Analysis of trace contaminants in hot gas streams using time-weighted average solid-phase microextraction: Proof of concept

Time-weighted average (TWA) passive sampling using solid-phase microextraction (SPME) and gas chromatography was investigated as a new method of collecting, identifying and quantifying contaminants in process gas streams. Unlike previous TWA-SPME techniques using the retracted fiber configuration (fiber within needle) to monitor ambient conditions or relatively stagnant gases, this method was developed for fast-moving process gas streams at temperatures approaching 300°C. The goal was to develop a consistent and reliable method of analyzing low concentrations of contaminants in hot gas streams without performing time-consuming exhaustive extraction with a slipstream. This work in particular aims to quantify trace tar compounds found in a syngas stream generated from biomass gasification. This paper evaluates the concept of retracted SPME at high temperatures by testing the three essential requirements for TWA passive sampling: (1) zero-sink assumption, (2) consistent and reliable response by the sampling device to changing concentrations, and (3) equal concentrations in the bulk gas stream relative to the face of the fiber syringe opening. Results indicated the method can accurately predict gas stream concentrations at elevated temperatures. Evidence was also discovered to validate the existence of a second boundary layer within the fiber during the adsorption/absorption process. This limits the technique to operating within reasonable mass loadings and loading rates, established by appropriate sampling depths and times for concentrations of interest. A limit of quantification for the benzene model tar system was estimated at 0.02gm⁻³ (8ppm) with a limit of detection of 0.5mgm⁻³ (200ppb). Using the appropriate conditions, the technique was applied to a pilot-scale fluidized-bed gasifier to verify its feasibility. Results from this test were in good agreement with literature and prior pilot plant operation, indicating the new method can measure low concentrations of tar in gasification streams.