油页岩灰渣改性制备吸附剂及其吸附特性的研究
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摘要
油页岩作为一种重要的补充能源资源以其巨大的储量、丰富的综合利用层次,引起了全世界的关注。油页岩含油率低、灰分含量高,经过循环流化床燃烧后会生成大量的底灰和飞灰。油页岩灰渣的矿物成分含量很高,存在微量的有毒有害重金属,如果只是单纯利用油页岩后,将油页岩灰渣作为废物丢弃,不仅对地球环境造成严重影响,而其还是一种对资源的浪费。
本文以吉林桦甸地区热电厂油页岩灰渣为研究对象,对其物理化学特性,合成NaX型沸石吸附剂的工艺操作参数,及其对模拟含镍废水的吸附特性进行了全面系统的研究,主要内容如下:
通过XRD,XRF,SEM,BET比表面积与BJH孔径分布等测试方法对其物理化学特性进行测试与表征,系统考察了其化学组成,矿物组成,表面特征,BET比表面积,BJH孔径分布等特性参数,为其合成沸石吸附剂提供基础。
探索以油页岩灰渣为原料,采用碱熔融水热合成法制备NaX沸石吸附剂,系统考察了体系碱度,晶化时间,晶化温度对合成沸石的影响因素,从而确定了制备NaX沸石吸附剂的最佳工艺参数。通过对制备NaX型沸石吸附剂物理化学特性进行测试,研究结果表明制备的沸石吸附剂具有较强的吸附性能,且该制备方法工艺简单,原料丰富,制备成本低。
以油页岩灰渣,制备沸石吸附剂为研究对象,采用静态吸附法研究了其对模拟含镍废水的吸附特性。试验研究了投加量、pH值、温度、离子初始浓吸附时间等因素对吸附特性的影响,对吸附动力学和吸附热力学进行了分析,并用Langmuir和Freundlich吸附等温线对吸附进行了分析。研究结果表明,油页岩灰渣和沸石吸附剂对镍离子(Ni~(2+))吸附的拟合曲线都能很好地与吸附动力学一级反应方程、吸附动力学准二级反应方程和Elovich方程相吻合。吸附是一个非自发进行的过程,Langmuir型和Freundlich型吸附等温线能较好地描述其对模拟含镍废水的吸附性能。
At present, there are increasing more and more concerns about the utilization of oil shale as an alternative source of energy due to the rich reserves. A large quantity of oil shale ash is generated annually in the combustion of oil shale for electricity generation because of oil shale with low-oil content and high-ash content. While oil shale is only utilized to produce electricity, a large quantity of oil shale ash is dumped in landfills as waste and not proposal. It is not only a waste of resource but also it may cause a serious environmental problem. This is due to that oil shale ash is potentially hazardous heavy pollutants containing a variety of heavy metal trace elements and various mineral.
Based on oil shale ash from the thermal power plant located in Huadian of Jinlin province, China, the physical and chemistry characteristics of oil, the key parameters of conversion of oil shale ash into NaX zeolite and the adsorption characteristics of Ni~(2+) from wastewater by oil shale ash and zeolite were studied systematically.
The physical and chemistry characteristics of oil shale ash such as the chemical composition, the mineral composition, BET specific surface area, BJH cumulative pore area, BJH cumulative pore volume were obtained by a series of testing methods such as XRD, XRF, SEM, BET specific surface area and BJH pore distribution, and the testing results were obtained to provide a basis of conversion of oil shale into zeolite.
An alkali fusion and hydrothermal synthesis method was studied to converse of oil shale ash into NaX zeolite. The parameters of synthesis zeolite such as H_2O/Na_2O, Na_2O/ SiO_2 molar ration, synthesis time and synthesis temperature on the process of synthesis of zeolite were discussed and the key parameters were obtained and optimized to achieve the best synthetical conditions. The physical and chemistry characteristics of zeolite were tested and it was found that the synthesis zeolite was a promising and efficient adsorbent with high adsorption capacity.
The adsorption characteristics of Ni~(2+) from wastewater by oil shale ash and zeolite were studied by a series of batch adsorption experiments. Effects of various parameters such adsorbent dose, pH, temperature, initial concentration, adsorption time were investigated, and the theoretical analysis of the adsorption kinetics, adsorption thermodynamics, Langmuir and Freundlich adsorption isotherm were utilized to fit the process of adsorption. It was showed that the process of adsorption was fitted to the Pseudo frist order kinetics model, Pseudo second order kinetics model and Elovich kinetics model, and the process of adsorption was a non-spontaneous process, and both the Langmuir model and Freundlich model were utilized to fit the process of adsorption with R~2 >0.98 in all cases.
本文以吉林桦甸地区热电厂油页岩灰渣为研究对象,对其物理化学特性,合成NaX型沸石吸附剂的工艺操作参数,及其对模拟含镍废水的吸附特性进行了全面系统的研究,主要内容如下:
通过XRD,XRF,SEM,BET比表面积与BJH孔径分布等测试方法对其物理化学特性进行测试与表征,系统考察了其化学组成,矿物组成,表面特征,BET比表面积,BJH孔径分布等特性参数,为其合成沸石吸附剂提供基础。
探索以油页岩灰渣为原料,采用碱熔融水热合成法制备NaX沸石吸附剂,系统考察了体系碱度,晶化时间,晶化温度对合成沸石的影响因素,从而确定了制备NaX沸石吸附剂的最佳工艺参数。通过对制备NaX型沸石吸附剂物理化学特性进行测试,研究结果表明制备的沸石吸附剂具有较强的吸附性能,且该制备方法工艺简单,原料丰富,制备成本低。
以油页岩灰渣,制备沸石吸附剂为研究对象,采用静态吸附法研究了其对模拟含镍废水的吸附特性。试验研究了投加量、pH值、温度、离子初始浓吸附时间等因素对吸附特性的影响,对吸附动力学和吸附热力学进行了分析,并用Langmuir和Freundlich吸附等温线对吸附进行了分析。研究结果表明,油页岩灰渣和沸石吸附剂对镍离子(Ni~(2+))吸附的拟合曲线都能很好地与吸附动力学一级反应方程、吸附动力学准二级反应方程和Elovich方程相吻合。吸附是一个非自发进行的过程,Langmuir型和Freundlich型吸附等温线能较好地描述其对模拟含镍废水的吸附性能。
At present, there are increasing more and more concerns about the utilization of oil shale as an alternative source of energy due to the rich reserves. A large quantity of oil shale ash is generated annually in the combustion of oil shale for electricity generation because of oil shale with low-oil content and high-ash content. While oil shale is only utilized to produce electricity, a large quantity of oil shale ash is dumped in landfills as waste and not proposal. It is not only a waste of resource but also it may cause a serious environmental problem. This is due to that oil shale ash is potentially hazardous heavy pollutants containing a variety of heavy metal trace elements and various mineral.
Based on oil shale ash from the thermal power plant located in Huadian of Jinlin province, China, the physical and chemistry characteristics of oil, the key parameters of conversion of oil shale ash into NaX zeolite and the adsorption characteristics of Ni~(2+) from wastewater by oil shale ash and zeolite were studied systematically.
The physical and chemistry characteristics of oil shale ash such as the chemical composition, the mineral composition, BET specific surface area, BJH cumulative pore area, BJH cumulative pore volume were obtained by a series of testing methods such as XRD, XRF, SEM, BET specific surface area and BJH pore distribution, and the testing results were obtained to provide a basis of conversion of oil shale into zeolite.
An alkali fusion and hydrothermal synthesis method was studied to converse of oil shale ash into NaX zeolite. The parameters of synthesis zeolite such as H_2O/Na_2O, Na_2O/ SiO_2 molar ration, synthesis time and synthesis temperature on the process of synthesis of zeolite were discussed and the key parameters were obtained and optimized to achieve the best synthetical conditions. The physical and chemistry characteristics of zeolite were tested and it was found that the synthesis zeolite was a promising and efficient adsorbent with high adsorption capacity.
The adsorption characteristics of Ni~(2+) from wastewater by oil shale ash and zeolite were studied by a series of batch adsorption experiments. Effects of various parameters such adsorbent dose, pH, temperature, initial concentration, adsorption time were investigated, and the theoretical analysis of the adsorption kinetics, adsorption thermodynamics, Langmuir and Freundlich adsorption isotherm were utilized to fit the process of adsorption. It was showed that the process of adsorption was fitted to the Pseudo frist order kinetics model, Pseudo second order kinetics model and Elovich kinetics model, and the process of adsorption was a non-spontaneous process, and both the Langmuir model and Freundlich model were utilized to fit the process of adsorption with R~2 >0.98 in all cases.
引文
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[2]张德义.关于中国能源形势的思考.当代石油石化[J],2008,16(2):1-8.
[3]杨鸿玺.国际能源形势与中国的发展进程.利平与发展[J],2009,104(2):28-32.
[4]周喜安.新形势下我国能源发展格局.中国党政干部论坛[J],2009,(5):23-25.
[5]钱家麟,王剑秋,李术元.世界油页岩资源利用和发展趋势.吉林大学学报(地球科学版)[J],2006,36(6):877-887.
[6]Jiang X.M.,Han X.X.,Cui Z.G.Progress and recent utilization trends in combustion of Chinese oil shale.Progress in Energy and Combustion Science[J],2007,33(6):552-579.
[7]柳蓉,刘招君.国内外油页岩资源现状及综合开发潜力分析.吉林大学学报[J],2006.36(6):869-876.
[8]Dyni.J.R.Geology and resources of some world oil-shale de-posits.Oil Shale[J],2003,20(3):193-252.
[9]K Brendow.Global oil shale issues and perspectives.Oil Shale[J],2003,20(1):81-92.
[10]姜秀民,韩向欣,崔志刚.油页岩综合利用技术的研究.自然科学进[J],2005,15(11):1342-1345.
[11]刘招君,柳蓉.中国油页岩特征及开发利用前景分析.地学前缘[J],2005,12(3):315-323.
[12]刘招君,董清水,叶松青.油页岩的综合开发与利用.吉林大学学报(地球科学版)[J],2006,36(6):869-876.
[13]游君君,叶松青,刘招君.油页岩的综合开发与利用.世界地质[J],2004,23(3):261-265.
[14]陈洁渝,严春杰,李子冲.油页岩渣的综合利J{j.矿产保护与利用[J],2006,6:41-45.
[15]柳蓉,刘招君,国内外油页岩资源现状及综合开发潜力分析.吉林大学学报(地球科学版)[J],2006,36(6):892-898.
[16]张袄民,关珺,何德民.几种典型的油页岩干馏技术.吉林大学学报(地球科学版)[J],2006,36(6):1019-1026.
[17]刘志逊,高健,赵寒冬.国内油页岩干馏技术现状与发展趋势.煤炭加工与综合利用[J],2007,1:45-49.
[18]李术元,岳长涛,王剑秋等.世界油页岩开发利用近况.中外能源[J].2009,14(2):16-24.
[19]何永光,宋岩.油页岩的综合利用.煤炭加工与综合利用[J],2005,1(1):53-56.
[20]Aunela,Tapola L.A.,Frandsen F.J.,Hasanen E.K.Trace metal emissions from the Estonian oil shale fired power plant.Fuel Processing Yechnology[J],1998,57(1):1-24.
[21]张丽萍,曾荣树,徐文东.抚顺西舍场油页岩的淋滤行为及其对周围水体的影响.矿物岩石地球化学通报[J],2007,26(2):160-163.
[22]赵剑剑,王春华.油页岩发电利用研究.广东电力[J],2008,21(9):20-22.
[23]Al-Qodah Z.Adsorption of dyes using shale oil ash.Water Research[J],2000,34(12):4295-4303.
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