含油污泥催化热解工艺的优化及热解产物分析
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摘要
随着环保意识的增强,含油污泥资源化与无害化处理问题成为研究的热点。分别用体积分数为5%、10%的HCl对活性白土进行改性,制得催化剂。采用扫描电镜、能量色散X射线光谱仪(EDX)、X-射线衍射、N_2-吸附脱附等分析手段对催化剂的结构进行表征。用催化剂对含油污泥进行催化热解,探讨了改性活性白土催化含油污泥热解的影响因素,并对热解产生的固、液产物进行了分析。结果表明:催化剂加量为1%,氮气流速为100 mL/min,反应温度为430℃,处理时间为3. 5 h时,油回收率可达到85. 49%,与未加催化剂时相比,油回收率提高了7. 22%,处理时间缩短了0. 5 h。由热解油组分分析可知,催化热解使得C_6～C_(15)的回收率提高,产物油品质得到改善。
With the enhancement of environmental protection consciousness,the problem of resource and harmless disposal of oily sludge has become the focus of attention. In this paper,the activated clay was modified by the HCl with volume fraction of 5% and10% to prepare the catalyst. The structure of the catalyst was characterized by scanning electron microscope( SEM),energy dispersive X-ray spectroscopy( EDX),X-ray diffraction( XRD) infrared spectroscopy,physical adsorption analyzer and other analytical methods. Then the catalyst was applied in the sludge pyrolysis process. The factors affecting the pyrolysis of oily sludge catalyzed by modified activated clay were discussed,and the solid and liquid products produced by pyrolysis were analyzed. The highest oil recovery rate reached 85. 49% under the optimum pyrolysis parameters when catalyst dosage was 1%,nitrogen gas flux was 100 mL/min,pyrolysis temperature was 430 ℃ and reaction last for 3. 5 h. Compared with blank experiment group,the oil recovery rate increased by 7. 22% percentage points,and the pyrolysis time shortens by 0. 5 h. The analysis of pyrolysis oil components showed that,the catalytic pyrolysis greatly improved the yield of C_6～ C_(15),as well as the product oil quality.
With the enhancement of environmental protection consciousness,the problem of resource and harmless disposal of oily sludge has become the focus of attention. In this paper,the activated clay was modified by the HCl with volume fraction of 5% and10% to prepare the catalyst. The structure of the catalyst was characterized by scanning electron microscope( SEM),energy dispersive X-ray spectroscopy( EDX),X-ray diffraction( XRD) infrared spectroscopy,physical adsorption analyzer and other analytical methods. Then the catalyst was applied in the sludge pyrolysis process. The factors affecting the pyrolysis of oily sludge catalyzed by modified activated clay were discussed,and the solid and liquid products produced by pyrolysis were analyzed. The highest oil recovery rate reached 85. 49% under the optimum pyrolysis parameters when catalyst dosage was 1%,nitrogen gas flux was 100 mL/min,pyrolysis temperature was 430 ℃ and reaction last for 3. 5 h. Compared with blank experiment group,the oil recovery rate increased by 7. 22% percentage points,and the pyrolysis time shortens by 0. 5 h. The analysis of pyrolysis oil components showed that,the catalytic pyrolysis greatly improved the yield of C_6～ C_(15),as well as the product oil quality.
引文
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[17]杨鹏辉,魏君,屈撑囤.延长油田含油污泥真空热解研究[J].环境工程,2015,33(10):101-103.
[18]胡海杰.含油污泥热解催化剂及应用技术研究[D].西安:西安石油大学,2018.
[19]管志超,胡艳军,钟英杰.不同升温速率下城市污水污泥热解特性及动力学研究[J].环境污染与防治,2012,34(3):35-39.
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[21]李金灵,屈撑囤,朱世东,等.含油污泥热解残渣特性及其资源化利用研究概述[J].材料导报,2018,32(17):3023-3032.
[2] Zhou X H,Jia H Z,Qu C T,et al. Low-temperature co-pyrolysis behaviours and kinetics of oily sludge:effect of agricultural biomass[J]. Environmental Technology,2017,38(3):361-369.
[3] Li S C A. High quality oil recovery from oil sludge employing a pyrolysis process with oil sludge ash catalyst[J]. International Journal of Waste Resources,2015,5(2):164-176.
[4]王飞飞,屈璇,张欢,等.含油污泥处理现状及新的研究进展[J].广州化工,2018,46(1):27-29,56.
[5] Cheng S,Li A,Yoshikawa K. High quality oil recovery from oil sludge employing a pyrolysis process with oil sludge ash catalyst[J]. International Journal of Waste Resour.,2015,5(2).
[6] Egazar’yants S B,Vinokurov V A,Vutolkina A V,et al. Oil sludge treatment processes[J]. Chemistry&Technology of Fuels&Oils,2015,51(5):506-515.
[7] Lin B C,Huang Q X,Ali M,et al. Continuous catalytic pyrolysis of oily sludge using U-shape reactor for producing saturatesenriched light oil[J]. Proceedings of the Combustion Institute,2019,37(3):3101-3108.
[8]刘鲁珍,李金灵,屈撑囤.TiO2/MCM-41的制备及对含油污泥热解过程的影响[J].环境工程学报,2016,10(12):7294-7298.
[9] Yang J K,Xu X Y,Liang S,et al. Enhanced hydrogen production in catalytic pyrolysis of sewage sludge by red mud:thermogravimetric kinetic analysis and pyrolysis characteristics[J].International Journal of Hydrogen Energy,2018,43(16):7795-7807.
[10]林炳丞,王君,黄群星,等.含油污泥在ZSM-5沸石上催化热解产物特性[J].化工学报,2018,69(6):2681-2687.
[11] Wang H,Jia H,Wang L,et al. The catalytic effect of modified bentonite on the pyrolysis of oily sludge[J]. Liquid Fuels Technology,2015,33(13/14):1388-1394.
[12]杨兆磊.改性膨润土催化剂的制备及催化有机反应研究[D].曲阜:曲阜师范大学,2012.
[13]高晓薇,韦藤幼,潘远凤,等.活性白土的化学改性及其作用机理研究[J].广西大学学报(自然科学版),2010,35(3):410-414,418.
[14]黄文.改性膨润土的制备表征及其应用研究[D].湘潭:湘潭大学,2017.
[15]王成成.改性活性白土的制备及对甲基橙染料废水的处理研究[D].西安:陕西师范大学,2012.
[16]刘鲁珍.含油污泥低温催化热解催化剂的合成与应用技术研究[D].西安:西安石油大学,2016.
[17]杨鹏辉,魏君,屈撑囤.延长油田含油污泥真空热解研究[J].环境工程,2015,33(10):101-103.
[18]胡海杰.含油污泥热解催化剂及应用技术研究[D].西安:西安石油大学,2018.
[19]管志超,胡艳军,钟英杰.不同升温速率下城市污水污泥热解特性及动力学研究[J].环境污染与防治,2012,34(3):35-39.
[20]孙丽娜,李凯,汤立红,等.常见金属氧化物烟气脱硫研究进展[J].化工进展,2017,36(1):181-188.
[21]李金灵,屈撑囤,朱世东,等.含油污泥热解残渣特性及其资源化利用研究概述[J].材料导报,2018,32(17):3023-3032.
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