Effect of starch and PVC interactions on characteristics of pyrolysis tar

doi:10.11949/j.issn.0438-1157.20161641

Abstract

Abstract:

During the pyrolysis of municipal solid wastes, different components may interact with each other. In order to search the possible interaction on characteristics of tar, starch, polyvinyl chloride (PVC) and their mixture at the weight ratio of 1:1 were pyrolyzed at the temperatures of 400, 500 and 600℃. Gas chromatography-mass spectrometry (GC-MS) and gel permeation chromatography (GPC) analyses were adopted to characterize the collected tar. According to the results, interaction was occurred during the co-pyrolysis of starch and PVC, which enhanced the generation of heavier hydrocarbons and polycyclic aromatic hydrocarbons. The molecular weight of tar showed an obvious increase of 44%—79%. The interaction was more significant at a higher pyrolysis temperature. The tar derived from mixture showed great similarity with that derived from PVC, indicating that during the co-pyrolysis of starch and PVC, PVC was the dominant contributor with respect to tar formation. In addition, as the pyrolysis temperature arose from 400 to 600℃, the yield and homogeneity of tar both decreased while the contents of polycyclic aromatic hydrocarbons and heavier hydrocarbons increased. Therefore, the co-pyrolysis and high pyrolysis temperature both contributed to yield less tar, but the tar was more difficult to handle with.

Key words: blend, pyrolysis, tar, GC-MS, GPC, interaction, waste treatment

摘要：

为研究城市生活垃圾热解过程中不同组分交互作用对焦油特性的影响，将淀粉、聚氯乙烯（PVC）及其质量比为1：1的混合物在温度为400，500和600℃的条件下热解，对收集的焦油进行气相色谱-质谱联用（GC-MS）分析和凝胶渗透色谱（GPC）分析。结果表明，淀粉和PVC共热解时发生了交互作用，促进了更多重质组分和多环芳烃的生成，使焦油的分子质量大幅增加，增幅达44%～79%，且二者的交互作用在高温下更加显著。混合物与PVC的热解焦油呈现明显的相似性，在淀粉和PVC共同热解的过程中，PVC对焦油的生成起主导作用。此外，随热解温度的升高，焦油的产率和同质性均降低，而多环芳烃和重质组分含量增加。因此，二者共热解和较高的热解温度均能减少焦油产率，却也使生成的焦油更难以处理。

关键词: 混合, 热解, 焦油, GC-MS, GPC, 交互作用, 废物处理

CLC Number:

X705

TANG Yijing, WANG Xiaohang, WANG Dongke, HE Shiyu, HUANG Qunxing, CHI Yong, YAN Jianhua. Effect of starch and PVC interactions on characteristics of pyrolysis tar[J]. CIESC Journal, 2017, 68(5): 2049-2056.

唐一菁, 王肖杭, 王东科, 何石鱼, 黄群星, 池涌, 严建华. 淀粉和聚氯乙烯交互作用对热解焦油特性的影响[J]. 化工学报, 2017, 68(5): 2049-2056.

References 31

[1]	韩雷. 城市生活垃圾热解产气特性研究及神经网络预测[D]. 杭州: 浙江大学, 2005. HAN L. Study on pyrolysis gas characteristics of MSW and neural networks predication[D]. Hangzhou: Zhejiang University, 2005.
[2]	肖睿, 金保升, 仲兆平, 等. 基于低温气化和高温熔融焚烧方法处理城市生活垃圾[J]. 能源研究与利用, 2001, 3: 28-30. XIAO R, JIN B S, ZHONG Z P, et al. Second generation of municipal solid waste incinerator-gasification & melting furnace[J]. Energy Research and Utilization, 2001, 3: 28-30.
[3]	闻望, 王宝生, 修同斌, 等. 城市垃圾气化处理法探索[J]. 环境科学, 1988, 9(2): 47-51. WEN W, WANG B S, XIU T B, et al. Research on gasification of municipal solid wastes[J]. Environmental Science, 1988, 9(2): 47-51.
[4]	沈祥智, 严建华, 白丛生, 等. 主要垃圾组分热解动力学模型的优化及比较[J]. 化工学报, 2006, 57(10): 2433-2438. SHEN X Z, YAN J H, BAI C S, et al. Optimization and comparison of pyrolysis kinetic model for typical MSW components[J]. Journal of Chemical Industry and Engineering(China), 2006, 57(10): 2433-2438.
[5]	吴旺明, 严建华, 温俊明, 等. 垃圾典型组分混合热解特性的实验研究[J]. 环境科学与技术, 2005, 28(5): 21-22. WU W M, YAN J H, WEN J M, et al. Experimental study on mixed pyrolysis characteristics of typical MSW components[J]. Environmental Science and Technology, 2005, 28(5): 21-22.
[6]	DEVI L, PTASINSKI K J, JANSSEN F J J G. A review of the primary measures for tar elimination in biomass gasification processes[J]. Biomass & Bioenergy, 2003, 24(2): 125-140.
[7]	CHO M H, MUN T Y, KIM J S. Production of low-tar producer gas from air gasification of mixed plastic waste in a two-stage gasifier using olivine combined with activated carbon[J]. Energy, 2013, 58(3): 688-694.
[8]	LI C, SUZUKI K. Tar property, analysis, reforming mechanism and model for biomass gasification—an overview[J]. Renewable and Sustainable Energy Reviews, 2009, 13(3): 594-604.
[9]	HERNÁNDEZ J J, BALLESTEROS R, ARANDA G. Characterisation of tars from biomass gasification: effect of the operating conditions[J]. Energy, 2013, 50: 333-342.
[10]	BLANCO P H, WU C, ONWUDILI J A, et al. Characterization of tar from the pyrolysis/gasification of refuse derived fuel: influence of process parameters and catalysis[J]. Energy & Fuels, 2012, 26(4): 2107-2115.
[11]	秦育红. 生物质气化过程中焦油形成的热化学模型[D]. 太原: 太原理工大学, 2009. QIN Y H. Thermochemical model of tar formation during biomass gasification[D]. Taiyuan: Taiyuan University of Technology, 2009.
[12]	YU H M, ZHANG Z, LI Z, et al. Characteristics of tar formation during cellulose, hemicellulose and lignin gasification[J]. Fuel, 2014, 118: 250-256.
[13]	SHI D, LI P, ZHANG C, et al. Levels and patterns of polychlorinated biphenyls in residues from incineration of established source-classified MSW in China[J]. Toxicological & Environmental Chemistry, 2015, 97(10): 1337-1349.
[14]	CHI Y, DONG J, TANG Y J, et al. Life cycle assessment of municipal solid waste source-separated collection and integrated waste management systems in Hangzhou, China[J]. Journal of Material Cycles & Waste Management, 2015, 17(4): 695-706.
[15]	杜吴鹏, 高庆先, 张恩琛, 等. 中国城市生活垃圾排放现状及成分分析[J]. 环境科学研究, 2006, 19(5): 85-90. DU W P, GAO Q X, ZHANG E C, et al. The emission status and composition analysis of municipal solid waste in China[J]. Research of Environmental Sciences, 2006, 19(5): 85-90.
[16]	刘海力. 厨余垃圾的燃烧与热解特性研究[D]. 广州: 华南理工大学, 2014. LIU H L. Study on combustion and pyrolysis characteristics of food waste[D]. Guangzhou: South China University of Technology, 2014.
[17]	李权柄, 汪华林, 张振华, 等. 两段式热解厨余垃圾实验研究[J]. 环境工程学报, 2009, 3(1): 175-178. LI Q B, WANG H L, ZHANG Z H, et al. Research on two-segment pyrolysis of food residue[J]. Chinese Journal of Environmental Engineering, 2009, 3(1): 175-178.
[18]	韩斌. 聚氯乙烯等塑料废弃物热解特性及动力学研究[D]. 天津: 天津大学, 2012. HAN B. Study on pyrolysis characteristics and kinetics of poly(vinyl chloride) and other plastics wastes[D]. Tianjin: Tianjin University, 2012.
[19]	刘义彬, 马晓波, 陈德珍, 等. 废塑料典型组分共热解特性及动力学分析[J]. 中国电机工程学报, 2010, (23): 56-61. LIU Y B, MA X B, CHEN D Z, et al. Copyrolysis characteristics and kinetic analysis of typical constituents of plastic wastes[J]. Proceedings of the CSEE, 2010, (23): 56-61.
[20]	ZHOU H, WU C, ONWUDILI J A, et al. Effect of interactions of PVC and biomass components on the formation of polycyclic aromatic hydrocarbons (PAH) during fast co-pyrolysis[J]. Rsc Advances, 2015, 5(15): 11371-11377.
[21]	MA S, LU J, GAO J. Study on the pyrolysis dechlorination of PVC waste[J]. Energy Sources, 2004, 26(4): 387-396.
[22]	ARACIL I, FONT R, CONESA J A. Semivolatile and volatile compounds from the pyrolysis and combustion of polyvinyl chloride[J]. Journal of Analytical & Applied Pyrolysis, 2005, 74(1): 465-478.
[23]	AL-HARAHSHEH M, KINGMAN S, AL-MAKHADMAH L, et al. Microwave treatment of electric arc furnace dust with PVC: dielectric characterization and pyrolysis-leaching[J]. Journal of Hazardous Materials, 2014, 274(12): 87-97.
[24]	MATSUZAWA Y, AYABE M, NISHINO J. Acceleration of cellulose co-pyrolysis with polymer[J]. Polymer Degradation & Stability, 2001, 71(3): 435-444.
[25]	HUANG Q X, TANG Y J, LU S Y, et al. Characterization of tar derived from principle components of municipal solid waste[J]. Energy & Fuels, 2015, 29(11): 7266-7274.
[26]	MILNE T A, EVANS R J, ABATZOGLOU N. Biomass gasifier “tars”: their nature, formation, destruction, and tolerance limits in energy conversion devices[C]//Proceedings of the 3rd Biomass Conference of the Americas: Making a Business from Biomass in Energy, Environment, Chemical, Fibers and Materials. Canada, 1997: 729-738.
[27]	LIU C, XIE H, WANG Z, et al. Composition determination of binary polymer mixtures by size exclusion chromatography with light scattering detection [J]. Chinese Journal of Polymer Science, 2010, 28(3): 291-297.
[28]	汪大受.凝胶色谱法[J].微生物学通报, 1978, 3: 33-43. WANG D S. Gel chromatography[J]. Microbiology, 1978, 3: 33-43.
[29]	KANDOLA B K, HORROCKS A R, COLEMAN D P G V. Flame-retardant treatments of cellulose and their influence on the mechanism of cellulose pyrolysis[J]. Journal of Macromolecular Science Part C: Polymer Reviews, 1996, 36(4): 721-794.
[30]	徐兴敏. 生物质热解油催化加氢脱氧提质研究[D]. 郑州: 郑州大学, 2014. XU X M. Upgrading of biomass pyrolysis oil via catalytic hydrodeoxygenation[D]. Zhengzhou: Zhengzhou University, 2005.
[31]	SAROWHA S L S. Determination of molecular weights of petroleum products using gel permeation chromatography[J]. Petroleum Science & Technology, 2005, 23(5/6): 573-578.