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Pyrolysis of Biodegradable Waste for Negative Carbon Emissions

Time: Fri 2021-12-17 10.00

Location: Sefström, Brinellvägen 23, Stockholm

Video link: https://kth-se.zoom.us/j/65800329663

Language: English

Subject area: Materials Science and Engineering Chemical Engineering Energy Technology

Doctoral student: Shule Wang , Materialvetenskap

Opponent: Dr Chunfei Wu, Queen's University Belfast

Supervisor: Docent Weihong Yang, Processer; Professor Pär Jönsson, Processer

Abstract

Bioenergy with Carbon Capture and Storage represents a crucial technology that enables an energy production with negative carbon emissions, which is needed to achieve global climate goals. Appropriated management of biodegradable waste, including biodegradable lignocellulosic waste, sewage sludge, organic fraction of municipal solid waste, can make this contribution. The implementation of pyrolysis process is able to produce biochar, liquid and gas product from biodegradable waste. Based on the pyrolysis technology, a sustainable management of biodegradable waste for negative carbon emission is proposed in this work. The proposed novel process combines an anaerobic digestion, pyrolysis of the digestate following by catalytic reforming the pyrolytic vapor, then methanation of the reforming gas, separating the stream of CH4 and CO2.  The storage of separated CO2 streams and biochar can be considered as negative emissions. Furthermore, the pyrolysis behaviors of the solid residue, which was produced from hydrothermal carbonization pretreatment of biodegradable wastes, are investigated.  The pyrolytic liquid was further upgraded to a higher quality product with a less oxygen content, a higher calorific value by using ex-situ and in-situ hydrogen donors. Carbon stability of the pyrolytic biochar, which is one of key parameters to assess the biochar as carbon sink, was evaluated by using the accelerated oxidation method. Finally, energy and mass balance on the proposed process was obtained.  

The pyrolysis behavior of hydrothermal carbonization-treated sewage sludge digestate, and paper sludges were investigated. Thermogravimetric analysis, Py- Gas chromatography–Mass spectrometry and bench-scale experiments were employed to fulfil this objective. The thermal degradation behavior of these two feedstocks was investigated. Initially, the compounds in the pyrolytic vapor were identified. Thereafter, the pyrolytic product from the bench-scale experiment was characterized. It was found that the pyrolysis reaction of both feedstocks was a two-stage reaction. The organic fraction with a higher heating value around 28.47 to 38.46 MJ/kg was produced from the pyrolysis of hydrothermal carbonization-treated biodegradable waste. More organic fraction can be produced from the pyrolysis of the paper sludge than that from sewage sludge digestate. It was also found that the fixed carbon content in raw materials is difficult to be determined by using the standard method due to the ash oxidation behavior in such materials. Therefore, a method to determine the sample's fixed carbon content without affected by the ash oxidation behavior was developed.

Introducing hydrogen donors to upgrade the pyrolytic liquid products for a higher quality product with a lower oxygen content and a higher calorific value is investigated. The H2 was used as an ex-situ hydrogen donor in the lignocellulosic waste pyrolysis in both non-catalytic and catalytic cases. The catalyst used in this study was a commercial HZSM-5, catalyst with a strong selectivity of aromatics. The hydrogen consumption during pyrolysis in the H2 atmosphere was indicated by experiments. The gas and liquid production were promoted while the biochar yield was suppressed in the presence of the H2 atmosphere. However, the presence of an H2 atmosphere was found to increase the acidity of the HZSM-5 and enhance the production of polyaromatics during the pyrolysis process. Further, the study using the sewage sludge digestate as an in-situ hydrogen donor to pyrolysis of lignocellulosic biomass obtained from the salix family was investigated. The sewage sludge digestate was premixed with salix in five blended ratios and pyrolyzed in a bench-scale reactor. The composite of 75% sludge digestate and 25% salix presented the highest mass and energy yields of the organic fraction in the liquid product. The yield of biochar was suppressed in this copyrolysis. The synergistic effect between the sludge digestate and salix was studied with respect to reaction mechanisms, carbon number distribution of the compounds in organic fraction, and biochar stability. The competition reaction between the short-chain carboxylic acid from salix pyrolysis and a long-chain carboxylic acid from digestate pyrolysis was one of the main reasons for the synergistic reaction regarding the composition of the organic fraction. This competition reaction results in a higher amount of long-chain carboxylic acid esters and N-heterocyclic compounds, a lower amount of the long-chain nitriles in the organic fraction produced from copyrolysis compared to it from individual pyrolysis.

The stabilities of the biochar products from the copyrolysis of sewage sludge digestate and salix, were determined by using the accelerated oxidation method. It was found that the biochar stabilities are promoted by this copyrolysis. The nitrogen yield in the biochar product was also enhanced by the copyrolysis process. 

The proposed CO2 negative process was modelled using the process simulation software, and the modelling results were validated by using an experimental data. The pyrolysis temperature and dewatering technology were used for sensitivity analysis. In this process, methane was chosen as the final product. Pyrolytic biochar and compressed CO2 was captured and stored as the negative carbon emission. It was found that for 1000 kg of dry matter digestate, one can obtain 151.4 kg CH4 in a purity of 96 vol%, 304.5kg compressed CO2, and 80.8 kg biochar. The latter two are equal to 355.64 kg negative CO2 emission.

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