CN105399983B - A kind of separation method of mixed plastic - Google Patents
A kind of separation method of mixed plastic Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种废旧混合塑料的分离方法，属于废旧塑料回收技术领域。The invention relates to a method for separating waste and old mixed plastics, belonging to the technical field of waste and old plastics recycling.
背景技术Background technique
塑料在人类的生活和生产中具有广泛的应用，塑料工业的迅速发展、塑料的大量消费以及塑料产品较短的使用周期使得塑料废弃物的数量急剧增加。废旧塑料的处理方式为焚烧和填埋，产生了严重的环境污染和资源的浪费。因此，对废旧塑料的回收利用已得到高度重视。对废旧塑料回收过程，需要对不同的塑料进行分离，目前塑料的分离是制约废旧塑料回收过程的瓶颈环节。Plastics are widely used in human life and production. The rapid development of the plastics industry, the large consumption of plastics and the short life cycle of plastic products have led to a sharp increase in the amount of plastic waste. The disposal methods of waste plastics are incineration and landfill, resulting in serious environmental pollution and waste of resources. Therefore, the recycling of waste plastics has been highly valued. For the recycling process of waste plastics, it is necessary to separate different plastics. At present, the separation of plastics is the bottleneck link restricting the recycling process of waste plastics.
开发的混合塑料分离技术包括手工分拣、重力分离、浮选、静电分离和选择性溶解等方法。塑料的手工分拣过程劳动强度大、工作环境恶劣、分离效率低。重力分离和静电分离对物理性质相近的混合塑料的分离有很大局限性。选择性溶剂成本高，并且有机溶剂具有很大毒性。目前，浮选可以实现对密度相近的混合塑料具有很好的优势，但是塑料大多具有相近的疏水性质，通过润湿剂的调整可以实现混合塑料的选择性分离。目前采用浮选对废旧塑料进行分离的研究相对较少，并且均采用润湿剂直接调整塑料进行浮选，一般润湿剂对不同塑料的吸附差异较小，因此分离效果不够理想。本发明首次提出润湿剂选择性脱附对混合塑料浮选分离，先采用润湿剂对塑料进行表面调控，然后通过搅拌或超声清洗使塑料表面吸附的润湿剂分子进一步脱附，脱附后不同塑料在浮选过程可浮性的差异显著增大，并且浮选结果更稳定，进而实现混合塑料的高效浮选分离。The mixed plastics separation technologies developed include methods such as manual sorting, gravity separation, flotation, electrostatic separation and selective dissolution. The manual sorting process of plastics is labor-intensive, the working environment is harsh, and the separation efficiency is low. Gravity separation and electrostatic separation have great limitations on the separation of mixed plastics with similar physical properties. Selective solvents are expensive and organic solvents are very toxic. At present, flotation can achieve good advantages for mixed plastics with similar densities, but most of the plastics have similar hydrophobic properties, and the selective separation of mixed plastics can be achieved through the adjustment of wetting agents. At present, there are relatively few studies on the separation of waste plastics by flotation, and wetting agents are used to directly adjust the plastics for flotation. Generally, the difference in the adsorption of different plastics by wetting agents is small, so the separation effect is not ideal. The present invention proposes for the first time the selective desorption of the wetting agent for the flotation separation of mixed plastics. First, the wetting agent is used to regulate the surface of the plastic, and then the wetting agent molecules adsorbed on the surface of the plastic are further desorbed by stirring or ultrasonic cleaning. After that, the difference in floatability of different plastics in the flotation process is significantly increased, and the flotation results are more stable, thereby realizing the efficient flotation separation of mixed plastics.
发明内容Contents of the invention
针对现有技术中对物理化学性质相近的塑料进行分离的方法存在的缺陷，本发明的目的是在于提供一种对混合塑料高效分离的方法，该方法操作简单、成本低，满足工业化应用生产。In view of the defects in the existing methods for separating plastics with similar physical and chemical properties, the purpose of the present invention is to provide a method for efficiently separating mixed plastics, which is simple to operate and low in cost, and can meet industrial application production.
本发明一种混合塑料的分离方法，包括下述步骤：A kind of separation method of mixed plastics of the present invention comprises the following steps:
步骤一step one
将混合塑料颗粒浸泡在含有润湿剂的水溶液进行表面改性后，固液分离，所得固体为表面改性后的混合塑料颗粒；所述润湿剂选自木质素磺酸盐、单宁酸、明胶、白雀树皮汁、司盘、褐煤蜡、月桂醇、水玻璃、醋酸纤维素中的至少一种、优选为木质素磺酸盐、单宁酸、水玻璃中的至少一种、进一步优选为木质素磺酸盐；表面改性后的混合塑料颗粒表面润湿剂的吸附量大于等于5g/t、优选为5～100g/t、进一步优选为5～20g/t；After soaking the mixed plastic particles in an aqueous solution containing a wetting agent for surface modification, the solid-liquid separation, the obtained solid is the mixed plastic particles after surface modification; the wetting agent is selected from lignosulfonate, tannic acid , gelatin, sparrow bark juice, span, montan wax, lauryl alcohol, water glass, at least one of cellulose acetate, preferably at least one of lignosulfonate, tannic acid, water glass, It is more preferably lignosulfonate; the adsorption amount of the surface wetting agent of mixed plastic particles after surface modification is greater than or equal to 5g/t, preferably 5-100g/t, more preferably 5-20g/t;
步骤二step two
将步骤一所得表面改性后的混合塑料颗粒置于水中洗脱不超过20分钟后，固液分离，所得固体为洗脱后混合塑料颗粒；The surface-modified mixed plastic particles obtained in step 1 are eluted in water for no more than 20 minutes, and the solid and liquid are separated, and the obtained solid is the mixed plastic particles after elution;
步骤三step three
对步骤二所得洗脱后混合塑料颗粒进行浮选；实现混合塑料的分离。Flotation is carried out on the eluted mixed plastic particles obtained in step 2; the separation of mixed plastics is realized.
本发明一种混合塑料的分离方法，所述混合塑料包括化学式不同的两种或两种以上的塑料。The invention discloses a method for separating mixed plastics, which includes two or more plastics with different chemical formulas.
本发明一种混合塑料的分离方法，混合塑料为聚氯乙烯和聚对苯二甲酸乙二醇酯塑料；或者为丙烯腈-丁二烯-苯乙烯和聚苯乙烯塑料。The invention discloses a method for separating mixed plastics. The mixed plastics are polyvinyl chloride and polyethylene terephthalate plastics; or acrylonitrile-butadiene-styrene and polystyrene plastics.
本发明一种混合塑料的分离方法，混合塑料颗粒的粒径小于2cm，并且90％颗粒的粒径小于1cm。进一步优选方案为：粒径为0.1～1cm的混合塑料颗粒的占全部混合塑料颗粒数目的70％以及70％以上。The invention discloses a method for separating mixed plastics. The particle size of the mixed plastic particles is less than 2 cm, and 90% of the particles have a particle size less than 1 cm. A further preferred solution is: mixed plastic particles with a particle size of 0.1-1 cm account for 70% or more of the total number of mixed plastic particles.
本发明一种混合塑料的分离方法，步骤一中，含有润湿剂的水溶液中，润湿剂的浓度为1～10g/L、优选为4～8g/L、进一步优选为5～6g/L。A method for separating mixed plastics according to the present invention, in step 1, in the aqueous solution containing a wetting agent, the concentration of the wetting agent is 1-10 g/L, preferably 4-8 g/L, more preferably 5-6 g/L .
本发明一种混合塑料的分离方法，步骤一中，含有润湿剂的水溶液的pH值为4.5～7.5。含有润湿剂的水溶液所用的水可以是自来水、去离子水、海水、蒸馏水中的至少一种。The invention discloses a method for separating mixed plastics. In step 1, the pH value of the aqueous solution containing a wetting agent is 4.5-7.5. The water used for the aqueous solution containing a wetting agent may be at least one of tap water, deionized water, seawater, and distilled water.
本发明一种混合塑料的分离方法，步骤一中，所述木质素磺酸盐包括木质素磺酸钠盐、木质素磺酸钾盐、木质素磺酸钙盐、木质素磺酸镁盐、木质素磺酸锰盐、木质素磺酸铵盐。A method for separating mixed plastics according to the present invention. In step 1, the lignosulfonate includes sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate, magnesium lignosulfonate, Manganese lignosulfonate, ammonium lignosulfonate.
本发明一种混合塑料的分离方法，步骤一中，含有润湿剂的水溶液中还含有1～100mg/L的无机盐，所述无机盐包括氯化钠、氯化铝、氯化钙、氯化钾、碳酸钠、碳酸钾、氯化镁、氯化铁、硫酸镁。A method for separating mixed plastics according to the present invention. In step 1, the aqueous solution containing the wetting agent also contains 1-100 mg/L of inorganic salts, and the inorganic salts include sodium chloride, aluminum chloride, calcium chloride, chlorine Potassium chloride, sodium carbonate, potassium carbonate, magnesium chloride, ferric chloride, magnesium sulfate.
本发明一种混合塑料的分离方法，步骤一中，将混合塑料颗粒浸泡在含有润湿剂的水溶液进行表面改性时，采用机械搅拌促进润湿剂的吸附，搅拌速率为50～200转/分，时间为10～120分钟、优选为20～40分钟，使得混合塑料表面润湿剂的吸附量不小于5g/t。The invention discloses a method for separating mixed plastics. In step 1, when the mixed plastic particles are soaked in an aqueous solution containing a wetting agent for surface modification, mechanical stirring is used to promote the adsorption of the wetting agent, and the stirring rate is 50-200 rpm The time is 10 to 120 minutes, preferably 20 to 40 minutes, so that the adsorption amount of the mixed plastic surface wetting agent is not less than 5 g/t.
本发明一种混合塑料的分离方法，步骤二中，将步骤一所得表面改性后的混合塑料颗粒置于水，在搅拌条件和/或超声条件下洗脱2～20分钟后，固液分离，所得固体为洗脱后混合塑料颗粒；所述搅拌的速率为200～800转/分钟、优选为300～500转/分钟、进一步优选为400转/分钟，所述超声的功率为20～100kW、优选为40～60kW、进一步优选为50kW。洗脱时，所用的水是自来水、去离子水、蒸馏水中的至少一种。A method for separating mixed plastics according to the present invention. In step 2, the surface-modified mixed plastic particles obtained in step 1 are placed in water, and after being eluted for 2 to 20 minutes under stirring conditions and/or ultrasonic conditions, solid-liquid separation is carried out. , the obtained solid is mixed plastic particles after elution; the stirring rate is 200-800 rpm, preferably 300-500 rpm, more preferably 400 rpm, and the ultrasonic power is 20-100kW , preferably 40 to 60 kW, more preferably 50 kW. During elution, the water used is at least one of tap water, deionized water and distilled water.
本发明一种混合塑料的分离方法，步骤三中，按质量比，浮选液：洗脱后混合塑料颗粒＝9-99：1，将步骤二所得洗脱后混合塑料颗粒加入浮选液中，进行浮选；所述浮选液由水和无机盐组成，且浮选液的pH值为4～8；浮选液中无机盐的浓度为100～2000mg/L；所述无机盐选自氯化钠、氯化铝、氯化钙、氯化钾、碳酸钠、碳酸钾、氯化镁、氯化铁、硫酸镁中的至少一种。The present invention is a method for separating mixed plastics. In step 3, according to the mass ratio, flotation liquid: mixed plastic particles after elution = 9-99: 1, and the eluted mixed plastic particles obtained in step 2 are added to the flotation liquid , carry out flotation; the flotation liquid is composed of water and inorganic salts, and the pH value of the flotation liquid is 4 to 8; the concentration of the inorganic salts in the flotation liquid is 100 to 2000 mg/L; the inorganic salts are selected from At least one of sodium chloride, aluminum chloride, calcium chloride, potassium chloride, sodium carbonate, potassium carbonate, magnesium chloride, ferric chloride, and magnesium sulfate.
本发明一种混合塑料的分离方法，步骤三中，浮选时，加入起泡剂，所述起泡剂选自松醇油、甲基异丁基甲醇、异辛醇中的至少一种，所述起泡剂用量为1～100g/t塑料、优选为1～50g/t塑料。A method for separating mixed plastics according to the present invention. In step 3, during flotation, a foaming agent is added, and the foaming agent is selected from at least one of terpineol oil, methyl isobutyl carbinol, and isooctyl alcohol, The foaming agent is used in an amount of 1-100 g/t plastic, preferably 1-50 g/t plastic.
本发明一种混合塑料的分离方法，浮选1～10分钟。即可实现至少一种塑料与其它塑料的分离。且分离出来的单一塑料纯度高。The invention discloses a method for separating mixed plastics, which involves flotation for 1 to 10 minutes. Separation of at least one plastic from other plastics is achieved. And the isolated single plastic has high purity.
本发明一种混合塑料的分离方法，能快速分离常规物理化学方法难以分离或高效分离的混合塑料。The invention discloses a method for separating mixed plastics, which can quickly separate mixed plastics that are difficult to separate or efficiently separated by conventional physical and chemical methods.
原理和优势Principles and advantages
本发明首次提出润湿剂选择性脱附对混合塑料浮选分离，先采用润湿剂对塑料进行表面改性，然后通过搅拌或超声清洗使塑料表面吸附的润湿剂分子进行适量的脱附，适量的脱附后，不同塑料在浮选过程可浮性的差异显著增大，并且浮选结果更稳定，进而实现混合塑料的高效浮选分离。The present invention proposes selective desorption of wetting agent for the flotation separation of mixed plastics for the first time. Firstly, the wetting agent is used to modify the surface of the plastic, and then the wetting agent molecules adsorbed on the surface of the plastic are desorbed in an appropriate amount by stirring or ultrasonic cleaning. After an appropriate amount of desorption, the difference in floatability of different plastics in the flotation process is significantly increased, and the flotation results are more stable, thereby realizing the efficient flotation separation of mixed plastics.
本发明基于现有技术中对物理性质相近的混合塑料难以实现分离，本发明首次采用润湿剂选择性脱附方法对混合塑料进行浮选分离，实现了混合塑料的高效分离。本发明的方法能高效从混合塑料中回收塑料，回收率高于98％，纯度达到99.6％；另外，本发明的工艺操作简单、成本低，具有很好的经济可行性，满足工业化应用。The present invention is based on the fact that it is difficult to separate mixed plastics with similar physical properties in the prior art. For the first time, the invention adopts a wetting agent selective desorption method to carry out flotation separation of mixed plastics, and realizes efficient separation of mixed plastics. The method of the invention can efficiently recover plastics from mixed plastics, the recovery rate is higher than 98%, and the purity reaches 99.6%. In addition, the process of the invention is simple in operation, low in cost, has good economic feasibility, and satisfies industrial applications.
具体实施方式Detailed ways
通过以下实施例进一步阐释本发明，实施例不以任何方式被解释成对本发明的范围强加限制。相反，应清楚理解，可以采取本领域的技术人员在阅读本文的描述之后可以看出的各种其他实施方案、修改及其等效物而不偏离本发明的精神和/或所附权利要求的范围。The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations on the scope of the present invention. On the contrary, it should be clearly understood that various other embodiments, modifications and their equivalents, which can be seen by those skilled in the art after reading the description herein, can be adopted without departing from the spirit of the invention and/or the spirit of the appended claims. scope.
实施例1Example 1
将PVC和PET混合塑料进行破碎，取0.5～1.0cm粒径的塑料颗粒150g，加入到10g/L的木质素磺酸钠水溶液中，向水溶液中加入90mg/L硫酸镁，并调整pH为7.5，机械搅拌速率为100转/分，搅拌时间为90分钟，然后将混合塑料放入自来水中，超声清洗，功率为20kW，时间为5分钟，然后进行浮选，浮选条件为：30g/t的甲基异丁基甲醇，浮选4min，pH为7.8，浮选介质中加入2000mg/L碳酸钠。分离后PVC和PET的纯度分别为99.6％和98.3％，回收率大于98％。Crush PVC and PET mixed plastics, take 150g of plastic particles with a particle size of 0.5-1.0cm, add them to 10g/L sodium lignosulfonate aqueous solution, add 90mg/L magnesium sulfate to the aqueous solution, and adjust the pH to 7.5 , the mechanical stirring rate is 100 rpm, the stirring time is 90 minutes, then put the mixed plastic into tap water, ultrasonic cleaning, the power is 20kW, the time is 5 minutes, and then carry out flotation, the flotation condition is: 30g/t Methyl isobutyl methanol, flotation for 4min, pH is 7.8, 2000mg/L sodium carbonate is added to the flotation medium. After separation, the purities of PVC and PET are respectively 99.6% and 98.3%, and the recovery rate is greater than 98%.
对比例1Comparative example 1
将PVC和PET混合塑料进行破碎，取0.5～1.0cm粒径的塑料颗粒150g，加入到10g/L的木质素磺酸钠水溶液中，向水溶液中加入90mg/L硫酸镁，并调整pH为7.5，机械搅拌速率为100转/分，搅拌时间为90分钟，然后进行浮选，浮选条件为：30g/t的甲基异丁基甲醇，浮选4min，pH为7.8，浮选介质中加入2000mg/L碳酸钠。分离后PVC和PET的纯度分别为80.3％和78.6％，回收率为70％。Crush PVC and PET mixed plastics, take 150g of plastic particles with a particle size of 0.5-1.0cm, add them to 10g/L sodium lignosulfonate aqueous solution, add 90mg/L magnesium sulfate to the aqueous solution, and adjust the pH to 7.5 , the mechanical stirring rate is 100 rev/min, the stirring time is 90 minutes, then carry out flotation, the flotation conditions are: 30g/t methyl isobutyl carbinol, flotation 4min, pH is 7.8, add in the flotation medium 2000mg/L sodium carbonate. After separation, the purities of PVC and PET were 80.3% and 78.6%, respectively, and the recovery rate was 70%.
通过对比实施例可以明显看出洗脱处理可以显著增加分离效果。It can be clearly seen from the comparative examples that the elution treatment can significantly increase the separation effect.
实施例2Example 2
将ABS和PS混合塑料进行破碎，取0.1～1.0cm粒径的塑料颗粒100g，加入到1g/L的木质素磺酸钙水溶液中，向水溶液中加入20mg/L氯化镁，并调整pH为4.8，机械搅拌速率为50转/分，搅拌时间为20分钟，然后将混合塑料放入自来水中，超声清洗，功率为80kW，时间为2分钟，然后进行浮选，浮选条件为：80g/t的异辛醇，浮选6min，pH为5，浮选介质中加入1000mg/L氯化镁。分离后PVC和PET的纯度分别为94.3％和95.3％，回收率大于96.2％。Crush the mixed plastic of ABS and PS, take 100g of plastic particles with a particle size of 0.1-1.0cm, add it to 1g/L calcium lignosulfonate aqueous solution, add 20mg/L magnesium chloride to the aqueous solution, and adjust the pH to 4.8, The mechanical stirring rate is 50 rpm, the stirring time is 20 minutes, then the mixed plastics are put into tap water, ultrasonically cleaned, the power is 80kW, the time is 2 minutes, and then flotation is carried out. The flotation conditions are: 80g/t Isooctyl alcohol, flotation for 6min, pH is 5, 1000mg/L magnesium chloride is added to the flotation medium. The purities of PVC and PET after separation are 94.3% and 95.3% respectively, and the recovery rate is greater than 96.2%.
对比例2Comparative example 2
将ABS和PS混合塑料进行破碎，取0.1～1.0cm粒径的塑料颗粒100g，加入到1g/L的木质素磺酸钙水溶液中，向水溶液中加入20mg/L氯化镁，并调整pH为4.8，机械搅拌速率为50转/分，搅拌时间为20分钟，然后将混合塑料放入自来水中，超声清洗，功率为120kW，时间为40分钟，然后进行浮选，浮选条件为：80g/t的异辛醇，浮选6min，pH为5，浮选介质中加入1000mg/L氯化镁。分离后PVC和PET的纯度分别为81.2％和84.5％，回收率为84.6％。Crush the mixed plastic of ABS and PS, take 100g of plastic particles with a particle size of 0.1-1.0cm, add it to 1g/L calcium lignosulfonate aqueous solution, add 20mg/L magnesium chloride to the aqueous solution, and adjust the pH to 4.8, The mechanical stirring rate is 50 rpm, the stirring time is 20 minutes, then the mixed plastics are put into tap water, ultrasonically cleaned, the power is 120kW, the time is 40 minutes, and then flotation is carried out. The flotation conditions are: 80g/t Isooctyl alcohol, flotation for 6min, pH is 5, 1000mg/L magnesium chloride is added to the flotation medium. After separation, the purities of PVC and PET were 81.2% and 84.5%, respectively, and the recovery rate was 84.6%.
实施例3Example 3
将PVC和PET混合塑料进行破碎，取0.5～2.0cm粒径的塑料颗粒100g，加入到8g/L的木质素磺酸铵水溶液中，向水溶液中加入10mg/L氯化钠，并调整pH为6.8，机械搅拌速率为180转/分，搅拌时间为110分钟，然后将混合塑料放入蒸馏水中，机械搅拌速率为800转/分，搅拌时间为20分钟，然后进行浮选，浮选条件为：40g/t的松醇油，浮选8min，pH为5，浮选介质中加入200mg/L氯化钙。分离后PVC和PET的纯度分别为92.6％和94.3％，回收率大于95.8％。Crush PVC and PET mixed plastics, take 100g of plastic particles with a particle size of 0.5-2.0cm, add them to 8g/L ammonium lignosulfonate aqueous solution, add 10mg/L sodium chloride to the aqueous solution, and adjust the pH to 6.8, the mechanical stirring rate is 180 rpm, the stirring time is 110 minutes, then put the mixed plastic into distilled water, the mechanical stirring rate is 800 rpm, the stirring time is 20 minutes, and then carry out flotation, the flotation conditions are : 40g/t pinitol oil, flotation 8min, pH is 5, 200mg/L calcium chloride is added in the flotation medium. After separation, the purities of PVC and PET are 92.6% and 94.3% respectively, and the recovery rate is greater than 95.8%.
对比例3Comparative example 3
将PVC和PET混合塑料进行破碎，取0.5～2.0cm粒径的塑料颗粒100g，加入到8g/L的木质素磺酸铵水溶液中，向水溶液中加入10mg/L氯化钠，并调整pH为6.8，机械搅拌速率为180转/分，搅拌时间为110分钟，然后将混合塑料放入蒸馏水中，机械搅拌速率为100转/分，搅拌时间为1分钟，然后进行浮选，浮选条件为：40g/t的松醇油，浮选8min，pH为5，浮选介质中加入200mg/L氯化钙。分离后PVC和PET的纯度分别为76.6％和80.3％，回收率为81.4％。Crush PVC and PET mixed plastics, take 100g of plastic particles with a particle size of 0.5-2.0cm, add them to 8g/L ammonium lignosulfonate aqueous solution, add 10mg/L sodium chloride to the aqueous solution, and adjust the pH to 6.8, the mechanical stirring rate is 180 rpm, the stirring time is 110 minutes, then put the mixed plastic into distilled water, the mechanical stirring rate is 100 rpm, the stirring time is 1 minute, and then carry out flotation, the flotation conditions are : 40g/t pinitol oil, flotation 8min, pH is 5, 200mg/L calcium chloride is added in the flotation medium. After separation, the purities of PVC and PET were 76.6% and 80.3%, respectively, and the recovery rate was 81.4%.
实施例4Example 4
将ABS和PS混合塑料进行破碎，取0.1～1.5cm粒径的塑料颗粒80g，加入到4g/L的木质素磺酸镁水溶液中，向水溶液中加入50mg/L氯化钙，并调整pH为5.5，机械搅拌速率为100转/分，搅拌时间为50分钟，然后将混合塑料放入去离子水中，机械搅拌速率为200转/分，搅拌时间为5分钟，然后进行浮选，浮选条件为：10g/t的松醇油，浮选3min，pH为7，浮选介质中加入1200mg/L氯化钾。分离后PVC和PET的纯度分别为96.3％和96.3％，回收率大于98.7％。Crush the mixed plastic of ABS and PS, take 80g of plastic particles with a particle size of 0.1-1.5cm, add it to a 4g/L aqueous solution of magnesium lignosulfonate, add 50mg/L calcium chloride to the aqueous solution, and adjust the pH to 5.5, the mechanical stirring rate is 100 rpm, the stirring time is 50 minutes, then put the mixed plastic into deionized water, the mechanical stirring rate is 200 rpm, the stirring time is 5 minutes, and then carry out flotation, flotation conditions For: 10g/t pinitol oil, flotation for 3min, pH is 7, 1200mg/L potassium chloride is added to the flotation medium. After separation, the purities of PVC and PET are 96.3% and 96.3% respectively, and the recovery rate is greater than 98.7%.
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