吸附型三元乙丙基水处理复合材料的制备与性能
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摘要
当前,水环境日益恶化,水污染呈加剧蔓延趋势,在冶金、化学、制革、食品,机械制造及采矿等工业部门排放的废水中会存在很多油类有机物和重金属离子等单一或复合污染物。处理水中这类污染物的材料研究势在必行。
本论文选用综合性能优良的三元乙丙橡胶作为基体,添加无机类或有机类功能型的填料,采用简便易行的熔融共混方法,对多组分体系进行配方设计,制备出吸附型环境保护水处理复合材料,包括四大类8种材料:Fe_2O_3/ EPDM、Fe_2O_3(焙烧)/ EPDM、MgO/EPDM、MgO(偶联剂)/EPDM、非泡沫废弃矿渣粉/EPDM、泡沫型废弃矿渣粉/EPDM、EPDM基两亲型吸附材料以及固定化微生物材料。这些新型水处理材料利用吸附原理对水中的油类及重金属离子等污染物进行吸附去除。本论文内容申请国家发明专利后,可转化为应用成果。
油类一般漂浮于水面,重金属离子则溶于水中,本论文中制备的水处理复合材料能够自动悬浮于油水界面处,不依靠机械外力对所处理的污染物进行吸附,提高了使用效率。
本论文针对水中油类有机物的污染:
(1)Fe_2O_3/EPDM和Fe_2O_3(焙烧)/ EPDM吸油材料:将Fe_2O_3在400℃下进行焙烧,焙烧后的Fe_2O_3粒径小于Fe_2O_3的粒径,在基体中具有更好的分散性。Fe_2O_3/EPDM的吸油率比交联后EPDM的吸油率提高了227%;而Fe_2O_3(焙烧)/EPDM的吸油率比Fe_2O_3/EPDM的吸油率又提高了64 %。这两种复合材料的吸油速率远大于EPDM和交联EPDM的吸油速率。并利用扫描电镜、XRD等表征手段深入讨论了这两种材料的吸油机理。
(2)MgO/EPDM和MgO(偶联剂)/EPDM吸油材料:尝试不同种类的金属氧化物作为填料,研究偶联剂在复合材料中的作用机理及对材料力学性能的影响。MgO/EPDM的吸油率比Fe_2O_3/EPDM的吸油率增加201.89%。偶联剂的加入使得复合材料的力学性能提高,但其吸油性能有所弱化,利用红外光谱分析了复合材料吸油性能弱化的原因。
(3)泡沫型废弃矿渣粉/EPDM吸油材料:该材料采用金矿提取后的废弃矿渣粉作为填料,利用熔融共混和模压发泡技术制备。其吸油性能不但优于Fe_2O_3/EPDM的吸油性能。同时优于非泡沫型废弃矿渣粉/EPDM。泡沫型废弃矿渣粉/EPDM与非泡沫型废弃矿渣粉/EPDM相比,不但实现废弃物再利用,其材料成本进一步降低;吸附表面积进一步增大;材料密度进一步降低。并成功探索出泡沫材料的模压发泡工艺。
本论文针对水中油类有机物和重金属离子的复合污染:
Fe_2O_3(焙烧)/阴离子交换树脂/ EPDM两亲型吸附材料:以EPDM作为基体,焙烧Fe_2O_3和阴离子交换树脂201Х7作为填料,制备出一种同时吸附油和六价铬离子的水处理复合材料。这种材料除了用于诸多工业部门排放的废水的处理,还可用于水源中的复合污染的治理。首次利用熔融共混方法制备的两亲吸附型复合材料,实验结果表明:在油水共存体系中,材料对油和Cr6+的总吸附能力要大于其在单一吸附介质中的吸附能力。
本论文针对被吸附油类的后处理问题:
Fe_2O_3(焙烧)/ EPDM /微生物固定化材料:以EPDM为基体,焙烧Fe_2O_3为填料,PEG-2000为致孔剂,采用熔融共混方法,制备出一种环境保护固定化微生物材料。该材料本身具有很好的吸油特性,其吸油率达到272.36%。其固定化菌群后实现了对被吸附原油的降解,不但增加了材料的除油率,更成功解决了吸油材料的后处理问题。材料对高效除油菌的固定化率可达8.44×105个/g,材料可以对固定化的菌群保持一定的活性。固定化菌群的原油去除率是材料本身原油去除率的近5倍。微生物的不断繁殖导致原油被不断降解,使得该材料可以长期循环使用。
At present, the freshwater resources are increasing depletion. However, the human demand for freshwater is increasing. The discharges of industrial wastewater and domestic wastewater have been significantly contaminated environment. A large number of wastewater which was not deal with has polluted the water environment. Water pollution has been seriously affected the ecological structure of water and efficient use of water resources, and it directly or indirectly hampered the sustainable development of industrial and agricultural production. In addition, it was major threat to human health. The major pollutants of Industrial and domestic sewage are oil and heavy metal ions. The treatment methods and techniques are also hot research problems for environmental researcher.
In recent years, offshore oil exploration and the tankers and oil pipelines on the marine accident have caused serious oil pollution. At restaurants, metals, cereals, oil and leather processing industries, especially at oil extraction, processing, transport and other industries, these industries will produce a large amount of oily wastewater.
The 30 percent oil pollution was from industrial wastewater discharge, 45 percent was from oil tanker spills in ocean. The majority research, development and application of oil sorbent materials are for the treatment of oily wastewater.
With the rapid development of the global economy, heavy metals get into the water through mining, metal smelting processing, chemical industry waste water, pesticides, chemical fertilizers, the abuse of livelihood, geological erosion, weathering and other natural sources.
The major pollutants in Industrial and domestic sewage are oil and heavy metal ions, its treatment methods and techniques is a hot issue in today's research.
In the first part of our study, a new kind of material for oil adsorption was prepared by melt blending with EPDM as the matrix and Fe_2O_3 as the filler. The effects of dicumylperoxide (DCP) and Fe_2O_3 contents on the oil absorptivity were studied. The results show that the oil absorbency reaches the highest value for the Fe_2O_3/EPDM composite with 3 wt % DCP and 25 wt % Fe_2O_3, while the same is true for Fe_2O_3 (calcination)/EPDM composite with 2 wt % DCP and 30 wt % Fe_2O_3. Comparing the two samples with the highest oil absorbency, the oil absorption rate of Fe_2O_3 (calcination)/EPDM composite is higher. The experimental result indicates that the oil absorbency of Fe_2O_3/EPDM composite is 227 % higher than that of EPDM (crosslinked); the oil absorbency of Fe_2O_3 (calcination)/EPDM composite is 64 % higher than that of Fe_2O_3/EPDM composite.
In the second part of our study, a new kind of material for oil adsorption was prepared by melt blend with EPDM as the matrix and MgO as the filler. The effects of Dicumylperoxide (DCP) and MgO contents on the oil absorbency were studied. Comparing the two samples with the highest oil adsorption rates, the experimental result indicates that the oil absorbency of EPDM (crosslinked) is 51% more than that of EPDM; the oil absorbency of MgO/EPDM composite is 886.54% more than that of EPDM (crosslinked); the oil absorbency of MgO/EPDM composite is 198.22% more than that of MgO (coupling agent)/EPDM composite. The absorbent characteristics of MgO/EPDM are better than these of MgO (coupling agent)/EPDM.
In the third part of our study, a new kind of foaming material for oil adsorption was prepared by melting blend and mold pressing, with EPDM as the matrix and waste dusty slag as the filler. The effects of foaming agent (AC) and waste dusty slag contents on the oil absorbency were studied. The results show that the oil absorbency reached the highest value with waste dusty slag loading 10 phr, DCP loading 2 phr and AC loading being fixed at 4 phr. The oil retentions were over 80% with AC loadings from 1 to 4 phr, but when AC was over 4 phr, the oil retention decreased deeply. We compared the oil absorption rates of the foaming composites with the non-foaming composites, the results indicate that the oil absorbency of non-foaming composite is 101.46% more than that of EPDM (crosslinked); the oil absorbency of foaming composite composite is 389.82% more than that of non-foaming composite. The breaking strength decreased as MgO loadings increased; the breaking strength of MgO (coupling agent)/EPDM is higher than that of MgO/EPDM. The oil absorbency of MgO (coupling agent)/EPDM is attenuation than that of MgO/EPDM. These reasons were analyzed by SEM and IR.
In the fourth part of our study, a new kind of material for oil and Cr (Ⅵ) absorption was prepared by melt blend, with EPDM as the matrix and calcinatory Fe_2O_3 and anion exchange resin 201Х7 as the filler. The absorbencies of composites were changed greatly with various ratios of calcinatory Fe_2O_3 and anion exchange resin 201Х7. The results show that the oil absorbencies increased continuously and Cr (Ⅵ) absorbencies were step-down as Ion exchange resin loadings from 1% to 7%. The optimum proportionings of calcinatory Fe_2O_3 and anion exchange resin 201Х7 were gotten with different oils when the absorbencies of composites for oils and Cr (Ⅵ) were reached maximum simultaneously. The total adsorptive capacity was much higher than that in only one adsorption medium.
In the last part of our study is basis in the previous chapter, a new kind of microbial composite carrier was prepared by melt blend, with (EPDM) as the matrix and calcinatory Fe_2O_3 as the filler. The oil degrading bacteria were screened in the crude oil, cultured and breed. We immobilized bacteria using adsorption method, and measured the immobilization rate in the composite carrier. The immobilization time of the largest number of oil degrading bacteria using the composite vector was 7h. The carrier immobilized bacteria cultured 24 h, and measured its absorbance to verify the effect of immobilized bacteria. The results confirmed that the bacteria have been immobilized in the carrier successfully and the bacteria were viable. The absorbent characteristics is good, the oil absorbency is 272.36%. Compared the removal oil rate with immobilization bacteria and the composite carrier, The results are that the removal oil rate of immobilization bacteria was much higher than that of the composite carrier, and the composite carrier was an effective microorganisms immobilized carrier.
本论文选用综合性能优良的三元乙丙橡胶作为基体,添加无机类或有机类功能型的填料,采用简便易行的熔融共混方法,对多组分体系进行配方设计,制备出吸附型环境保护水处理复合材料,包括四大类8种材料:Fe_2O_3/ EPDM、Fe_2O_3(焙烧)/ EPDM、MgO/EPDM、MgO(偶联剂)/EPDM、非泡沫废弃矿渣粉/EPDM、泡沫型废弃矿渣粉/EPDM、EPDM基两亲型吸附材料以及固定化微生物材料。这些新型水处理材料利用吸附原理对水中的油类及重金属离子等污染物进行吸附去除。本论文内容申请国家发明专利后,可转化为应用成果。
油类一般漂浮于水面,重金属离子则溶于水中,本论文中制备的水处理复合材料能够自动悬浮于油水界面处,不依靠机械外力对所处理的污染物进行吸附,提高了使用效率。
本论文针对水中油类有机物的污染:
(1)Fe_2O_3/EPDM和Fe_2O_3(焙烧)/ EPDM吸油材料:将Fe_2O_3在400℃下进行焙烧,焙烧后的Fe_2O_3粒径小于Fe_2O_3的粒径,在基体中具有更好的分散性。Fe_2O_3/EPDM的吸油率比交联后EPDM的吸油率提高了227%;而Fe_2O_3(焙烧)/EPDM的吸油率比Fe_2O_3/EPDM的吸油率又提高了64 %。这两种复合材料的吸油速率远大于EPDM和交联EPDM的吸油速率。并利用扫描电镜、XRD等表征手段深入讨论了这两种材料的吸油机理。
(2)MgO/EPDM和MgO(偶联剂)/EPDM吸油材料:尝试不同种类的金属氧化物作为填料,研究偶联剂在复合材料中的作用机理及对材料力学性能的影响。MgO/EPDM的吸油率比Fe_2O_3/EPDM的吸油率增加201.89%。偶联剂的加入使得复合材料的力学性能提高,但其吸油性能有所弱化,利用红外光谱分析了复合材料吸油性能弱化的原因。
(3)泡沫型废弃矿渣粉/EPDM吸油材料:该材料采用金矿提取后的废弃矿渣粉作为填料,利用熔融共混和模压发泡技术制备。其吸油性能不但优于Fe_2O_3/EPDM的吸油性能。同时优于非泡沫型废弃矿渣粉/EPDM。泡沫型废弃矿渣粉/EPDM与非泡沫型废弃矿渣粉/EPDM相比,不但实现废弃物再利用,其材料成本进一步降低;吸附表面积进一步增大;材料密度进一步降低。并成功探索出泡沫材料的模压发泡工艺。
本论文针对水中油类有机物和重金属离子的复合污染:
Fe_2O_3(焙烧)/阴离子交换树脂/ EPDM两亲型吸附材料:以EPDM作为基体,焙烧Fe_2O_3和阴离子交换树脂201Х7作为填料,制备出一种同时吸附油和六价铬离子的水处理复合材料。这种材料除了用于诸多工业部门排放的废水的处理,还可用于水源中的复合污染的治理。首次利用熔融共混方法制备的两亲吸附型复合材料,实验结果表明:在油水共存体系中,材料对油和Cr6+的总吸附能力要大于其在单一吸附介质中的吸附能力。
本论文针对被吸附油类的后处理问题:
Fe_2O_3(焙烧)/ EPDM /微生物固定化材料:以EPDM为基体,焙烧Fe_2O_3为填料,PEG-2000为致孔剂,采用熔融共混方法,制备出一种环境保护固定化微生物材料。该材料本身具有很好的吸油特性,其吸油率达到272.36%。其固定化菌群后实现了对被吸附原油的降解,不但增加了材料的除油率,更成功解决了吸油材料的后处理问题。材料对高效除油菌的固定化率可达8.44×105个/g,材料可以对固定化的菌群保持一定的活性。固定化菌群的原油去除率是材料本身原油去除率的近5倍。微生物的不断繁殖导致原油被不断降解,使得该材料可以长期循环使用。
At present, the freshwater resources are increasing depletion. However, the human demand for freshwater is increasing. The discharges of industrial wastewater and domestic wastewater have been significantly contaminated environment. A large number of wastewater which was not deal with has polluted the water environment. Water pollution has been seriously affected the ecological structure of water and efficient use of water resources, and it directly or indirectly hampered the sustainable development of industrial and agricultural production. In addition, it was major threat to human health. The major pollutants of Industrial and domestic sewage are oil and heavy metal ions. The treatment methods and techniques are also hot research problems for environmental researcher.
In recent years, offshore oil exploration and the tankers and oil pipelines on the marine accident have caused serious oil pollution. At restaurants, metals, cereals, oil and leather processing industries, especially at oil extraction, processing, transport and other industries, these industries will produce a large amount of oily wastewater.
The 30 percent oil pollution was from industrial wastewater discharge, 45 percent was from oil tanker spills in ocean. The majority research, development and application of oil sorbent materials are for the treatment of oily wastewater.
With the rapid development of the global economy, heavy metals get into the water through mining, metal smelting processing, chemical industry waste water, pesticides, chemical fertilizers, the abuse of livelihood, geological erosion, weathering and other natural sources.
The major pollutants in Industrial and domestic sewage are oil and heavy metal ions, its treatment methods and techniques is a hot issue in today's research.
In the first part of our study, a new kind of material for oil adsorption was prepared by melt blending with EPDM as the matrix and Fe_2O_3 as the filler. The effects of dicumylperoxide (DCP) and Fe_2O_3 contents on the oil absorptivity were studied. The results show that the oil absorbency reaches the highest value for the Fe_2O_3/EPDM composite with 3 wt % DCP and 25 wt % Fe_2O_3, while the same is true for Fe_2O_3 (calcination)/EPDM composite with 2 wt % DCP and 30 wt % Fe_2O_3. Comparing the two samples with the highest oil absorbency, the oil absorption rate of Fe_2O_3 (calcination)/EPDM composite is higher. The experimental result indicates that the oil absorbency of Fe_2O_3/EPDM composite is 227 % higher than that of EPDM (crosslinked); the oil absorbency of Fe_2O_3 (calcination)/EPDM composite is 64 % higher than that of Fe_2O_3/EPDM composite.
In the second part of our study, a new kind of material for oil adsorption was prepared by melt blend with EPDM as the matrix and MgO as the filler. The effects of Dicumylperoxide (DCP) and MgO contents on the oil absorbency were studied. Comparing the two samples with the highest oil adsorption rates, the experimental result indicates that the oil absorbency of EPDM (crosslinked) is 51% more than that of EPDM; the oil absorbency of MgO/EPDM composite is 886.54% more than that of EPDM (crosslinked); the oil absorbency of MgO/EPDM composite is 198.22% more than that of MgO (coupling agent)/EPDM composite. The absorbent characteristics of MgO/EPDM are better than these of MgO (coupling agent)/EPDM.
In the third part of our study, a new kind of foaming material for oil adsorption was prepared by melting blend and mold pressing, with EPDM as the matrix and waste dusty slag as the filler. The effects of foaming agent (AC) and waste dusty slag contents on the oil absorbency were studied. The results show that the oil absorbency reached the highest value with waste dusty slag loading 10 phr, DCP loading 2 phr and AC loading being fixed at 4 phr. The oil retentions were over 80% with AC loadings from 1 to 4 phr, but when AC was over 4 phr, the oil retention decreased deeply. We compared the oil absorption rates of the foaming composites with the non-foaming composites, the results indicate that the oil absorbency of non-foaming composite is 101.46% more than that of EPDM (crosslinked); the oil absorbency of foaming composite composite is 389.82% more than that of non-foaming composite. The breaking strength decreased as MgO loadings increased; the breaking strength of MgO (coupling agent)/EPDM is higher than that of MgO/EPDM. The oil absorbency of MgO (coupling agent)/EPDM is attenuation than that of MgO/EPDM. These reasons were analyzed by SEM and IR.
In the fourth part of our study, a new kind of material for oil and Cr (Ⅵ) absorption was prepared by melt blend, with EPDM as the matrix and calcinatory Fe_2O_3 and anion exchange resin 201Х7 as the filler. The absorbencies of composites were changed greatly with various ratios of calcinatory Fe_2O_3 and anion exchange resin 201Х7. The results show that the oil absorbencies increased continuously and Cr (Ⅵ) absorbencies were step-down as Ion exchange resin loadings from 1% to 7%. The optimum proportionings of calcinatory Fe_2O_3 and anion exchange resin 201Х7 were gotten with different oils when the absorbencies of composites for oils and Cr (Ⅵ) were reached maximum simultaneously. The total adsorptive capacity was much higher than that in only one adsorption medium.
In the last part of our study is basis in the previous chapter, a new kind of microbial composite carrier was prepared by melt blend, with (EPDM) as the matrix and calcinatory Fe_2O_3 as the filler. The oil degrading bacteria were screened in the crude oil, cultured and breed. We immobilized bacteria using adsorption method, and measured the immobilization rate in the composite carrier. The immobilization time of the largest number of oil degrading bacteria using the composite vector was 7h. The carrier immobilized bacteria cultured 24 h, and measured its absorbance to verify the effect of immobilized bacteria. The results confirmed that the bacteria have been immobilized in the carrier successfully and the bacteria were viable. The absorbent characteristics is good, the oil absorbency is 272.36%. Compared the removal oil rate with immobilization bacteria and the composite carrier, The results are that the removal oil rate of immobilization bacteria was much higher than that of the composite carrier, and the composite carrier was an effective microorganisms immobilized carrier.
引文
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