and the mass ratio of industrial grade Li 2 CO 3 to deionized water is 1:20-25.
进一步地，步骤1)中，浆料a的进料温度5-25℃，混合气体的进气温度5-25℃。Further, in step 1), the feed temperature of the slurry a is 5-25°C, and the inlet temperature of the mixed gas is 5-25°C.
进一步地，步骤1)中，碳化反应的Li2CO3与CO2和空气的摩尔流量比范围为：1.0:1.0-1.6:0.3-0.6。Further, in step 1), the molar flow ratio of Li 2 CO 3 to CO 2 and air in the carbonization reaction ranges from 1.0:1.0-1.6:0.3-0.6.
进一步地，步骤1)中，碳化反应的温度范围为5.0-25.0℃；反应器内的背压压力范围为0.1-1.5MPa，优选为0.6-0.8MPa；反应液停留时间范围为0.5-1.5min。Further, in step 1), the temperature range of the carbonization reaction is 5.0-25.0°C; the back pressure in the reactor is in the range of 0.1-1.5MPa, preferably 0.6-0.8MPa; the residence time of the reaction solution is in the range of 0.5-1.5min .
进一步地，所述微泡立式反应器的底部内设置有气体微泡板，浆料a和混合气体分别输入至气体微泡板的上下两方，气体微泡板的曝气气孔大小范围为0.1μm-30.0μm。Further, the bottom of the microbubble vertical reactor is provided with a gas microbubble plate, the slurry a and the mixed gas are respectively input to the upper and lower sides of the gas microbubble plate, and the size range of the aeration pores of the gas microbubble plate is 0.1μm-30.0μm.
进一步地，所述微泡立式反应器包括立式反应管道，其内径为1.0-10.0cm。Further, the microbubble vertical reactor includes a vertical reaction pipe with an inner diameter of 1.0-10.0 cm.
本发明还提供了一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的装置，包括浆料控制和输送模块、气体控制和输送模块、气体分布模块和反应器主体模块。反应器主体模块包括立式反应管道、背压阀、反应液储罐和循环换热设备，立式反应管道的顶部出口通过背压阀和反应液储罐由管路连接；立式反应管道外侧设有换热夹套，换热夹套的进出口分别通过管道与循环换热设备连接。立式反应管道的内直径范围为1.0-10cm。所述浆料控制和输送模块包括配料罐和计量泵，计量泵将配料罐内的浆料a输送至立式反应管道底部内。所述的气体控制和输送模块包括空气钢瓶、CO2钢瓶、气体流量计、气体混合器、气体控温系统；空气钢瓶和CO2钢瓶均通过气体流量计与气体混合器由管路连接，气体混合器排出的混合气体经气体控温系统调节温度后输入至立式反应管道底部内。The present invention also provides a device for preparing pure Li2CO3 by continuous flow carbonization reaction in the process of purifying industrial Li2CO3 by carbonization method, including a slurry control and delivery module, a gas control and delivery module, a gas distribution module and a reactor Main module. The main module of the reactor includes a vertical reaction pipeline, a back pressure valve, a reaction liquid storage tank and a circulation heat exchange device. The top outlet of the vertical reaction pipeline is connected by a pipeline through a back pressure valve and a reaction liquid storage tank; A heat exchange jacket is provided, and the inlet and outlet of the heat exchange jacket are respectively connected to the circulating heat exchange equipment through pipes. The inner diameter of the vertical reaction pipe is in the range of 1.0-10 cm. The slurry control and delivery module includes a batching tank and a metering pump, and the metering pump delivers the slurry a in the batching tank to the bottom of the vertical reaction pipeline. The gas control and delivery module includes an air cylinder, a CO2 cylinder, a gas flowmeter, a gas mixer, and a gas temperature control system; both the air cylinder and the CO2 cylinder are connected to the gas mixer by a pipeline through the gas flowmeter, and the gas The mixed gas discharged from the mixer is input into the bottom of the vertical reaction pipeline after the temperature is adjusted by the gas temperature control system.
本发明取得的有益效果是：The beneficial effects that the present invention obtains are:
本发明采用的连续流管式碳化反应技术与现有传统釜式工艺相比，通过鼓入空气增强混合气体的流速避免浆料的沉降(空气的加入是为了代替二氧化碳提升流化，从而节省二氧化碳的消耗量，减少二氧化碳的消耗)，并且强化了碳化反应的传质传热过程，便于实现自动化操作，提高生产过程的安全性。碳化反应的时间从数小时缩短至几十秒，效率显著提高，同时大大降低CO2的消耗量，更加低碳环保，十分有利于工业应用。Compared with the existing traditional kettle-type process, the continuous flow tube carbonization reaction technology adopted in the present invention can enhance the flow rate of the mixed gas by blowing air to avoid the sedimentation of the slurry (the addition of air is to replace carbon dioxide to promote fluidization, thereby saving carbon dioxide consumption, reduce carbon dioxide consumption), and strengthen the mass transfer and heat transfer process of carbonization reaction, which is convenient for automatic operation and improves the safety of production process. The carbonization reaction time is shortened from several hours to tens of seconds, and the efficiency is significantly improved. At the same time, the consumption of CO 2 is greatly reduced, which is more low-carbon and environmentally friendly, and is very beneficial to industrial applications.
附图说明Description of drawings
图1为本发明提供的一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的装置的结构示意图。Fig. 1 is a schematic structural diagram of a device for preparing pure Li 2 CO 3 by continuous flow carbonization reaction in the process of purifying industrial Li 2 CO 3 by carbonization method provided by the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步说明，但本发明的保护范围并不限于此。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
实施例：参见图1Example: See Figure 1
本申请提供的一种碳化法提纯工业Li2CO3过程中连续流碳化反应制备纯Li2CO3的装置，包括浆料控制和输送模块A、气体控制和输送模块B、气体分布模块C和反应器主体模块D。The present application provides a device for preparing pure Li 2 CO 3 by continuous flow carbonization reaction in the industrial Li 2 CO 3 purification process by carbonization method, including a slurry control and delivery module A, a gas control and delivery module B, a gas distribution module C and Reactor main module D.
反应器主体模块D包括立式反应管道D1、背压阀D3、反应液储罐D4和循环换热设备D5，立式反应管道D1的顶部出口通过背压阀D3和反应液储罐D4由管路连接；立式反应管道D1外侧设有换热夹套D2，换热夹套D2的进出口分别通过管道与循环换热设备D5连接，由循环换热设备D5控制进入换热夹套D2的换热流体的温度，进而对立式反应管道D1的温度进行调控。The reactor main module D includes a vertical reaction pipeline D1, a back pressure valve D3, a reaction liquid storage tank D4 and a circulating heat exchange device D5. The top outlet of the vertical reaction pipeline D1 passes through the back pressure valve D3 and the reaction liquid storage tank D4. There is a heat exchange jacket D2 on the outside of the vertical reaction pipe D1, and the inlet and outlet of the heat exchange jacket D2 are respectively connected to the circulation heat exchange equipment D5 through pipelines, and the circulation heat exchange equipment D5 controls the flow into the heat exchange jacket D2. The temperature of the heat exchange fluid is used to regulate the temperature of the vertical reaction pipeline D1.
所述浆料控制和输送模块A包括配料罐A1和计量泵A2，计量泵A2将配料罐A1内的浆料a输送至立式反应管道D1底部内。The slurry control and delivery module A includes a batching tank A1 and a metering pump A2, and the metering pump A2 transfers the slurry a in the batching tank A1 to the bottom of the vertical reaction pipeline D1.
气体控制和输送模块B包括空气钢瓶B1、CO2钢瓶B2、气体流量计B3、气体混合器B4、气体控温系统B5；空气钢瓶B1和CO2钢瓶B2均通过气体流量计B3与气体混合器B4由管路连接，气体混合器B4排出的混合气体经气体控温系统B5调节温度后输入至立式反应管道D1底部内。The gas control and delivery module B includes air cylinder B1, CO2 cylinder B2, gas flowmeter B3, gas mixer B4, and gas temperature control system B5; air cylinder B1 and CO2 cylinder B2 pass through gas flowmeter B3 and gas mixer B4 is connected by a pipeline, and the mixed gas discharged from the gas mixer B4 is input into the bottom of the vertical reaction pipeline D1 after the temperature is adjusted by the gas temperature control system B5.
其中，所述气体分布模块C包括设置于立式反应管道D1底部内的气体微泡板C1，利用气体微泡板C1分布气体微泡。Wherein, the gas distribution module C includes a gas microbubble plate C1 arranged in the bottom of the vertical reaction pipeline D1, and the gas microbubble plate C1 is used to distribute the gas microbubbles.
本发明实施例中，设定气体质量流量控制器流量输入数值，根据该控制器对不同气体的标准换算系数进行计算，可得单位时间输入的各气体摩尔量。根据不同配比浆料液密度，进行换算得到单位时间输入的摩尔量。最终推算碳化反应的Li2CO3与CO2和空气三者的摩尔流量之比。In the embodiment of the present invention, the flow input value of the gas mass flow controller is set, and the standard conversion coefficients of different gases are calculated according to the controller, and the molar quantities of each gas input per unit time can be obtained. According to the density of slurry with different proportions, conversion is performed to obtain the molar quantity input per unit time. Finally calculate the molar flow ratio of Li 2 CO 3 to CO 2 and air in the carbonization reaction.
实施例1Example 1
向装有100.0L去离子水的配料罐中分批加入5.0kg工业级Li2CO3(纯度99.50％，平均粒径20μm)，在搅拌下配制浆料a，控制温度在20℃左右。浆料a经计量泵A2(浆料流量为40mL/min)注入立式反应管道内(内直径1.5cm)，打开空气钢瓶B1和CO2气体钢瓶B2，通过质量流量控制器控制各自气体流量为0.30L/min和1.0L/min，Li2CO3与CO2和空气的摩尔流量比为1.0:1.25:0.51。流经气体混合器后通过气体控温系统B5控制进气温度为15℃，经气体微泡板C1分布微泡(曝气孔径30μm)。换热夹套D2控制反应温度在20℃，调节背压阀D3维持反应体系压力在0.6MPa。反应液停留时间为90s，待运行稳定后，接收反应液置于反应液储罐D4，反应液澄清，得到LiHCO3溶液。LiHCO3溶液经2.5μm的精密滤膜过滤后，通过计量泵注入填有阳离子树脂的交换柱中，接收料液，获得LiHCO3纯化液。搅拌下加热LiHCO3纯化液至95℃，反应90min，释放大量CO2。所得Li2CO3沉淀混合液经离心、洗涤、烘干破碎后得电池级Li2CO3产品。Add 5.0 kg of industrial-grade Li 2 CO 3 (purity 99.50%, average particle size 20 μm) in batches to a batching tank filled with 100.0 L of deionized water, prepare slurry a under stirring, and control the temperature at about 20° C. The slurry a is injected into the vertical reaction pipeline (inner diameter 1.5cm) through the metering pump A2 (the slurry flow rate is 40mL/min), the air cylinder B1 and the CO2 gas cylinder B2 are opened, and the respective gas flow rates are controlled by the mass flow controller as 0.30L/min and 1.0L/min, the molar flow ratio of Li 2 CO 3 to CO 2 and air is 1.0:1.25:0.51. After passing through the gas mixer, the gas temperature control system B5 controls the inlet temperature to 15°C, and distributes microbubbles through the gas microbubble plate C1 (aeration pore size 30μm). The heat exchange jacket D2 controls the reaction temperature at 20°C, and adjusts the back pressure valve D3 to maintain the pressure of the reaction system at 0.6 MPa. The residence time of the reaction solution is 90s. After the operation is stable, the received reaction solution is placed in the reaction solution storage tank D4, and the reaction solution is clarified to obtain LiHCO 3 solution. After the LiHCO 3 solution is filtered through a 2.5 μm precision filter membrane, it is injected into an exchange column filled with a cationic resin through a metering pump, and the feed liquid is received to obtain a LiHCO 3 purified liquid. Heat the purified LiHCO 3 solution to 95°C under stirring, and react for 90 minutes to release a large amount of CO 2 . The obtained Li 2 CO 3 precipitation mixture is centrifuged, washed, dried and crushed to obtain a battery-grade Li 2 CO 3 product.
实施例2Example 2
在搅拌下向装有125.0L去离子水的配料罐中加入5.0kg工业级Li2CO3(纯度99.5％，平均5μm)配制浆料a，控制浆料a温度为10℃，充分搅拌浆料a使混合均匀。浆料a通过计量泵A2(流量为40mL/min)注入反应立式管道内(内直径1.5cm)，同时打开空气钢瓶B1和CO2气体钢瓶B2，通过质量流量控制器调节各自气体流量为0.29L/min和0.74L/min，Li2CO3与CO2和空气的摩尔流量比为：1.0:1.15:0.6，气体混合后通过气体控温系统B5使进气温度达到10℃，最后利用气体微泡板C1分布气体微泡(曝气孔径5μm)。调控换热夹套D2使反应温度控制在10℃左右，调节背压阀D3使反应体系的压力维持在0.8MPa。待运行稳定后，反应液经80s的停留时间后接收反应液置于反应液储罐D4，反应液澄清，测得pH值为7.2，得到LiHCO3溶液。经过纯化和热裂解(具体步骤同实施例1)后可得到电池级Li2CO3产品。Add 5.0kg of industrial grade Li 2 CO 3 (purity 99.5%, average 5 μm) to the batching tank equipped with 125.0L deionized water under stirring to prepare slurry a, control the temperature of slurry a to 10°C, and fully stir the slurry a Make the mix homogeneous. Slurry a is injected into the reaction vertical pipeline (inner diameter 1.5cm) through the metering pump A2 (flow rate of 40mL/min), and the air cylinder B1 and CO2 gas cylinder B2 are opened at the same time, and the respective gas flow rates are adjusted to 0.29 by mass flow controllers. L/min and 0.74L/min, the molar flow ratio of Li 2 CO 3 to CO 2 and air is: 1.0:1.15:0.6, after the gas is mixed, it passes through the gas temperature control system B5 to make the inlet temperature reach 10°C, and finally uses the gas Microbubble plate C1 distributes gas microbubbles (aeration aperture 5 μm). Adjust the heat exchange jacket D2 to control the reaction temperature at about 10°C, and adjust the back pressure valve D3 to maintain the pressure of the reaction system at 0.8 MPa. After the operation is stable, the reaction solution is received after a residence time of 80s and placed in the reaction solution storage tank D4, the reaction solution is clarified, the measured pH value is 7.2, and the LiHCO 3 solution is obtained. After purification and thermal cracking (the specific steps are the same as in Example 1), the battery-grade Li 2 CO 3 product can be obtained.
实施例3Example 3
称取5.0kg工业级Li2CO3(纯度99.5％，平均粒径1μm)在搅拌下加入装有100.0L离心母液(即为实施例1的Li2CO3沉淀混合液经离心后的母液)的配料罐中配制浆料a，控制浆料a温度为10℃，充分搅拌使其混合均匀。浆料a经计量泵A2(浆料流量为80mL/min)注入立式反应管道内(内直径3.0cm)，同时打开空气钢瓶B1和CO2气体钢瓶B2，通过质量流量控制器控制各自气体流量为0.6L/min和2.4L/min，Li2CO3与CO2和空气的摩尔流量比为：1.0:1.50:0.51，经过气体混合器后通过气体控温系统B5控制进气温度为10℃，经气体微泡板C1分布微泡(曝气孔径0.1μm)。使用换热夹套D2控制反应温度为10℃，调节背压阀D3控制反应体系压力为0.8MPa。待运行稳定后，经60s的停留时间后接收反应液置于反应液储罐D4，反应液澄清，测得pH值为7.2，得到LiHCO3溶液。经纯化和热裂解(具体步骤同实施例1)后可得到电池级Li2CO3产品。Weigh 5.0kg of industrial grade Li2CO3 (purity 99.5%, average particle size 1μm) and add 100.0L of centrifuged mother liquor (that is, the centrifuged mother liquor of the Li2CO3 precipitation mixture in Example 1) under stirring. Prepare slurry a in a batching tank, control the temperature of slurry a to 10°C, stir well to make it evenly mixed. Slurry a is injected into the vertical reaction pipeline (inner diameter 3.0cm) through metering pump A2 (slurry flow rate is 80mL/min), and the air cylinder B1 and CO2 gas cylinder B2 are opened at the same time, and the respective gas flows are controlled by mass flow controllers 0.6L/min and 2.4L/min, the molar flow ratio of Li 2 CO 3 to CO 2 and air is: 1.0:1.50:0.51, after passing through the gas mixer, the gas temperature control system B5 controls the inlet temperature to 10°C , Distributing microbubbles (aeration pore size 0.1 μm) through the gas microbubble plate C1. Use the heat exchange jacket D2 to control the reaction temperature to 10°C, and adjust the back pressure valve D3 to control the reaction system pressure to 0.8 MPa. After the operation is stable, after a residence time of 60s, the received reaction solution is placed in the reaction solution storage tank D4, the reaction solution is clarified, and the measured pH value is 7.2 to obtain a LiHCO 3 solution. After purification and thermal cracking (the specific steps are the same as in Example 1), the battery-grade Li 2 CO 3 product can be obtained.
实施例4Example 4
称取5.0kg工业级Li2CO3(纯度99.5％，平均粒径5μm)加入到装有100.0L去离子水的配料罐中配制浆料a，控制浆料a温度为15℃，充分搅拌使其混合均匀，后经计量泵A2(浆料流量为40mL/min)注入立式反应管道内(内直径1.5cm)，打开CO2气体钢瓶B2，控制其输入温度为15℃，调节质量流量控制器参数为0.9L/min，Li2CO3与CO2摩尔流量比为1.0:1.12，经气体微泡板C1分布微泡(曝气孔径5μm)。使用换热夹套D2控制反应温度为15℃，调节背压阀D3控制反应体系压力为0.8MPa。待运行稳定后，经120s的停留时间后接收反应液置于反应液储罐D4，反应液澄清。LiHCO3溶液经纯化和热裂解(具体步骤同实施例1)后可得到电池级Li2CO3产品，纯度为99.93％，收率87.5％。经运行稳定性测试，经数小时的运行过程中，计量泵A2的泵压升高，出管口料液的碳酸氢锂溶液浓度与理论值偏差较大，导致整体收率偏低，且浆料a在反应器内沉积体积偏离持液体积。Weigh 5.0kg of industrial grade Li 2 CO 3 (purity 99.5%, average particle size 5 μm) and add it to a batching tank equipped with 100.0L deionized water to prepare slurry a, control the temperature of slurry a to 15°C, and stir fully to make It is mixed evenly, and then injected into the vertical reaction pipeline ( inner diameter 1.5cm) through the metering pump A2 (the slurry flow rate is 40mL/min). The device parameter is 0.9L/min, the molar flow ratio of Li 2 CO 3 and CO 2 is 1.0:1.12, and microbubbles are distributed through the gas microbubble plate C1 (aeration pore size 5μm). Use the heat exchange jacket D2 to control the reaction temperature to 15° C., and adjust the back pressure valve D3 to control the reaction system pressure to 0.8 MPa. After the operation is stable, after a residence time of 120s, the reaction liquid is received and placed in the reaction liquid storage tank D4, and the reaction liquid is clarified. After the LiHCO 3 solution was purified and thermally cracked (the specific steps were the same as in Example 1), the battery-grade Li 2 CO 3 product could be obtained, with a purity of 99.93% and a yield of 87.5%. Through the operation stability test, after several hours of operation, the pump pressure of the metering pump A2 increased, and the concentration of the lithium bicarbonate solution in the feed liquid at the outlet of the pipe had a large deviation from the theoretical value, resulting in a low overall yield, and the slurry The deposition volume of material a in the reactor deviates from the liquid holding volume.
进一步优化选择增加空气增强流化，减少二氧化碳用量，在实施例1、2、3长久运行中获得了良好的稳定性。Further optimize the choice to increase air to enhance fluidization and reduce the amount of carbon dioxide, and obtain good stability in the long-term operation of Examples 1, 2, and 3.
为检验连续流碳化反应对产品质量的影响，对实施例1-实施例3的Li2CO3产品进行含量测定，其结果如下表所示：In order to check the impact of continuous flow carbonization reaction on product quality, the Li of embodiment 1-embodiment 3 CO product is assayed, and its result is as shown in the table below:
本说明书所述的内容仅仅是对发明构思实现形式的列举，本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。The content described in this specification is only an enumeration of the implementation forms of the inventive concepts, and the protection scope of the present invention should not be regarded as limited to the specific forms stated in the embodiments.
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