Product Chemistry and Process Efficiency of Biomass Torrefaction, Pyrolysis and Gasification Studied by High-Throughput Techniques and Multivariate Analysis.

摘要

Despite the great passion and endless efforts on development of renewable energy from biomass, the commercialization and scale up of biofuel production is still under pressure and facing challenges. New ideas and facilities are being tested around the world targeting at reducing cost and improving product value. Cutting edge technologies involving analytical chemistry, statistics analysis, industrial engineering, computer simulation, and mathematics modeling, etc. keep integrating modern elements into this classic research. One of those challenges of commercializing biofuel production is the complexity from chemical composition of biomass feedstock and the products. Because of this, feedstock selection and process optimization cannot be conducted efficiently.;This dissertation attempts to further evaluate biomass thermal decomposition process using both traditional methods and advanced technique (Pyrolysis Molecular Beam Mass Spectrometry). Focus has been made on data base generation of thermal decomposition products from biomass at different temperatures, finding out the relationship between traditional methods and advanced techniques, evaluating process efficiency and optimizing reaction conditions, comparison of typically utilized biomass feedstock and new search on innovative species for economical viable feedstock preparation concepts, etc.;Lab scale quartz tube reactors and 80il stainless steel sample cups coupled with auto-sampling system were utilized to simulate the complicated reactions happened in real fluidized or entrained flow reactors. Two main high throughput analytical techniques used are Near Infrared Spectroscopy (NIR) and Pyrolysis Molecular Beam Mass Spectrometry (Py-MBMS). Mass balance, carbon balance, and product distribution are presented in detail. Variations of thermal decomposition temperature range from 200°C to 950°C. Feedstocks used in the study involve typical hardwood and softwood (red oak, white oak, yellow poplar, loblolly pine), fast growing energy crops (switchgrass), and popular forage crop (alfalfa), as well as biochar derived from those materials and their mixtures.;It demonstrated that Py-MBMS coupled with MVA could be used as fast analytical tools for the study of not only biomass composition but also its thermal decomposition behaviors. It found that the impact of biomass composition heavily depends on the thermal decomposition temperature because at different temperature, the composition of biomass decomposed and the impact of minerals on the decomposition reaction varies. At low temperature (200-500°C), organic compounds attribute to the majority of variation in thermal decomposition products. At higher temperature, inorganics dramatically changed the pyrolysis pathway of carbohydrates and possibly lignin. In gasification, gasification tar formation is also observed to be impacted by ash content in vapor and char. In real reactor, biochar structure also has interactions with other fractions to make the final pyrolysis and gasification product. Based on the evaluation of process efficiencies during torrefaction, temperature ranging from 275°C to 300°C with short residence time (<10min) are proposed to be optimal torrefaction conditions. 500°C is preferred to 700°C as primary pyrolysis temperature in two stage gasification because higher primary pyrolysis temperature resulted in more tar and less gasification char. Also, in terms of carbon yield, more carbon is lost in tar while less carbon is retained in gas product using 700°C as primary pyrolysis temperature. In addition, pyrolysis char is found to produce less tar and more gas during steam gasification compared with gasification of pyrolysis vapor. Thus it is suggested that torrefaction might be an efficient pretreatment for biomass gasification because it can largely improve the yield of pyrolysis char during the primary pyrolysis step of gasification thus reduce the total tar of the overall gasification products. Future work is suggested in the end.