Determination of silicon in biomass and products of pyrolysis process via high-resolution continuum source atomic absorption spectrometry

Abstract

Thermochemical processes can convert the biomass into fuels, such as bio-oil. The biomass submitted to pyrolysis process, such as fibers, are generally rich in silicon, an element that can lead to damages in an engine when there is high concentration in a fuel. High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) is an interesting alternative for Si determination in the products and byproducts of the pyrolysis process because, besides the flame (F) and graphite furnace (GF) atomizers, it has enhanced the application of direct analysis of solid samples (SS) within GF. This study aimed the development of methods to determine Si in biomass samples, their products and byproducts using HR-CS AAS. A high-resolution continuum source atomic absorption spectrometer contrAA 700 equipped with F and GF atomizers was used throughout the study. HR-CS F AAS (λ = 251.611nm, 1 detection pixel, N2O/C2H2 flame) was used to evaluate Si content in biomass and ash, after a microwave-assisted acid digestion with HNO3 and HF. HR-CS GF AAS (Tpyr = 1400°C, Tatom = 2650°C) has evaluated Si in pyrolysis water and bio-oil at 251.611nm, and in peach pit biomass and ash at 221.174nm using SS, both wavelengths with 1 detection pixel. Rhodium (300μg) was applied as permanent modifier and 10μgPd + 6μg Mg were pipetted onto the standards/samples at each analysis. Three different biomass samples were studied: palm tree fiber, coconut fiber and peach pit, and three certified reference materials (CRM) were used to verify the accuracy of the methods. The figures of merit were LOD 0.09–20mgkg–1, and LOQ 0.3–20mgkg–1, considering all the methods. There were no significant differences between the CRM certified values and the determined ones, using a Student t-test with a confidence interval of 95% (n = 5). Si concentration ranged from 0.11–0.92% mm–1, 1.1–1.7mgkg–1, 3.3–13mgkg–1, and 0.41–1.4%mm–1, in biomass, bio-oil, pyrolysis water and ash, respectively. Si remained mostly in the ash, leading to a mass fraction of up to 103%, even when the Si loss is not considered. Silicon concentration in bio-oil was below 1.7mgkg–1, which is suitable for its application as a fuel. The developed methods using HR-CS AAS are suitable for Si determination in biomass, bio-oil, pyrolysis water, and ash. The application of bio-oil as an alternative fuel would be possible evaluating its Si content due to its low levels. The mass balance for Si has proved to be an important tool in order to evaluate the correct disposal of pyrolysis process byproducts.