Stable polycyclic aromatic carbon (SPAC) content as an improved parameter for determining biochar stability

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Impact of solvent type and condition on biomass liquefaction to produce heavy oils in high yield with low oxygen contents

Bio-oils produced by processes such as slow or fast pyrolysis typically contain high water and oxygen contents, which make them incompatible with conventional fuels. It is therefore necessary to upgrade the bio-oils to reduce their oxygen and water contents. The bio-oil upgrading process can consume up to 84 wt% of the initial bio-oil it is therefore important to develop other alternative approaches to generate high quality bio-oil. Thermolytic liquid solvent extraction (LSE) has been considered as a potential viable process due to the high liquid yield, better product quality and water free nature of the final products. In this study, a novel LSE process of biomass liquefaction has been studied under various conditions of solvent type, temperature, and biomass species. Compared to currently available commercial pyrolysis approaches, this process using tetralin as a solvent is shown to be capable of generating high quality bio-oil with low oxygen contents (ca. 5.9%) at extremely high overall conversions of up to 87 and 92 (%) dry and ash free basis (DAF) from Scotch pine and miscanthus, respectively. Overall, the study has demonstrated the advantages of LSE for bio-oil generation from biomass, in terms of producing high conversions to liquid products that are compatible with existing petroleum heavy feedstocks

High pressure water pyrolysis of coal to evaluate the role of pressure on hydrocarbon generation and source rock maturation at high maturities under geological conditions

This study investigates the effect of water pressure on hydrocarbon generation and source rock maturation at high maturities for a perhydrous Tertiary Arctic coal, Svalbard. Using a 25 ml Hastalloy vessel, the coal was pyrolysed under low water pressure (230–300 bar) and high water pressure (500, 700 and 900 bar) conditions between 380 °C and 420 °C for 24 h. At 380 °C and 420 °C, gas yields were not affected by pressure up to 700 bar, but were reduced slightly at 900 bar. At 380 °C, the expelled oil yield was highest at 230 bar, but reduced significantly at 900 bar. At 420 °C cracking of expelled oil to gas was retarded at 700 and 900 bar. As well as direct cracking of the coal, the main source of gas generation at high pressure at both 380 °C and 420 °C is from bitumen trapped in the coal, indicating that this is a key mechanism in high pressure geological basins. Vitrinite reflectance (VR) was reduced by 0.16 %Ro at 380 °C and by 0.27 %Ro at 420 °C at 900 bar compared to the low pressure runs, indicating that source rock maturation will be more retarded at higher maturities in high pressure geological basins

Should IQOS Emissions Be Considered as Smoke and Harmful to Health? A Review of the Chemical Evidence

The chemical evidence that IQOS emissions fit the definition of both an aerosol and smoke, and that IQOS and potentially other heated tobacco products (HTPs) pose some harmful health threats from the range of compounds released even at somewhat lower concentrations is reviewed. Further, we address the yields of harmful and potentially harmful compounds (HPHCs), including polycyclic aromatic hydrocarbons (PAHs), and the constituents of IQOS emission that are diagnostic of pyrolysis to provide information on the temperatures reached in IQOS tobacco sticks. The HPHCs present in IQOS emissions are the same as in conventional cigarette smoke (CCs), analogous to emissions from earlier generation of HTPs classed as smoke. However, Philip Morris International (PMI) studies have to some degree underestimated IQOS aerosol HPHC yields, which are a factor of between 3.2 and 3.6 higher when expressed on a tobacco rather than an IQOS stick basis compared to the reference 3R4F cigarette. Further, IQOS emissions contain carbon particles, which fit definition of both aerosol and smoke. Continual reheating of deposited tar in the IQOS device will occur with real-life use, likely leading to generation of even higher concentrations of HPHCs and particulate matter. Despite IQOS not exceeding 350 °C, local hot spots could exist, causing formation of species (phenol/cresols, PAHs). It is recommended that the impact of repeated use to determine the levels of black carbon (insoluble organic matter) in the particulate matter, and the extent to which compounds in IQOS emissions are formed by pyrolysis need to be assessed rigorously. To address whether uneven temperature profiles in heat sticks can lead to potential hot spots that could, for example, lead to PAH formation, it is recommended that pyrolysis studies on tobacco and other constituents of HTPs are required in conjunction with more effort on heating tobacco blends under controlled temperature/time conditions

Study of pyrolysis for biochar production from biomass feedstocks using a simplified Aspen Plus model

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Investigation of the fluid behavior of asphaltenes and toluene insolubles by high-temperature proton nuclear magnetic resonance and rheometry and their application to visbreaking

The fluid behavior of asphaltenes at elevated temperatures impacts coke formation in a number of hydrocarbon conversion processes, including visbreaking and delayed coking. In this study, the asphaltenes from a number of sources, namely, a vacuum residue, a petroleum source rock (Kimmeridge clay) bitumen obtained by hydrous pyrolysis, and bitumen products from a sub-bituminous coal and pine wood obtained by thermolytic solvent extraction using tetralin, have been characterized using high-temperature proton nuclear magnetic resonance (1H NMR), and the results correlated with those from small-amplitude oscillatory shear rheometry. Further for comparison, the coke (toluene insolubles) obtained from visbreaking the vacuum residue was also characterized. All of the asphaltenes became completely fluid by 300 °C, with hydrogen being completely mobile with coke formation, identified as a solid phase, not occurring to a significant extent until 450 °C. Extremely good agreement was obtained between high-temperature 1H NMR and rheometry results, which confirmed that the asphaltenes were highly fluid from 300 °C, with initial signs of resolidification being observed at temperatures of around 450 °C. During softening, extremely good correlations between fluid hydrogen and phase angle were obtained as the asphaltenes softened. The toluene insolubles however did contain some fluid material; thus, it cannot be regarded as strictly solid coke, but clearly, with increasing temperature, the fluid material did convert to coke. Under actual process conditions, this fluid material could be responsible for coke adhering to reactor surfaces

Retardation of oil cracking to gas and pressure induced combination reactions to account for viscous oil in deep petroleum basins: evidence from oil and n-hexadecane pyrolysis at water pressures up to 900bar

This study reports a laboratory pyrolysis experimental study on oil and n-hexadecane to rationalise the thermal stability of oil in deep petroleum reservoirs. Using a 25 ml Hastelloy pressure vessel, a 35° API North Sea oil (Oseberg) and n-hexadecane (n-C16), were pyrolysed separately under non-hydrous (20 bar), low pressure hydrous (175 bar) and high liquid water pressure (500 and 900 bar) at 350°C for 24 h. This study reports a laboratory pyrolysis experimental study on oil and n-hexadecane to rationalise the thermal stability of oil in deep petroleum reservoirs. Using a 25 ml Hastelloy pressure vessel, a 35° API North Sea oil (Oseberg) and n-hexadecane (n-C16), were pyrolysed separately under non-hydrous (20 bar), low pressure hydrous (175 bar) and high liquid water pressure (500 and 900 bar) at 350 °C for 24 h. This study shows that the initial cracking of oil and n-hexadecane to hydrocarbon gases was retarded in the presence of water (175 bar hydrous conditions) compared to low pressures in the absence of water (non-hydrous conditions). At 900 bar water pressure, the retardation of oil and n-hexadecane cracking was more significant compared to 175 bar hydrous and 500 bar water pressure conditions. Combination reactions have been observed for the first time in pressurised water experiments during the initial stages of cracking, resulting in the increased abundance of heavier n-alkane hydrocarbons (> C20), the amount of unresolved complex material (UCM), as well as the asphaltene content of the oil. These reactions, favoured by increasing water pressure provide a new mechanism for rationalising the thermal stability of oils, and for producing heavy oils at temperatures above which biodegradation can occur. Indeed, we demonstrate that bitumen from the high pressure Gulf of Mexico basin has been formed from lighter oil components and it possesses similar characteristics to the laboratory oils generated

Thermal cracking of oil under water pressure up to 900 bar at high thermal maturities. 1. gas compositions and carbon isotopes

In this study, a C9+ fraction of saturate-rich Tertiary source rock-derived oil from the South China Sea basin was pyrolyzed in normal and supercritical water using a 25 mL vessel at a range of temperature from 350 to 425 °C for 24 h, to probe pressure effects up to 900 bar on gas yields and their stable carbon isotopic compositions during thermal cracking. Pressure generally retards oil cracking, as evidenced by reduced gas yields, but the trends depend upon the level of thermal evolution. In the early stages of cracking (350 and 373 °C, equivalent vitrinite reflectance of 1.3% R0), pressure still has a strong suppression effect from 200 to 470 bar, which then levels off or is reversed as the pressure is increased further to 750 and 900 bar. Interestingly, the stable carbon isotopic composition of the generated methane becomes enriched in 13C as the pressure increases from 200 to 900 bar. A maximum fractionation effect of ∼3‰ is observed over this pressure range. Due to pressure retardation, the isotopically heaviest methane signature does not coincide with the maximum gas yield, contrary to what might be expected. In contrast, pressure has little effect on ethane, propane, and butane carbon isotope ratios, which show a maximum variation of ∼1‰. The results suggest that the rates of methane-forming reactions affected by pressure control methane carbon isotope fractionation. Based on distinctive carbon isotope patterns of methane and wet gases from pressurized oil cracking, a conceptual model using “natural gas plot” is constructed to identify pressure effect on in situ oil cracking providing other factors excluded. The transition in going from dry conditions to normal and supercritical water does not have a significant effect on oil-cracking reactions as evidenced by gold bag hydrous and anhydrous pyrolysis results at the same temperatures as used in the pressure vessel

Impact of high water pressure on oil generation and maturation in Kimmeridge Clay and Monterey source rocks: implications for petroleum retention and gas generation in shale gas systems

This study presents results for pyrolysis experiments conducted on immature Type II and IIs source rocks (Kimmeridge Clay, Dorset UK, and Monterey shale, California, USA respectively) to investigate the impact of high water pressure on source rock maturation and petroleum (oil and gas) generation. Using a 25 ml Hastalloy vessel, the source rocks were pyrolysed at low (180 and 245 bar) and high (500, 700 and 900 bar) water pressure hydrous conditions at 350 °C and 380 °C for between 6 and 24 h. For the Kimmeridge Clay (KCF) at 350 °C, Rock Eval HI of the pyrolysed rock residues were 30–44 mg/g higher between 6 h and 12 h at 900 bar than at 180 bar. Also at 350 °C for 24 h the gas, expelled oil, and vitrinite reflectance (VR) were all reduced by 46%, 61%, and 0.25% Ro respectively at 900 bar compared with 180 bar. At 380 °C the retardation effect of pressure on the KCF was less significant for gas generation. However, oil yield and VR were reduced by 47% and 0.3% Ro respectively, and Rock Eval HI was also higher by 28 mg/g at 900 bar compared with 245 bar at 12 h. The huge decrease in gas and oil yields and the VR observed with an increase in water pressure at 350 °C for 24 h and 380 °C for 12 h (maximum oil generation) were also observed for all other times and temperatures investigated for the KCF and the Monterey shale. This shows that high water pressure significantly retards petroleum generation and source rock maturation. The retardation of oil generation and expulsion resulted in significant amounts of bitumen and oil being retained in the rocks pyrolysed at high pressures, suggesting that pressure is a possible mechanism for retaining petroleum (bitumen and oil) in source rocks. This retention of petroleum within the rock provides a mechanism for oil-prone source rocks to become potential shale gas reservoirs. The implications from this study are that in geological basins, pressure, temperature and time will all exert significant control on the extent of petroleum generation and source rock maturation for Type II source rocks, and that the petroleum retained in the rocks at high pressures may explain in part why oil-prone source rocks contain the most prolific shale gas resources

Pore structural evolution of shale following thermochemical treatment

Shales experience heat treatment concurrent with the presence of water or steam during reservoir engineering interventions, such as high pressure water fracking and in-situ combustion of hydrocarbons. This work utilises a novel technique, which is a combination of gas sorption overcondensation and integrated mercury porosimetry experiments, not used before for any type of porous material, to study the pore structure of a shale rock, and its evolution following thermal treatment in the presence of water. Overcondensation allows the extension of gas sorption beyond the limits of conventional experiments to enable direct study of macroporosity. Scanning curve experiments, initiated from the complete boundary desorption isotherm, that can only be obtained for macropores by overcondensation experiments, has revealed details of the relative pore size spatial disposition within the network. In particular, it has been found that the new large voids formed by treatment are shielded by relatively much narrower pore windows. Use of a range of different adsorbates, with differing polarity, has allowed the chemical nature of the pore surface before and after treatment to be probed. Integrated rate of gas sorption and mercury porosimetry experiments have determined the level of the particular contribution to mass transport rates of the newly introduced porosity generated by thermal treatment. Combined CXT and mercury porosimetry have allowed the mapping of the macroscopic spatial distribution of even the new mesoporosity, and revealed the degree of pervasiveness of the new voids that leads to a thousand-fold increase in mass transport on thermal treatment