School of Environmental Science and Engineering, Shandong Key Laboratory of Water Pollution Control and Resource Reuse, Shandong University, Jinan, 266237, China; Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP(3)), Shanghai, 200433, China; School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250100, China.
School of Municipal and Environmental Engineering, Shandong Jianzhu University, Jinan, 250100, China.
J Environ Sci (China). 2020 May;91:54-61. doi: 10.1016/j.jes.2020.01.005. Epub 2020 Jan 25.
Landfill biogas is a potential alternative for fossil fuel, but the containing impurities, volatile methyl siloxanes (simplified as siloxanes), often cause serious problems in gas turbines when applied to generate electricity. In this research, a collecting and analyzing method based on solvent adsorption and purge and trap-gas chromatography-mass spectrometry was established to determine the siloxanes in biogas from a landfill in Jinan, China, and adjacent ambient samples, such as soil, air, and leachate of the landfill. The results showed that, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) accounted for 63% of total siloxanes; and without considering D4 and D5, the order of detected siloxanes in concentration was found relating to Gibbs free energies of molecules, namely that higher abundant siloxane (except for D4 and D5) usually had lower Gibbs free energy. Additionally, the mass ratio between D4 and octamethyltrisiloxane (L3) in the biogas varied with different garbage age in landfills, possibly revealing the breaking-down of larger siloxane molecules with time. The samples, which were collected from environmental samples adjacent to the landfill, such as soil, water, and air, presented much higher siloxane level than urban or rural area away from landfills. The current HS scrubber of the landfill biogas could decrease the total siloxanes from 10.7 to 5.75 mg/m due to FeO and a refrigerant drier in a purification system and cyclic siloxanes were more easily removed than linear ones.
垃圾填埋沼气是化石燃料的潜在替代品,但其中含有的杂质——挥发性甲基硅氧烷(简称硅氧烷),在用于发电时经常会给燃气轮机带来严重问题。在这项研究中,建立了一种基于溶剂吸附和吹扫捕集-气相色谱-质谱联用的收集和分析方法,以测定来自中国济南垃圾填埋场及周边环境样品(如土壤、空气和渗滤液)中的沼气中的硅氧烷。结果表明,八甲基环四硅氧烷(D4)和十甲基环五硅氧烷(D5)占总硅氧烷的 63%;不考虑 D4 和 D5 时,检测到的硅氧烷按浓度顺序排列与分子吉布斯自由能有关,即丰度较高的硅氧烷(除 D4 和 D5 外)通常具有较低的吉布斯自由能。此外,沼气中 D4 和八甲基三硅氧烷(L3)的质量比随垃圾填埋场中垃圾年龄的不同而变化,这可能反映了较大硅氧烷分子随时间的分解。从垃圾填埋场附近的环境样品(如土壤、水和空气)中采集的样品,其硅氧烷含量远高于远离垃圾填埋场的城市或农村地区。由于净化系统中的 FeO 和制冷剂干燥器,当前垃圾填埋沼气的 HS 洗涤器可将总硅氧烷从 10.7 降至 5.75mg/m,且环状硅氧烷比线性硅氧烷更容易去除。