Pyrolysis of mixtures of palm shell and polystyrene: An optional method to produce a highgrade of pyrolysis oil (original) (raw)
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Catalytic Upgrading of Pyrolytic Oil via In-situ Hydrodeoxygenation
Waste and Biomass Valorization, 2019
Lignocellulosic biomass derived from non-food crops cultivated on lands that are increasingly marginal for more favoured major crops is a potential source of sustainable renewable energy. This study explores the transformation of crude organic phase pyrolytic oil derived from Napier grass biomass into high-grade biofuel precursors via hydrodeoxygenation reaction over platinum and palladium catalysts with in-situ hydrogen generation from methanol. The reaction was conducted in a high-pressure stainless steel batch reactor at 350 °C, 20 wt% methanol ratio, 2 wt% catalyst loading and 60 min reaction time. The result of physicochemical analysis showed that the higher heating value of the organic liquid products collected over the catalysts increased by 35-40% relative to the raw sample. Gas chromatography-mass spectrometry results revealed significant reductions in the oxygenated compounds such as methoxyaromatics, methoxyphenols, acids, aldehydes. The degree of deoxygenation and overall extent of upgrading observed was 50-54% and 56-60%, respectively. The gas products collected were mainly carbon monoxide, carbon dioxide, hydrogen and methane. Hydrodeoxygenation, hydrogenolysis, hydrogenation, dehydration, demethylation, hydrocracking, decarbonylation and decarboxylation were the main upgrading reactions, and a multiple reaction network was proposed.
Catalytic hydrothermal upgrading of pyrolysis oil
2016
Pyrolysis oil from wood pellets was upgraded in this research by catalytic hydrotreatment in a 100 ml batch reactor. Four heterogeneous 5% metal catalysts (Ru, Ni, Rh, and Ni) were used at different hydrotreatment temperatures (250 oC and 300 oC). Two different set-ups were also used with formic acid and with only bio-oil. The products of the reforming using two temperature conditions were then analysed and compared. The results showed that higher temperature yielded a lot of char compared to lower temperature giving low bio-oil recovery and poor carbon yield in the bio-oil. Also higher temperature resulted into the production of more carbon dioxide gas and hydrocarbon gases. Ru catalyst appeared to be the best among all the catalysts in reducing the amount oxygen wt-% by 42.12% at 250 oC. Ru treated bio-oil also registered the highest composition of the lightest compounds of about 88.5% compared to initial bio-oil which only had 30.6%. Elemental analyses results show that all the u...
Recovery of liquid fuel from the aqueous phase of pyrolysis oil by using catalytic conversion
Energy & Fuels, 2014
Oil from the pyrolysis of biomass typically consists of two different layers defined as the aqueous and organic phases. The objective of this study was to determine the yield of liquid fuel that can be produced from the aqueous phase using a catalytic conversion. The process was supported by two different HZSM-5 catalysts with temperatures set at 405, 455, 505, and 555°C. The oils obtained were then analyzed using Karl Fischer titration, FTIR spectroscopy, GC/MS, TGA, and CHNS/O analysis. The results showed that the oil yields obtained from catalytic cracking of the aqueous phase ranged from 4 to 9.16 wt % depending on the catalyst type and temperature. The optimum performance of deoxygenation activity was obtained with the HZSM-5/50 catalyst at a temperature of 555°C. The oil produced under the optimum conditions was dominated by aromatics and phenols and had an HHV of 38.44 MJ/kg.
Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5
Fuel Processing Technology, 2017
While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Catalytic cracking is one such alternative industrial practice that is carried out at near-atmospheric pressure using zeolite-based FCC catalysts. The present study focuses on the catalytic cracking of pyrolysis oil of different starting compositions over HZSM-5 to inform the extent of upgrading in the liquid phase. After establishing a catalyst bed temperature of 500 ⁰C as optimum operating condition with regard to deoxygenation and yield of mono-aromatics in the products obtained the performance of the use of conventional pyrolysis and TGRP bio-oils as starting liquids for the cracking were compared. The results indicate that the formation of naphthalenes was favored, while the formation of BTEX compounds was slightly depressed in the case of the TGRP oil. We attribute this finding to the formation of naphthalenes from BTEX molecules already found in the TGRP oil. Subsequent reuse of the catalysts showed that the cracking of TGRP bio-oil exhibited slightly greater deactivation after a third cycle, likely due to the increased formation of naphthalenes and coke which block HZSM-5 pores. The results obtained from this study will help determine the issues that need to be addressed when developing a catalytic cracker with HZSM-5 for regular pyrolysis oil and TGRP oil.
Second-generation biofuels by co-processing catalytic pyrolysis oil in FCC units
Applied Catalysis B-environmental, 2014
Previous research showed that hydrodeoxygenated (HDO) pyrolysis-oils could successfully be coprocessed with vacuum gasoil (VGO) in a labscale fluid catalytic cracking (FCC) unit to bio-fuels. Typically the hydrodeoxygenation step takes place at ∼300 • C under 200-300 bar of hydrogen. Eliminating or replacing this step by a less energy demanding upgrading step would largely benefit the FCC co-processing of pyrolysis oils to bio-fuels. In this paper a bio-oil that has been produced by catalytic pyrolysis (catalytic pyrolysis oil or CPO) is used directly, without further upgrading, in catalytic cracking co-processing mode with VGO. The results are compared to the co-processing of upgraded (via HDO) thermal pyrolysis oil. Though small but significant differences in the product distribution and quality have been observed between the co-processing of either HDO or CPO, they could be corrected by further catalyst development (pyrolysis and/or FCC), which would eliminate the need for an upstream hydrodeoxygenation step. Moreover, the organic yield of the catalytic pyrolysis route is estimated at approximately 30 wt.% compared to an overall yield for the thermal pyrolysis followed by a hydrodeoxygenation step of 24 wt.%.
Pyrolysis Bio-Oil Upgrading to Renewable Fuels
2014
This study aims to upgrade woody biomass pyrolysis bio-oil into transportation fuels by catalytic hydrodeoxygenation (HDO) using nanospring (NS) supported catalyst via the following research objectives: (1) develop nanospring-based catalysts (nanocatalyst) and (2) evaluate the nanocatalysts for the hydrogenation of pyrolysis bio-oil into liquid fuels. The authors developed protocols for HDO treatment of bio-oil and model compounds and product evaluation using commercial nickel (Ni) and ruthenium (Ru) based catalysts initially. The authors successfully synthesized Ni decorated NS catalysts (Ni-NS), in small amounts (mg level) and characterized the catalysts. It was shown that the Ni-NS catalyst had to be reduced (activated) before use. The Ni based catalysts were able to hydrodeoxygenate the model compounds and bio-oil and conversion was Ni content and temperature dependent. Low conversions using the Ni-NS catalysts were obtained, but only very small amounts of catalyst were used. Fu...
Upgrading of Pyrolysis Oils Review.docx
A review on upgrading of pyrolysis oil from biomass was presented. Effects of greenhouse gas emissions on the environment and the role of biomass in reducing greenhouse gas emissions were discussed. Biomass processing through to production of bio-oils through fast pyrolysis was reviewed and the significance of pyrolysis oil upgrading pointed out. The physical and chemical properties of pyrolysis oils from various feedstocks (pine, birch, poplar) were discussed. Key process parameters and the importance of the mechanism of oxygen removal (deoxygenation) were also discussed. The importance of oxygen in the bio-oil and the various methods for upgrading pyrolysis oils including zeolite cracking to hydro-deoxygenation were reviewed. A review was also carried out on modern developments in bio-oil upgrading such as the BIOCOUP Project- Co-processing of upgraded bio-oils with fossil fuels in standard refinery units. It was noted that modern approaches such as hydrodeoxygenation showed promising results for cofeeding/co-processing with fossil fuels in a petroleum refinery.
Fuel Processing Technology, 2014
In this paper, we sought to elucidate the relationships between biomass feedstock type and the suitability of their fast-pyrolysis bio-oils for hydrodeoxygenation (HDO) upgrading. Switchgrass, Eucalyptus benthamii, and equine manure feedstocks were pyrolyzed into bio-oil using a continuous fast-pyrolysis system. We also synthesized variations of switchgrass bio-oil using catalytic pyrolysis methods (HZSM-5 catalyst or tail-gas recycle method). Bio-oil samples underwent batch HDO reactions at 320°C under~2100 psi H 2 atmosphere for 4 h, using Pt, Ru, or Pd on carbon supports. Hydrogen consumption was measured and correlated with compositional trends. The resulting organic, aqueous, and gas phases were analyzed for their chemical compositions. Mass balances indicate little coke formation. Switchgrass bio-oil over Pt/C performed the best in terms of hydrogen consumption efficiency, deoxygenation efficiency, and types of upgraded bio-oil compounds. Eucalyptus feedstocks consistently consumed more than twice the normal amount of hydrogen gas per run, primarily due to the elevated syringol content. Catalytically pyrolyzed bio-oils deoxygenated poorly over Pt/C but hydrogenated more extensively than other oils. Although the relative deoxygenation (%DO rel ) varied based on feedstock and catalyst, the absolute deoxygenation (%DO abs ) depended only on the overall yield. The total extent of upgrading (hydrogenation + deoxygenation) remained independent of feedstock and catalyst.
Renewable chemical commodity feedstocks from integrated catalytic processing of pyrolysis oils
2010
Abstract Fast pyrolysis of lignocellulosic biomass produces a renewable liquid fuel called pyrolysis oil that is the cheapest liquid fuel produced from biomass today. Here we show that pyrolysis oils can be converted into industrial commodity chemical feedstocks using an integrated catalytic approach that combines hydroprocessing with zeolite catalysis. The hydroprocessing increases the intrinsic hydrogen content of the pyrolysis oil, producing polyols and alcohols.