WO2013123746A1 - 一种废旧锂电池正极材料用于火电厂co2捕集的方法 - Google Patents

一种废旧锂电池正极材料用于火电厂co2捕集的方法 Download PDF

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WO2013123746A1
WO2013123746A1 PCT/CN2012/077276 CN2012077276W WO2013123746A1 WO 2013123746 A1 WO2013123746 A1 WO 2013123746A1 CN 2012077276 W CN2012077276 W CN 2012077276W WO 2013123746 A1 WO2013123746 A1 WO 2013123746A1
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carbon dioxide
lithium battery
bed
absorption
thermal power
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English (en)
French (fr)
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王刚
赵光金
郭阳
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Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
State Grid Corp of China SGCC
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Electric Power Research Institute of State Grid Henan Electric Power Co Ltd
State Grid Corp of China SGCC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/302—Alkali metal compounds of lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention belongs to the technical field of recycling and utilization of waste lithium batteries, and particularly relates to a method for using a cathode material of a waste lithium battery for CO 2 capture in a thermal power plant.
  • Lithium-ion batteries have become the absolute main products of target markets such as mobile phones, digital products and portable DVDs because of their high working voltage, small size, light weight, high energy, low pollution and long cycle life.
  • Huge battery production consumption has brought an amazing number of waste batteries.
  • the lithium-ion battery has a relatively small impact on the environment compared to the primary battery, the positive and negative materials of the lithium ion battery, the electrolyte and the like are still very harmful to the environment and human health.
  • the recovery rate of lithium batteries is still very low (less than 2%), which poses a huge threat to the environment and pollution, and is also a waste of resources.
  • lithium salts including lithium ferrite (LiFeO 2 ), lithium nickelate (LiNiO 2 ), lithium titanate (Li 2 TiO 3 ), lithium zirconate (Li 2 ZrO 3 ), lithium metasilicate (Li 2 SiO 3 ), lithium silicate (Li 4 SiO 4 ), etc. have good CO 2 adsorption-desorption properties at high temperatures.
  • the waste lithium battery is subjected to recycling treatment, and the lithium-containing cathode material is extracted, and then the CO 2 trapping agent is obtained by a purification process or the like, and waste treatment can be realized.
  • the object of the present invention is to provide a method for using a cathode material of a waste lithium battery for CO 2 capture in a thermal power plant, which can realize waste treatment by recycling the cathode material of the waste lithium battery.
  • the present invention adopts the following technical solutions:
  • a method for using a lithium battery positive electrode material for CO 2 capture in a thermal power plant comprising the following steps:
  • the carbon dioxide absorption tower is placed in the boiler at a temperature of 500-750 ° C.
  • the flue gas flows through the absorption bed and directly contacts the adsorbent for carbon dioxide capture.
  • the absorption bed is transferred to carbon dioxide regeneration. Desorption is carried out in the tower.
  • the carbon dioxide regeneration tower can be placed in a position where the temperature of the flue gas in the boiler is 760 to 950 ° C, and the adsorption bed of the saturated adsorbed carbon dioxide is heated by the flue gas to desorb the carbon dioxide on the adsorbent; then the desorbed absorption bed is desorbed.
  • the temperature is lowered to 500-750 ° C, and it is again placed in the carbon dioxide absorption tower for a new round of carbon dioxide capture and desorption, thus achieving cyclic adsorption and desorption.
  • the cathode material of the waste lithium battery includes lithium cobaltate, lithium nickelate, lithium manganate, ternary material, lithium iron phosphate or a mixture thereof; the ternary material refers to three metals including nickel, cobalt and manganese.
  • the positive electrode material of the element includes lithium cobaltate, lithium nickelate, lithium manganate, ternary material, lithium iron phosphate or a mixture thereof; the ternary material refers to three metals including nickel, cobalt and manganese.
  • the absorbent bed may be arranged in two or more layers, the absorbent bed being a mobile absorbent bed, and each absorbent bed consisting of 4 to 10 adsorbent units.
  • the unit size of the adsorbent is preferably 60 to 100 mm in length, width and height, and the number of adsorbent units arranged in the single layer absorbent bed is 4 to 10.
  • the adsorbent pitch is 3.8 to 9.0 mm, and the specific surface area of the adsorbent is 406 to 553 m 2 *m -3 .
  • Common specifications of the absorption tower: length ⁇ width ⁇ height are 400 ⁇ 400 ⁇ 400mm.
  • the flue gas enters the absorption tower from the bottom or top of the carbon dioxide absorption tower or from the horizontal direction.
  • the absorption bed of a certain layer When the absorption bed of a certain layer reaches saturation, it moves up or down at a certain speed into the regeneration tower. In a particular operation, the absorbent bed after complete desorption of carbon dioxide moves up or down at a rate into the absorber.
  • the carbon dioxide absorption tower and the carbon dioxide regeneration tower used in the method of the present application are conventional apparatuses in the art, and thus will not be described again.
  • the cooling of the absorption bed is carried out in a heat exchanger, and the cooling method is spray desuperheating water (the desuperheating water is derived from the high temperature hydrophobic system of the power plant).
  • the movement of the absorbent bed is achieved by a helical mechanical device.
  • the cathode material of the used lithium battery can be obtained by complete discharge ⁇ battery breaking ⁇ positive and negative sheet separation ⁇ positive sheet crushing ⁇ organic solvent dissolution separation ⁇ depletion treatment, and the specific steps are as follows:
  • the positive electrode piece is broken by a crusher, and the positive electrode piece is placed in an organic solvent N-methylpyrrolidone (NMP) for every 10 ml.
  • NMP organic solvent N-methylpyrrolidone
  • the complete separation of the current collector separates the positive electrode powder material.
  • the obtained positive electrode powder material is dried at 110 to 120 ° C for 3 to 5 hours, and then the waste material is crushed to a maximum particle size of less than 100 ⁇ m by a crusher, and finally heat-treated at 400 to 600 ° C for 5 to 8 hours in an air atmosphere furnace (using The removal of the positive electrode material is completed by removing impurities such as a conductive agent.
  • an effective lithium-based CO 2 capture agent is prepared, which is suitable for coal-fired power plants, gas power plants and other thermal power plants. It is found through experiments that the flue gas flow rate is controlled at 3.5-6.1 m/s (carbon dioxide content in flue gas is 10.6-15.8%). After saturated adsorption, the adsorbent adsorption amount is 8.0 ⁇ 13.2 wt%; after desorption, CO2 desorption rate Maintained at 98.6 ⁇ 99.8%.
  • the carbon dioxide adsorbent used in the present invention has good cycle performance and can maintain an adsorption capacity of 60 to 78% after 40 cycles.
  • the adsorption amount of the adsorbent is based on the mass percentage of the adsorbent before the adsorption and after the saturated adsorption.
  • a method for using a lithium battery positive electrode material for CO 2 capture in a thermal power plant comprising the following steps:
  • the lithium cobalt oxide cathode material of the recovered 10 kg waste lithium battery was used as a carbon dioxide adsorbent to prepare a honeycomb absorption bed (the absorption bed was arranged in two layers, which is a mobile absorption bed), and was placed in a carbon dioxide absorption tower.
  • the adsorbent unit size is 100 ⁇ 100 ⁇ 100mm
  • the number of adsorbent units arranged in a single-layer absorption bed is 4
  • the honeycomb holes are square (the number of holes is not equal)
  • the adsorbent pitch is 6.7 mm
  • the specific surface area is 426 m 2 * m. -3 .
  • Absorption tower specifications: length ⁇ width ⁇ height are 400 ⁇ 400 ⁇ 400 mm;
  • the carbon dioxide absorber is placed in the boiler at a temperature of 650 ° C.
  • the flue gas flows through the absorption bed and is directly in contact with the carbon dioxide capture agent for carbon dioxide capture.
  • the flue gas flow rate is 3.5. m/s (the carbon dioxide content in the flue gas is 15.8%), the adsorption is saturated for about 1 h (the adsorbent adsorption amount is 8.3 wt%), and then the absorption bed is transferred to the carbon dioxide regeneration tower;
  • the carbon dioxide regeneration tower is placed at a temperature of 850 ° C in the boiler, and the adsorbent bed saturated with carbon dioxide is heated by the flue gas to desorb the carbon dioxide adsorbed on the cathode material of the waste lithium battery (desorption time 1 h, CO 2 desorption) The rate is 98.6%);
  • the carbon dioxide adsorbent can maintain 70% adsorption capacity after 40 cycles, and the adsorption and circulation performance is good.
  • the above carbon dioxide adsorbent is derived from the recovered product of the cathode material of the waste lithium cobalt oxide battery, and the recovery steps include: discharge ⁇ battery breaking ⁇ positive and negative electrode separation ⁇ positive electrode chip breaking ⁇ organic solvent dissolution separation ⁇ high temperature impurity removal, the specific steps are as follows :
  • the positive electrode piece is broken by a crusher, and the lithium cobaltate positive electrode piece is placed in NMP every 10 ml.
  • NMP was added with 2.0 g of a positive electrode sheet (that is, a liquid-solid ratio of 5:1 ml/g), and the mixture was stirred at 75 ° C for 2 hours to obtain a positive electrode powder material.
  • the obtained positive electrode powder material was dried at 120 ° C for 5 h, and then the waste was crushed to a maximum particle size of 60 ⁇ m by a crusher, and finally heat-treated at 580 ° C for 7 h in an air atmosphere furnace (to remove impurities such as conductive agent), and completed. Recovery of positive electrode material.
  • the difference is that lithium cobaltate is used as the adsorbent in step 1, and the absorbent bed has a plate structure with a sorbent pitch of 7.1 mm and a specific surface area of 406 m 2 * m -3 .
  • the carbon dioxide absorption tower is placed in the boiler at a temperature of 690 ° C, the flue gas flow rate is 4.5 m / s (the carbon dioxide content in the flue gas is 12.5%), and the adsorbent adsorption amount is 10.0 wt%.
  • the carbon dioxide regeneration tower is placed in a position where the flue gas temperature in the boiler is about 900 ° C, and the CO 2 desorption rate is 99.3%.
  • the desuperheated water is sprayed to bring the absorption bed temperature down to 690 °C. The adsorbent still retains 60% adsorption capacity after 40 cycles.
  • the operation procedure of the waste battery recycling treatment was as described in Example 1, except that in the step 3), the liquid-solid ratio was 6:1 ml/g, and the mixture was stirred at 80 ° C for 2 hours.
  • the obtained positive electrode powder material was dried at 115 ° C for 3 hours, and then the waste was crushed by a crusher to a maximum particle size of 50 ⁇ m, and finally heat-treated at 490 ° C for 6 hours in an air atmosphere furnace.
  • the difference is that lithium cobalt oxide is replaced by lithium manganate as the adsorbent in step 1, and the absorption bed has a plate structure with a sorbent pitch of 3.8 mm and a specific surface area of 553 m 2 * m -3 .
  • the carbon dioxide absorption tower is placed in the boiler at a temperature of about 720 ° C, the flue gas flow rate is 5.7 m / s (the carbon dioxide content in the flue gas is 10.6%), and the adsorbent adsorption amount is 8.0 wt%.
  • the carbon dioxide regeneration tower is placed in a position where the flue gas temperature in the boiler is about 930 ° C, and the CO 2 desorption rate is 99.0%.
  • the desuperheated water is sprayed to bring the absorption bed temperature down to 720 °C.
  • the adsorbent maintained a 67% adsorption capacity after 40 cycles.
  • the operation procedure of the waste battery recovery treatment was as described in Example 1, except that in the step 3), the liquid-solid ratio was 8:1 ml/g, and the mixture was stirred at 90 ° C for 2 hours.
  • the obtained positive electrode powder material was dried at 110 ° C for 4 h, and then the waste was crushed by a crusher to a maximum particle size of 40 ⁇ m, and finally heat-treated at 410 ° C for 6 h in an air atmosphere furnace.
  • step 1 the lithium silicate is replaced by a ternary material as the adsorbent, and the absorption bed has a plate structure with a sorbent pitch of 9.0 mm and a specific surface area of 489 m 2 * m - 3 .
  • step 2 the carbon dioxide absorption tower is placed in the boiler at a temperature of about 730 ° C, the flue gas flow rate is 6.1 m / s (the carbon dioxide content in the flue gas is 14.6%), and the adsorbent adsorption amount is 11.1 wt%.
  • step 3 the carbon dioxide regeneration tower is placed in a position where the temperature of the flue gas in the boiler is about 880 ° C, and the CO 2 desorption rate is 99.8%.
  • step 4 the desuperheated water is sprayed to bring the absorption bed temperature down to 730 °C. The adsorbent still retains 76% adsorption capacity after 40 cycles.
  • the operation procedure of the waste battery recovery treatment was as described in Example 1, except that in the step 3), the liquid-solid ratio was 5:1 ml/g, and the mixture was stirred at 70 ° C for 2 hours.
  • the obtained positive electrode powder material was dried at 118 ° C for 4 h, and then the waste was crushed by a crusher to a maximum particle size of 90 ⁇ m, and finally heat-treated at 550 ° C for 5 h in an air atmosphere furnace.
  • step 1 lithium cobalt phosphate is replaced by lithium iron phosphate as the adsorbent, the absorption bed is a plate structure, the adsorbent pitch is 8.5 mm, and the specific surface area is 466 m 2 * m - 3 .
  • step 2 the carbon dioxide absorption tower is placed in the boiler at a temperature of about 710 ° C, the flue gas flow rate is 5.9 m / s (the carbon dioxide content in the flue gas is 10.8%), and the adsorbent adsorption amount is 13.2 wt%.
  • step 3 the carbon dioxide regeneration tower is placed in a position where the flue gas temperature in the boiler is about 900 ° C, and the CO 2 desorption rate is 99.3%.
  • step 4 the desuperheated water is sprayed to bring the absorption bed temperature down to 710 °C.
  • the adsorbent maintained a 78% adsorption capacity after 40 cycles.
  • the operation procedure of the waste battery recycling treatment was as described in Example 1, except that in the step 3), the liquid-solid ratio was 6:1 ml/g, and the mixture was stirred at 80 ° C for 2 hours.
  • the obtained positive electrode powder material was dried at 120 ° C for 3.5 h, and then the waste was crushed to a maximum particle size of 70 ⁇ m by a crusher, and finally heat-treated at 460 ° C for 7.5 h in an air atmosphere furnace.

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Abstract

一种废旧锂电池正极材料用于火电厂CO2捕集的方法，包括以下步骤：①将回收得到的锂电池正极材料作为二氧化碳吸附剂制成板式、蜂窝式或波纹板式吸收床，置于二氧化碳吸收塔中；②将二氧化碳吸收塔置于锅炉内烟气温度在500〜750°C的位置，烟气流过吸收床与吸附剂直接接触进行二氧化碳捕集，当吸附达到饱和状态后，将吸收床转入二氧化碳再生塔中进行解吸。

Description

一种废旧锂电池正极材料用于火电厂 CO2 捕集的方法
技术领域
本发明属于废旧锂电池回收利用技术领域，具体涉及一种废旧锂电池正极材料用于火电厂CO2 捕集的方法。
背景技术
近年来随着人们环境保护意识的不断提高，及自然资源的不断消耗，环境友好的锂离子电池被开发出来并得到广泛使用。锂离子电池因其具有工作电压高、体积小、质量轻、能量高、低污染、循环寿命长等优点，已成为移动电话、数码产品、便携式DVD等目标市场的绝对主力产品，而且也已成为电动汽车采用的最重要的动力蓄电池之一。巨大的电池生产消费带来了数目惊人的废电池。虽然相对于一次电池，锂离子电池对环境的影响相对较小，但是锂离子电池的正、负极材料、电解液等物质对环境和人类的健康还是有很大危害的。目前锂电池回收率还很低（不到2%），给环境造成巨大威胁和污染，同时对资源也是一种浪费。
目前，石油、煤炭、天然气等化石燃料仍然是发电厂等很多工业生产中的主要能源。在化石燃料燃烧过程中会有大量的 CO2 气体释放出来，其中二氧化碳的排放50%来自于火电厂，2007年火电厂二氧化碳排放量超过27亿吨。大量二氧化碳的排放导致了人们十分关注的温室效应， CO2 对大气温升的贡献超过60%。过去十年，大气中 CO2 浓度迅猛增长，因此 CO2 减排已成为全人类面临的共同责任。
通常从火电厂高温炉中排出的烟气温度比较高，因此利用在高温下能高效、迅速吸收 CO2 的材料来减少 CO2 的排放，已经成为解决该问题的一个重要途径。本研究发现：锂盐，包括铁酸锂（ LiFeO2 ）、镍酸锂（ LiNiO2 ）、钛酸锂（ Li2TiO3 ）、锆酸锂（ Li2ZrO3 ）、偏硅酸锂（ Li2SiO3 ）、硅酸锂（ Li4SiO4 ）等在高温下具有良好的 CO2 吸附-脱附性能。此外，研究发现，当向锆酸锂、硅酸锂等材料中掺入少量Na、K、Al、Fe等元素后，其二氧化碳吸附性能会显著提高。本申请对废旧锂电池实施回收处理，提取其中的含锂正极材料，再通过纯化等工艺得到 CO2 捕获剂，可以实现以废治废。
发明内容
本发明目的在于提供一种废旧锂电池正极材料用于火电厂 CO2 捕集的方法，该方法通过对废旧锂电池正极材料的回收处理，可以实现以废治废。
为实现上述目的，本发明采用如下技术方案：
一种废旧锂电池正极材料用于火电厂 CO2 捕集的方法，其包括以下步骤：
①将回收得到的锂电池正极材料作为二氧化碳吸附剂制成板式、蜂窝式或波纹板式吸收床，置于二氧化碳吸收塔中；
②将二氧化碳吸收塔置于锅炉内烟气温度在500～750℃的位置，烟气流过吸收床与吸附剂直接接触进行二氧化碳捕集，当吸附达到饱和状态后，将吸收床转入二氧化碳再生塔中进行解吸。
具体的，可以把二氧化碳再生塔置于锅炉内烟气温度在760～950℃的位置，利用烟气加热已饱和吸附二氧化碳的吸附床，将吸附剂上的二氧化碳解吸；然后将解吸过的吸收床温度降至500～750℃，再次置于二氧化碳吸收塔中进行新一轮的二氧化碳捕集和解吸，如此实现循环吸附、解吸。
所述废旧锂电池正极材料包括钴酸锂、镍酸锂、锰酸锂、三元系材料、磷酸亚铁锂或其混合物；所述三元系材料是指含镍、钴、锰三种金属元素的正极材料。
所述吸收床可以以两层或者两层以上的形式布置，吸收床为移动式吸收床，每层吸收床由4～10个吸附剂单元组成。吸附剂的单元尺寸以长宽高均在60～100mm为宜，单层吸收床布置的吸附剂单元数量为4～10个。吸附剂节距为3.8～9.0 mm，吸附剂比表面积在406～553m2*m-3。吸收塔常用规格：长×宽×高分别为400 × 400 × 400mm。在步骤②中，烟气从二氧化碳吸收塔的底部或者顶部，又或者从水平方向进入吸收塔，当某一层吸收床达到饱和后，以一定速度向上或向下移动进入再生塔。在具体操作中，完全解吸二氧化碳后的吸收床以一定速度向上或向下移动进入吸收塔。本申请方法中所用到的二氧化碳吸收塔和二氧化碳再生塔均为本领域的常规装置，故此不再赘述。
吸收床的降温在热交换器中进行，降温方式为喷减温水（减温水来源于电厂高温疏水系统）。吸收床的移动是通过螺旋机械装置实现的。
所述废旧锂电池正极材料可以经完全放电→电池破壳→正负极片分离→正极片破碎→有机溶剂溶解分离→除杂处理后得到，具体步骤如下：
1）完全放电处理：借助于剪切机和粉碎机，去除废旧锂离子电池的外包装得到单体电池，把单体电池置于饱和氯化钠水溶液中进行放电。
2）电池破壳：把完全放电过的电池取出，使用破壳机打开电池外壳，然后立即放入纯净水中，消除电解液的环境污染隐患，分离取出正、负极片（负极片另作处理，并利用浮选法分离出电池隔膜）。
3）使用破碎机将正极片破碎，将正极碎片置于有机溶剂N-甲基吡咯烷酮（NMP）中，每10ml NMP添加1.0～2.0g正极片（即控制液固比为10～5：1 ml/g），于60～100℃搅拌1～3h（正极粉末一般是通过粘结剂粘附于铝箔集流体表面，此处通过把粘结剂溶解于有机溶剂中，来实现正极粉末与铝箔集流体的完全分离），分离得到正极粉末材料。
4）将得到的正极粉末材料于110～120℃下干燥3～5h，然后用破碎机将废料破碎至最大粒度小于100μm，最后在空气气氛炉中于400～600℃恒温热处理5～8h（用以除去导电剂等杂质），完成正极材料的回收。
和现有技术相比，本发明方法的有益效果：
通过回收处理废旧锂电池正极材料，并将其用于 CO2 捕获，不仅可以提升锂电池回收处理的经济价值，避免电池的二次污染，降低电池成本；还能以废治废。通过废旧锂电池正极材料的回收-纯化，制备出有效的锂基 CO2 捕获剂，适用于燃煤电厂、燃气电站等火力发电厂。经试验得知：烟气流速控制在3.5～6.1 m/s（烟气中二氧化碳含量10.6～15.8%），饱和吸附后，吸附剂的吸附量为8.0～13.2 wt%；解吸后，CO2解吸率保持在98.6～99.8%。本发明中所用的二氧化碳吸附剂具有良好的循环性能，在40次循环后仍能保持60～78%的吸附能力。吸附剂的吸附量以吸附前、饱和吸附后吸附剂增重的质量百分比计。
具体实施方式
以下通过优选实施例对本发明作进一步详细说明，但本发明的保护范围并不局限于此。
实施例1
一种废旧锂电池正极材料用于火电厂 CO2 捕集的方法，其包括以下步骤：
①将回收得到的10 kg废旧锂电池正极材料钴酸锂作为二氧化碳吸附剂，制成蜂窝式吸收床（该吸收床以2层形式布置，为移动式吸收床），置于二氧化碳吸收塔中。吸附剂单元尺寸100 × 100 × 100mm，单层吸收床布置的吸附剂单元数量为4个，蜂窝孔为方形（孔数不等），吸附剂节距为6.7 mm，比表面积为426m2 * m-3 。吸收塔规格：长×宽×高分别为400 × 400 × 400 mm；
②将二氧化碳吸收塔置于锅炉内烟气温度在650℃的位置，烟气流过吸收床与二氧化碳捕获剂直接接触进行二氧化碳捕集，烟气流速3.5 m/s（烟气中二氧化碳含量15.8%），吸附1h左右吸附达到饱和状态（吸附剂吸附量为8.3 wt%），然后将吸收床转入二氧化碳再生塔中；
③将二氧化碳再生塔置于锅炉内烟气温度为850℃的位置，利用烟气加热已饱和吸附二氧化碳的吸附床，将吸附在废旧锂电池正极材料上的二氧化碳解吸（解吸时间1h， CO2 解吸率为98.6%）；
④将解吸后的吸收床转入热交换器中，喷减温水使其温度降至650℃，然后再次置于二氧化碳吸收塔中进行新一轮的二氧化碳捕集和解吸，如此实现循环吸附、解吸。该二氧化碳吸附剂在40次循环后仍能保持70%的吸附能力，吸附和循环性能良好。
上述的二氧化碳吸附剂来源于废旧钴酸锂电池正极材料的回收产物，回收步骤包括：放电→电池破壳→正负极片分离→正极片破碎→有机溶剂溶解分离→高温除杂，具体步骤如下：
1）完全放电处理：借助于剪切机和粉碎机，去除废旧锂离子电池的外包装得到单体电池，把单体电池置于饱和氯化钠水溶液中进行放电。
2）电池破壳：把完全放电过的电池取出，使用破壳机打开电池外壳，然后立即放入纯净水中，消除电解液的环境污染隐患，分离取出正、负极片（负极片另作处理，并利用浮选法分离出电池隔膜）。
3）使用破碎机将正极片破碎，将钴酸锂正极碎片置于NMP中，每10ml NMP添加2.0g正极片（即液固比为5:1 ml/g），于75℃搅拌2h，分离得到正极粉末材料。
4）将得到的正极粉末材料于120℃干燥5h，然后用破碎机将废料破碎至最大粒度为60μm，最后在空气气氛炉中于580℃恒温热处理7h（用以除去导电剂等杂质），完成正极材料的回收。
实施例2
参照实施例1，所不同的是：在步骤①中用镍酸锂替换钴酸锂作为吸附剂，吸收床为板式结构，吸附剂节距为7.1 mm，比表面积406 m2* m-3 。在步骤②中，将二氧化碳吸收塔置于锅炉内烟气温度在690℃的位置，烟气流速4.5 m/s（烟气中二氧化碳含量12.5%），吸附剂吸附量为10.0 wt%。在步骤③中，将二氧化碳再生塔置于锅炉内烟气温度在900℃左右的位置，CO2解吸率为99.3%。在步骤④中，喷减温水使吸收床温度降至690℃。该吸附剂在40次循环后仍能保持60%的吸附能力。
废旧电池回收处理操作步骤参照实施例1，所不同的是：在步骤3）中，液固比为6:1ml/g，于80℃搅拌2h。在步骤4）中，将得到的正极粉末材料于115℃干燥3h，然后用破碎机将废料破碎至最大粒度为50μm，最后在空气气氛炉中于490℃恒温热处理6h。
实施例3
参照实施例1，所不同的是：在步骤①中用锰酸锂替换钴酸锂作为吸附剂，吸收床为板式结构，吸附剂节距为3.8 mm，比表面积为553m2 * m-3 。在步骤②中，将二氧化碳吸收塔置于锅炉内烟气温度在720℃左右的位置，烟气流速5.7 m/s（烟气中二氧化碳含量10.6%），吸附剂吸附量为8.0 wt%。在步骤③中，将二氧化碳再生塔置于锅炉内烟气温度在930℃左右的位置， CO2 解吸率为99.0%。在步骤④中，喷减温水使吸收床温度降至720℃。该吸附剂在40次循环后仍能保持67%的吸附能力。
废旧电池回收处理操作步骤参照实施例1，所不同的是：在步骤3）中，液固比为8:1ml/g，于90℃搅拌2h。在步骤4）中，将得到的正极粉末材料于110℃干燥4h，然后用破碎机将废料破碎至最大粒度为40μm，最后在空气气氛炉中于410℃恒温热处理6h。
实施例4
参照实施例1，所不同的是：在步骤①中用三元系材料替换钴酸锂作为吸附剂，吸收床为板式结构，吸附剂节距为9.0 mm，比表面积为489 m2 * m-3 。在步骤②中，将二氧化碳吸收塔置于锅炉内烟气温度在730℃左右的位置，烟气流速6.1 m/s（烟气中二氧化碳含量14.6%），吸附剂吸附量为11.1 wt%。在步骤③中，将二氧化碳再生塔置于锅炉内烟气温度在880℃左右的位置， CO2 解吸率为99.8%。在步骤④中，喷减温水使吸收床温度降至730℃。该吸附剂在40次循环后仍能保持76%的吸附能力。
废旧电池回收处理操作步骤参照实施例1，所不同的是：在步骤3）中，液固比为5:1ml/g，于70℃搅拌2h。在步骤4）中，将得到的正极粉末材料于118℃干燥4h，然后用破碎机将废料破碎至最大粒度为90μm，最后在空气气氛炉中于550℃恒温热处理5h。
实施例5
参照实施例1，所不同的是：在步骤①中用磷酸亚铁锂替换钴酸锂作为吸附剂，吸收床为板式结构，吸附剂节距为8.5 mm，比表面积为466 m2 * m-3 。在步骤②中，将二氧化碳吸收塔置于锅炉内烟气温度在710℃左右的位置，烟气流速5.9 m/s（烟气中二氧化碳含量10.8%），吸附剂吸附量为13.2 wt%。在步骤③中，将二氧化碳再生塔置于锅炉内烟气温度在900℃左右的位置， CO2 解吸率为99.3%。在步骤④中，喷减温水使吸收床温度降至710℃。该吸附剂在40次循环后仍能保持78%的吸附能力。
废旧电池回收处理操作步骤参照实施例1，所不同的是：在步骤3）中，液固比为6:1ml/g，于80℃搅拌2h。在步骤4）中，将得到的正极粉末材料于120℃干燥3.5h，然后用破碎机将废料破碎至最大粒度为70μm，最后在空气气氛炉中于460℃恒温热处理7.5h。

Claims (7)

  1. 一种废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，包括以下步骤：
    ①将回收得到的锂电池正极材料作为二氧化碳吸附剂制成板式、蜂窝式或波纹板式吸收床，置于二氧化碳吸收塔中；
    ②将二氧化碳吸收塔置于锅炉内烟气温度在500～750℃的位置，烟气流过吸收床与吸附剂直接接触进行二氧化碳捕集，当吸附达到饱和状态后，将吸收床转入二氧化碳再生塔中进行解吸。
  2. 如权利要求1所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，把二氧化碳再生塔置于锅炉内烟气温度在760～950℃的位置，利用烟气加热已饱和吸附二氧化碳的吸附床，将吸附剂上的二氧化碳解吸；然后将解吸过的吸收床温度降至500～750℃，再次置于二氧化碳吸收塔中进行新一轮的二氧化碳捕集和解吸，如此实现循环吸附、解吸。
  3. 如权利要求1所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，所述废旧锂电池正极材料包括钴酸锂、镍酸锂、锰酸锂、三元系材料、磷酸亚铁锂或其混合物；所述三元系材料是指含镍、钴、锰三种金属元素的正极材料。
  4. 如权利要求1所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，所述废旧锂电池正极材料经完全放电→电池破壳→正负极片分离→正极片破碎→有机溶剂溶解分离→除杂处理后得到。
  5. 如权利要求1或2所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，所述吸收床以两层或者两层以上的形式布置，吸收床为移动式吸收床。
  6. 如权利要求2所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，吸收床的降温在热交换器中进行，降温方式为喷减温水。
  7. 如权利要求1或2所述废旧锂电池正极材料用于火电厂CO2 捕集的方法，其特征在于，吸收床的移动是通过螺旋机械装置实现的。
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