废电路板热解渣氧化制备活性炭及表征分析研究
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摘要
废电路板(简称PCB)的回收是一个相当复杂的过程。目前,国内外主要着重于对贵重金属回收的研究,但是关于非金属材料无害化和资源化的研究相对较少。从PCB的组成能够看出,树脂塑料等高分子材料占废PCB重量的30%左右,加上与树脂粘结在一起的玻璃纤维等增强材料,其重量达到电路板总重量60%以上。电路板的增强材料主要是玻璃纤维布,因此具有很高的回收利用价值。
本研究利用微波在热解方面的优越性,根据活性炭的制备方法,在低真空条件下微波辐照热解废电路板,对热解后的热解渣用硝酸氧化改性制备活性炭,并对热解渣和活性炭进行表征分析和预测活性炭的应用,为废电路板非金属材料的资源化利用提供理论基础。
微波真空辐照热解废电路板,热解渣用硝酸氧化改性制备活性炭,考察微波辐照时间、微波功率、电路板粒度大小、硝酸浸渍时间、硝酸浸渍浓度(质量分数)对活性炭吸附能力的影响,通过正交试验确定各因素对吸附性能的影响和最佳试验条件。试验表明：微波辐照时间、微波功率、电路板粒度大小、硝酸浸渍时间、硝酸浸渍浓度(质量分数)对活性炭吸附性能都有影响；对亚甲基蓝吸附值影响的主次顺序为：微波功率>硝酸浓度>粒度大小>硝酸浸渍时间>辐照时间,对碘吸附值影响的主次顺序为：微波功率>粒度大小>硝酸浸渍时间>辐照时间>硝酸浓度。分析各因素最佳水平顺序,既考虑亚甲基蓝吸附性能,又考虑碘吸附性能,可得到本试验条件下的最佳工艺为：微波辐照时间15min,微波功率633W,粒度大小1.5～2.0,硝酸浓度20%,浸渍时间16h,制得产品亚甲基蓝吸附值94.8mg/g,碘吸附值496.6mg/g。
选取吸附性能最好的活性炭,即微波辐照时间15min,微波功率633W,粒度大小1.5～2.0,硝酸浓度20%,浸渍时间16h；用等离子发射光谱仪、X光电子能谱仪、傅里叶变换红外光谱仪及扫描电子显微镜(SEM-EDS)对热解渣和活性炭进行表征分析。分析结果表明：热解渣经过硝酸浸渍后制备的活性炭一方面金属含量大大减少,另一方面引进了含氧基团,—C—C,或芳香族和脂肪族化合物含量减少(由原来的90.71%变到86.05%,),而C—0含量则增大(由原来的5.01%变到13.95%,),且变化明显,而C=0基本上消失了；表面的氧以羟基、羰基、羧基和内酯基形式存在,其中羟基含量(286.23eV)的增幅较大,而内酯基(284.80eV)的含量则降低；活性炭的结构形态较热解渣更不规则,孔洞和孔隙的差异性则较小,表面明显被氧化,一些骨架被氧化,出现了部分塌陷和大小不等的孔洞,孔周边变得更加平滑。
对该试验所制备的活性炭进行表征分析后,得出该活性炭的主要特征是碘吸附值和亚甲蓝吸附值(最佳活性炭产品碘吸附值496.6mg/g,亚甲基蓝吸附值94.8mg/g)并不理想,由此可以得出孔径和比表面积在吸附过程中不占优势,但是该活性炭引入了含氧官能团,增加了活性炭表面酸性基团的含量，减少了碱性基团的含量,从而提高活性炭的表面极性和亲水性。因此该活性炭用于液相吸附时,应占很大优势。结合本试验所产生的废水,废水中含有有价金属,在对废水的有价金属进行回收后,用该活性炭处理该试验所产生的废水应该是可行的；同时本试验所产生的热解气体可以作为城市煤气使用,热解液体可以作为燃料或者化工原料使用,都可以实现资源回收和环境保护的双重效果。
本试验在工艺流程上有所创新,既回收了其中的有价金属,又回收了其中的非金属材料,技术上切实可行,所用的试剂少(仅用到硝酸)、工艺简单、成本低,具有经济和环境双重效益。
The recycling of printed circuit boards is a complex processing. Currently domestic and international countries developed vast research on the recycling of printed circuit board (PCB) particular emphasizing on more the metal recycling while less the nonmetal. It can be seen the composition of PCB which the macromolecule materials such as resin is about30%and plus the reinforcing material together with the fiber glass is about60%. The reinforcing material of PCB is mainly fiber glass which has high resource.
This paper combining the superiority of the microwave and pyrolysis and according to the preparation of activated carbon, investigated the preparation and characterization of activated carbon modified by nitric acid from solid residues of PCB with microwave vacuum pyrolysis. which, in order to provide for theoretical basis recycling PCB.
The effect on microwave time, microwave power, particle size, nitric acid concentrate and soak time on the adsorption properties of the activated carbon were discussed. Adopting different analysis, its result shown, the sequence of methylene blue were:microwave power>nitric acid concentrate>particle size>soak time>microwave time, the sequence of iodine were:microwave power>particle size>soak time>microwave time>nitric acid concentrate. Analyzing the best horizontal of each factor while considering the value of methylene blue and iodine, it could be gained the optimized experimental conditions were microwave time15min, microwave power633W, particle size1.5-2.0, nitric acid concentrate20%, and soak time16h and the value of methylene blue, iodine were94.8mg/g and496.6mg/g, respectively.
The characterization of the optimized activated carbon was studied. The surface features of the optimized activated carbon were studied in virtue of ICP,XPS,FTIR and SEM. The results showed that the surface oxygen content increased (from5.01%to13.95%, respectively), while the metal contact and—C—C or the compounds of aromatic and aliphatic decreased obviously(from90.71%to86.05%, respectively)and the C=O species disappeared on the surface of the activated carbon; The functional groups on the activated carbon surface,such as carboxyl, phenol hydroxyl, lactonic and hydroxyl group, which the hydroxyl content increased obviously, while lactonic content decreased; The structure and morphology of the activated carbon is more irregular, while the differ of the holes and pores is smaller; The surface of activated carbon is oxidized significantly, some of which is subsidence and formed holes of varying size, while the around hole becomes smooth.
It obtained the features of activated carbon was that the value of methylene blue and iodine were not ideal (the optimized activated carbon of the value of methylene blue and iodine were94.8mg/g and496.6mg/g.),which can be drawn the pore diameter and specific surface area during the adsorption process was not dominant, but the oxygen functional groups of activated carbon, increasing the content of the surface acidic groups, reducing the content of alkali groups, so improving the surface polarity and hydrophilicity of the activated carbon. Therefore, the activated carbon would attribute to the great advantage of the liquid phase adsorption. In this experiment, The activated carbon treating the wastewater recycling of the valuable metals is feasible; At the same time, the pyrolysis products from PCB which the gases could be used as coal gas applied in the city; the liquid is well engineering material for making chemical; It can achieved the dual effect of recovering resource and environmental protection.
The treatment process of this experiment is innovative,which not noly recycled the metals,but also recycled the nonmetals.It can generated the economic and environmental benefits because of technoically practicable, less reagents(only to nitric acid),simply process and low cost.
本研究利用微波在热解方面的优越性,根据活性炭的制备方法,在低真空条件下微波辐照热解废电路板,对热解后的热解渣用硝酸氧化改性制备活性炭,并对热解渣和活性炭进行表征分析和预测活性炭的应用,为废电路板非金属材料的资源化利用提供理论基础。
微波真空辐照热解废电路板,热解渣用硝酸氧化改性制备活性炭,考察微波辐照时间、微波功率、电路板粒度大小、硝酸浸渍时间、硝酸浸渍浓度(质量分数)对活性炭吸附能力的影响,通过正交试验确定各因素对吸附性能的影响和最佳试验条件。试验表明：微波辐照时间、微波功率、电路板粒度大小、硝酸浸渍时间、硝酸浸渍浓度(质量分数)对活性炭吸附性能都有影响；对亚甲基蓝吸附值影响的主次顺序为：微波功率>硝酸浓度>粒度大小>硝酸浸渍时间>辐照时间,对碘吸附值影响的主次顺序为：微波功率>粒度大小>硝酸浸渍时间>辐照时间>硝酸浓度。分析各因素最佳水平顺序,既考虑亚甲基蓝吸附性能,又考虑碘吸附性能,可得到本试验条件下的最佳工艺为：微波辐照时间15min,微波功率633W,粒度大小1.5～2.0,硝酸浓度20%,浸渍时间16h,制得产品亚甲基蓝吸附值94.8mg/g,碘吸附值496.6mg/g。
选取吸附性能最好的活性炭,即微波辐照时间15min,微波功率633W,粒度大小1.5～2.0,硝酸浓度20%,浸渍时间16h；用等离子发射光谱仪、X光电子能谱仪、傅里叶变换红外光谱仪及扫描电子显微镜(SEM-EDS)对热解渣和活性炭进行表征分析。分析结果表明：热解渣经过硝酸浸渍后制备的活性炭一方面金属含量大大减少,另一方面引进了含氧基团,—C—C,或芳香族和脂肪族化合物含量减少(由原来的90.71%变到86.05%,),而C—0含量则增大(由原来的5.01%变到13.95%,),且变化明显,而C=0基本上消失了；表面的氧以羟基、羰基、羧基和内酯基形式存在,其中羟基含量(286.23eV)的增幅较大,而内酯基(284.80eV)的含量则降低；活性炭的结构形态较热解渣更不规则,孔洞和孔隙的差异性则较小,表面明显被氧化,一些骨架被氧化,出现了部分塌陷和大小不等的孔洞,孔周边变得更加平滑。
对该试验所制备的活性炭进行表征分析后,得出该活性炭的主要特征是碘吸附值和亚甲蓝吸附值(最佳活性炭产品碘吸附值496.6mg/g,亚甲基蓝吸附值94.8mg/g)并不理想,由此可以得出孔径和比表面积在吸附过程中不占优势,但是该活性炭引入了含氧官能团,增加了活性炭表面酸性基团的含量，减少了碱性基团的含量,从而提高活性炭的表面极性和亲水性。因此该活性炭用于液相吸附时,应占很大优势。结合本试验所产生的废水,废水中含有有价金属,在对废水的有价金属进行回收后,用该活性炭处理该试验所产生的废水应该是可行的；同时本试验所产生的热解气体可以作为城市煤气使用,热解液体可以作为燃料或者化工原料使用,都可以实现资源回收和环境保护的双重效果。
本试验在工艺流程上有所创新,既回收了其中的有价金属,又回收了其中的非金属材料,技术上切实可行,所用的试剂少(仅用到硝酸)、工艺简单、成本低,具有经济和环境双重效益。
The recycling of printed circuit boards is a complex processing. Currently domestic and international countries developed vast research on the recycling of printed circuit board (PCB) particular emphasizing on more the metal recycling while less the nonmetal. It can be seen the composition of PCB which the macromolecule materials such as resin is about30%and plus the reinforcing material together with the fiber glass is about60%. The reinforcing material of PCB is mainly fiber glass which has high resource.
This paper combining the superiority of the microwave and pyrolysis and according to the preparation of activated carbon, investigated the preparation and characterization of activated carbon modified by nitric acid from solid residues of PCB with microwave vacuum pyrolysis. which, in order to provide for theoretical basis recycling PCB.
The effect on microwave time, microwave power, particle size, nitric acid concentrate and soak time on the adsorption properties of the activated carbon were discussed. Adopting different analysis, its result shown, the sequence of methylene blue were:microwave power>nitric acid concentrate>particle size>soak time>microwave time, the sequence of iodine were:microwave power>particle size>soak time>microwave time>nitric acid concentrate. Analyzing the best horizontal of each factor while considering the value of methylene blue and iodine, it could be gained the optimized experimental conditions were microwave time15min, microwave power633W, particle size1.5-2.0, nitric acid concentrate20%, and soak time16h and the value of methylene blue, iodine were94.8mg/g and496.6mg/g, respectively.
The characterization of the optimized activated carbon was studied. The surface features of the optimized activated carbon were studied in virtue of ICP,XPS,FTIR and SEM. The results showed that the surface oxygen content increased (from5.01%to13.95%, respectively), while the metal contact and—C—C or the compounds of aromatic and aliphatic decreased obviously(from90.71%to86.05%, respectively)and the C=O species disappeared on the surface of the activated carbon; The functional groups on the activated carbon surface,such as carboxyl, phenol hydroxyl, lactonic and hydroxyl group, which the hydroxyl content increased obviously, while lactonic content decreased; The structure and morphology of the activated carbon is more irregular, while the differ of the holes and pores is smaller; The surface of activated carbon is oxidized significantly, some of which is subsidence and formed holes of varying size, while the around hole becomes smooth.
It obtained the features of activated carbon was that the value of methylene blue and iodine were not ideal (the optimized activated carbon of the value of methylene blue and iodine were94.8mg/g and496.6mg/g.),which can be drawn the pore diameter and specific surface area during the adsorption process was not dominant, but the oxygen functional groups of activated carbon, increasing the content of the surface acidic groups, reducing the content of alkali groups, so improving the surface polarity and hydrophilicity of the activated carbon. Therefore, the activated carbon would attribute to the great advantage of the liquid phase adsorption. In this experiment, The activated carbon treating the wastewater recycling of the valuable metals is feasible; At the same time, the pyrolysis products from PCB which the gases could be used as coal gas applied in the city; the liquid is well engineering material for making chemical; It can achieved the dual effect of recovering resource and environmental protection.
The treatment process of this experiment is innovative,which not noly recycled the metals,but also recycled the nonmetals.It can generated the economic and environmental benefits because of technoically practicable, less reagents(only to nitric acid),simply process and low cost.
引文
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