Volatile gas release characteristics of three typical Chinese coals under various pyrolysis conditions

In order to reveal the volatile gas release characteristics under various conditions (pyrolysis temperature, particle size, coal rank and pyrolysis time), three different rank coals (Shenhua 2# bituminous coal, Baorixile coal, and Zhaotong lignite coal) were pyrolyzed in a tubular furnace and the pyrolysis gas was analyzed by online balance and gas chromatography. Results suggest that increasing pyrolysis temperature causes increased release volume of volatile compounds and higher calorific value due to substantial increase of H₂, an incremental increase of CH₄ and the changes in molecule ingredients of C₂C₄ structures. Meanwhile, larger particle size can significantly reduce the released volume for its longer diffusion distance and lower specific surface area. Compared with bituminite, lignite yielded more valuable pyrolysis gases and lower primary reaction temperature. The ideal pyrolysis temperature is 700–800 °C for low rank lignite and 800–900 °C for bituminites. Basically, the productions of CO and CO₂ are associated with oxygen element content in coal while CO₂ releases early mainly by the decarboxylation reaction. Based on the results in the whole pyrolysis process, the CH₄ of higher rank coals is mostly produced by the rupture of aliphatic side chain while the main CH₄ source in lignite is the rupture of alkyl side chains in aromatics.     

Distribution of Nitrogen Species During Vitrinite Pyrolysis and Gasification

The formation of HCN and NH₃ during pyrolysis in Ar and gasification in CO₂ and steam/Ar was investigated. Vitrinites were separated and purified from different rank coal from lignite to anthracite. Pyrolysis and gasification were carried out in the drop-tube/fixed-bed reactor at temperatures of 600–900°C. Results showed that with increase of reaction temperature the yield of HCN increased significantly during pyrolysis and gasification. Decrease of coal rank also increased the yield of HCN. Vitrinite from lower rank of coal with high volatile content released more HCN. The yield of NH₃ was the highest at 800°C during pyrolysis and gasification. And the yield of NH₃ from gasification in steam/Ar was far higher than that from gasification in CO₂, where the hydrogen radicals play a key role. Nitrogen retained in char was also investigated. The yield of char-N decreased with an increase of pyrolysis temperature. Vitrinite from lower rank coal had lower yield of char-N than that from the high rank coal.     

Production of benzenepolycarboxylic acids by oxidation of pre-pyrolyzed Shengli lignite

Lignite oxidation would produce benzene polycarboxylic acids (BPCAs), however, the coexisting aliphatic acids in the resulting oxidation products seriously affect the separation of BPCAs. In the study, Shengli lignite was pre-pyrolyzed at different temperatures from 250°C to 550°C, and then the obtained pyrolyzed residues were subjected to oxidation under the same condition. Oxidation reactivity of pyrolyzed residues decreased with increasing pyrolysis temperature. However, compared with Shengli lignite, its pyrolyzed residues at proper temperatures (250°C and 350°C) generated more BPCAs, especially mellitic acid with more yield and relative content. By XRD analyses of the pyrolyzed residues, more condensed aromatic structures would result in decreasing oxidation reaction activity of the pyrolyzed residues, while more amounts of aromatic species and larger aromatic unit would contribute to the increase of BPCAs and mellitic acid, respectively.     

Influence of temperature and steam on the products from the flash pyrolysis of Jordan oil shale

Oil shale samples from the Sultani deposit in the south of Jordan, were pyrolysed in a semi‐continuous fluidized bed reactor under nitrogen and nitrogen/steam atmosphere. The pyrolysis temperature between 400 and 650°C were investigated. Increasing the pyrolysis temperature from 400 to 520°C caused a large increase in the oil yield. Further increase of the pyrolysis temperature resulted in a decrease in oil yield and a large increase in the evolved gases. This increase in the hydrocarbon gas yield was attributed to oil thermal cracking reactions. The evolved gases were composed of H₂, CO, CO₂, and hydrocarbons from C₁ to C₄. The presence of steam improved the oil yield which may be a result of reducing the degree of decomposition. The derived oils were fractionated into chemical classes using mini‐column liquid chromatography. Copyright © 2002 John Wiley & Sons, Ltd.     

Transient gasification and syngas formation from coal particles in a fixed‐bed reactor

An experimental investigation on gasification and syngas formation from coal particles in a fixed‐bed reactor is conducted; particular attention is paid to the transient reaction dynamics. Three different coals, including two high‐volatile coals and a low‐volatile coal, are taken into consideration. In the initial reaction period, a two‐stage reaction is clearly observed; specifically, an exothermic reaction followed by an endothermic reaction is exhibited. Meanwhile, seeing that the devolatilization and pyrolysis reactions are pronounced, the initial concentrations of H₂ and CH₄ are relatively high, especially for the former. With increasing time, the interaction between coal and char particles is dominated by the latter, the concentrations of CO and CO₂ thus become higher. From the observation of syngas combustion, the entire gasification intensity proceeds from intensified growth, rapid decay, and then to progressive decay with increasing reaction time. For the two high‐volatile coals, the mass depletion is enhanced markedly once the reaction temperature is as high as 1000°C, whereas it is insensitive to the temperature for the low‐volatile coal. Nevertheless, it is found that, based on the weights of moisture and volatile matter, their relative release ratio from the low‐volatile coal is better than that from the high‐volatile coals. This implies that the final devolatilization and pyrolysis extent is not determined by coal grade. Copyright © 2006 John Wiley & Sons, Ltd.     

Underground in situ coal thermal treatment for synthetic fuels production

Underground coal thermal treatment (UCTT) is a promising concept that was recently proposed for extracting high-value hydrocarbon fuels from deep coal seams, which are economically unattractive for mining. UCTT is essentially an in situ pyrolysis process that converts underground coals into synthetic liquid and gaseous fuels, while leaving most of the carbon underground as a char matrix. The produced synthetic fuels have higher H/C ratios than coals. The remaining char matrix is an ideal reservoir for CO₂ sequestration because pyrolysis significantly increases the surface area of the char. The UCTT concept is relatively new, and there is little research in this area. However, underground oil shale retorting, which is also an in-situ hydrocarbon fuels conversion process, shares key features with UCTT and has gained momentum in demonstration and commercial development. As such, there is a large body of literature available in this area. A review of the studies on underground oil shale retorting that are closely related to UCTT will shed light on the UCTT process. This paper presents a review of the recent literature on underground oil shale retorting that are most relevant to UCTT process. The review provides a background to the reader by comparing the properties of coal with oil shale, with an emphasis on the feasibility of applying oil shale retorting techniques to UCTT process. The review further discusses the coal and oil shale conversion issues and uses the knowledge of the latter as guidance for the development of UCTT. Published data on pyrolysis of large coal blocks at conditions relevant to UCTT process is scarce. Therefore, literature on conventional coal pyrolysis is reviewed for optimization of the UCTT process. Despite the abundant studies on pulverized coal pyrolysis, there are still many open questions on whether they can be directly applied to UCTT. A comparison of the unique environment of UCTT with conditions of conventional pulverized coal pyrolysis clearly shows there are knowledge gaps. Future research needs are then proposed to close these gaps.     

Investigation of gasification characteristics of some coals in Turkey by the thermogravimetric analysis method

When the coal is heated, conversion process starting with moisture loss passes through pyrolysis, burning and gasification processes depending on the atmosphere, temperature rise rates, final temperature and other parameters. Since coal has a heterogeneous structure, interpretation of these phases is difficult. Thermogravimetric analysis, on the other hand, has a wide range of applications and allows valid approaches to the physical and chemical properties of coal. Therefore, the thermogravimetric analysis makes it possible to analyze the characteristics of the coal gasification phase in a practical and rapid manner.

In this study, the gasification characteristics of coal samples taken from Ilg?n, Ermenek and Zonguldak regions in Turkey were determined. Conversion time and gasification rates of Ilg?n and Ermenek coals were investigated using thermogravimetric analyzer at 700°C, 750°C, 800°C and 850°C in CO₂ atmosphere and comparisons were made between samples. In addition, conversion and gasification rates of coal samples taken from Zonguldak region at 1150°C were investigated. It was observed that the conversion time of the Ilg?n coal at 800°C and the Ermenek coal at 850°C was shorter than the other temperatures. When the 80% conversion rates of Ilg?n coal at 800°C, Ermenek coal at 850°C, and Zonguldak at 1150°C, are compared; it is observed that there exist a 1,2 min difference between Ilg?n-Zonguldak, 1,05 min between Ilg?n-Ermenek and 1,96 min between Ermenek and Zonguldak coals.     

Effect of Olive Kernel thermal treatment (torrefaction vs. slow pyrolysis) on the physicochemical characteristics and the CO2 or H2O gasification performance of as-prepared biochars

The thermochemical conversion of biomass through its gasification has been widely explored during the last decades. The generated bio-syngas mixture can be directly used as fuel in thermal engines and fuel cells or as intermediate building block to produce synthetic liquid fuels and/or value added chemicals at large scales. In the present work, the effect of Greek olive kernel (OK) thermal treatment (torrefaction at 300 °C vs. slow pyrolysis at 500 and 800 °C) on the physicochemical characteristics and CO₂ or H₂O gasification performance of as-produced biochars is examined. Both the pristine OK sample and biochars (OK300, OK500, OK800) were fully characterized by employing a variety of physicochemical methods. The results clearly revealed the beneficial effect of thermal pretreatment on the gasification performance of as-prepared biochars. Α close relationship between the physicochemical properties of fuel samples and gas production was disclosed. Carbon dioxide gasification leads mainly to CO with minor amounts of H₂ and CH₄, whereas steam gasification results in a mixture containing CO₂, CO, H₂ and CH₄ with a H₂/CO ratio varied between 1.3 and 2.3. The optimum gasification performance was obtained for the slowly pyrolyzed samples (OK500 and OK800), due to their higher carbon and ash content as well as to their higher porosity and less ordered structure compared to pristine (OK) and torrefied (OK300) samples.     

Performance of active nickel loaded lignite char catalyst on conversion of coffee residue into rich-synthesis gas by gasification

Performance of nickel-loaded lignite char catalyst on conversion of coffee residue into synthesis gas by catalytic steam gasification was carried out at low reaction temperatures ranging from 500 °C to 650 °C in the two-stage quartz fixed bed reactor. The effects of steam pressures (30, 36 and 50 kPa corresponding to S/B = 2.23, 2.92 5.16, respectively) and catalyst to biomass ratios (C/B ratio = 0, 1, 3) were considered. Nickel-loaded lignite char was prepared as a catalyst with a low nickel loading amount of 12.9 wt%. The gas yields in the catalytic steam gasification process strongly depended on the reaction temperature and C/B ratio. The total gas yields obtained in catalytic steam gasification was higher than that of catalytic pyrolysis, steam gasification and non-catalytic pyrolysis with steam absence by factors of 3.0, 3.8 and 7.7, respectively. To produce the high synthesis gas, it could be taken at 600 °C with total gas yields of 67.13 and 127.18 mmol/g biomass-d.a.f. for C/B ratios of 1.0 and 3.0, respectively. However, the maximum H₂/CO ratio was 3.57 at a reaction temperature of 600 °C, S/B of 2.23 and C/B of 1.0. Considering the conversion of coffee residue by catalytic steam gasification using the nickel-loaded lignite char catalyst, it is possible to covert the coffee residue volatiles into rich synthesis gas.     

Experimental study of the pyrolysis of waste bitumen for oil production

This work focuses on bitumen slow pyrolysis. Mass and energy yields of oil, solid and gas were obtained from pyrolysis experiments using a semi-batch reactor in a nitrogen atmosphere, under three non-isothermal conditions (maximum temperature: 450 °C, 500 °C and 550 °C). The effect of temperature on the product yields was discussed. The gas compositions were analysed using gas chromatography (GC) and the heating value of oil and solid residue was also measured. Using a thermo-gravimetric analyser, kinetic parameters were evaluated through Ozawa-Flynn-Wall (OFW) method. Results showed that oil yield is maximum at 500 °C (50%). Moreover, gas yield increased with increasing pyrolysis temperature from 18% to 36%. On the other hand, solid yield showed an opposite trend: it decreased from 39% to 32%. As regard energy yields, they showed a similar trend with the mass ones. H_2, CH₄, C₂H₄, C₂H₆ and C₃H₈ are the main components of the produced gas phase. It has been noticed that the recovery of bitumen to liquid oil through pyrolysis process had a great potential since the oil produced had high calorific value comparable with commercial fuels.     

Steam gasification of Greek lignite and its chars by co-feeding CO2 toward syngas production with an adjustable H2/CO ratio

Low-rank lignite is among the most abundant and cheap fossil fuels, linked, however, to serious environmental implications when employed as feedstock in conventional thermoelectric power plants. Hence, toward a low-carbon energy transition, the role of coal in world's energy mix should be reconsidered. In this regard, coal gasification for synthesis gas generation and consequently through its upgrade to a variety of value-added chemicals and fuels constitutes a promising alternative. Herein, we thoroughly explored for a first time the steam gasification reactivity of Greek Lignite (LG) and its derived chars obtained by raw LG thermal treatment at 300, 500 and 800 °C. Moreover, the impact of CO₂ addition on H₂O gasifying agent mixtures was also investigated. Both the pristine and char samples were fully characterized by various physicochemical techniques to gain insight into possible structure-gasification relationships. The highest syngas yield was obtained for chars derived after LG thermal treatment at 800 °C, due mainly to their high content in fixed carbon, improved textural properties and high alkali index. Steam gasification of lignite and char samples led to H₂-rich syngas mixtures with a H₂/CO ratio of approximately 3.8. However, upon co-feeding CO₂ and H₂O, the H₂/CO ratio can be suitably adjusted for several potential downstream processes.     

Pyrolysis characteristics of Turkish lignites in N2 and CO2 environments

Pyrolysis characteristics and kinetic parameters of two Turkish lignites having different ash contents (Orhaneli as low ash and Soma as high ash sample) were studied under N₂ and CO₂ atmospheres by means of thermogravimetric analysis. The isoconversional kinetic methods of Flynn?Wall??Ozawa, Kissinger??Akahira??Sunose, and Friedman were employed to estimate the activation energy and pre-exponential factors. The experiments were conducted at four different heating rates of 5, 10, 15, and 20°C/min within the temperature range of 50??950ºC. The obtained results indicated that changing the pyrolysis ambient had no significant effect on the devolatilization region up to 700°C. The char formation region in N₂ atmosphere was due to the CaCO₃ decomposition and was more significant for Soma lignite due to its high ash content. However, in CO₂ atmosphere, the gasification reaction took place at temperatures higher than 700°C. The decomposition process of CaCO₃ in CO₂ atmosphere was hampered up to temperatures higher than 900°C. The estimated activation energies were found to have approximately similar trends under different atmospheres. For Orhaneli lignite, the average activation energy values were higher in CO₂ environment. However, for Soma lignite due to decomposition of CaCO₃, the activation energy values were higher in N₂ atmosphere. The mean uncertainty values were assessed for the activation energy values obtained for all test cases.     

Characterization of the physicochemical and structural evolution of biomass particles during combined pyrolysis and CO2 gasification

The combination of pyrolysis and CO₂ gasification was studied to synergistically improve the syngas yield and biochar quality. The subsequent 60-min CO₂ gasification at 800 °C after pyrolysis increased the syngas yield from 23.4% to 40.7% while decreasing the yields of biochar and bio-oil from 27.3% to 17.1% and from 49.3% to 42.2%, respectively. The BET area of the biochar obtained by the subsequent 60-min CO₂ gasification at 800 °C was 384.5 m²/g, compared to 6.8 m²/g for the biochar obtained by the 60-min pyrolysis at 800 °C, and 1.4 m²/g for the raw biomass. The biochar obtained above 500 °C was virtually amorphous.     

Mechanism study of nitric oxide reduction by light gases from typical Chinese coals

Coal devolatilization plays an important role in NO formation and reduction. In this study, the coal pyrolysis experiment was performed in an entrained flow reactor to obtain the light gas release characteristics. Six typical Chinese coals with volatile content ranged from 8.8% to 38.3% were studied. The pyrolysis temperature was in the range from 600 to 1200 °C. A significant rank dependence of HCN, CO and C₂H₂/C₂H₄/C₂H₆ was observed and their release for high volatile coals was higher than that for low volatile coals. The HCN–N/NH₃–N ratio ranged from 0.00 to 0.66 for anthracite coals and ranged from 1.63 to 3.90 for high volatile coals. Based on the experimental results, the effect of coal pyrolysis gas on NO reduction in a plug flow reactor at reducing atmosphere was kinetically calculated. The optimal excess air ratio(α_opt) corresponding to the maximum NO removal efficiency decreased with an increase in reduction temperature. For the light gas from the HL coal pyrolyzed at 800 °C, the α_opt decreased from 0.73 to 0.17 when the reduction temperature increased from 927 to 1327 °C. The rate of production analysis indicated that NO removal efficiency was determined by 3 competing reaction paths: NO reduction, NO formation and oxygen consumption by combustible species.     

CO2 gasification of dairy and swine manure: A life cycle assessment approach

CO₂ gasification of three different chars obtained from the pyrolysis of two dairy manure samples and a swine manure sample was evaluated. Dairy samples were firstly pretreated by anaerobic digestion process and swine sample by bio-drying process. Subsequently, manure samples were pyrolyzed between 30 °C and 980 °C obtaining a solid fuel (biochar), which was later gasified using different vol.% CO₂ (15–90%) which was the gasifying agent. Gasification was conducted at 900 °C. Thermal behavior and gasification characteristics were studied by means of the thermogravimetric-mass spectrometric analysis. In this sense, the reactivity of the samples was influenced by the catalytic activity of the mineral matter contained in the remaining biomass ashes. On the other hand, the viability of the manure gasification process vs the traditional use of manure as fertilizer was studied by means of the life cycle assessment (LCA) methodology. Two different scenarios were analyzed: gasification of manure sample before anaerobic digestion (Pre) and gasification of manure after anaerobic digestion (Dig R). According to the results obtained, the gasification of char Pre was the most viable scenario from the economic and environmental viewpoints whereas the gasification of char Dig R was the best energetic option.     

Olive residues (cuttings and kernels) rapid pyrolysis product yields and kinetics

A study of pyrolysis of olive residues (cuttings and kernels) at a temperature range from 300 to 600°C, has been carried out. The experiments were performed in a captive sample reactor at atmospheric pressure under helium. The yields of the derived gases, pyrolytic liquids and char were determined in relation to pyrolysis temperature, at heating rates of about 200°C/s.As the pyrolysis temperature was increased the percentage mass of char decreased whilst gas and oil products increased. The oil products increased to a maximum value of ∼30 wt% of dry biomass at about 450–550°C. The major gaseous products are CO and CO₂.A simple first order kinetic model has been applied to the evolution of total losses and gases. Kinetic parameters have been estimated and compared with other reported similar data.     

Conversion of oil shale to liquid hydrocarbons

Oil shale is a complex fossil material that is composed of organic matter and mineral matrix. The thermal decomposition of the organic matter generates liquid and gaseous products. Oil shale is a porous rock containing kerogen, an organic bituminous material. Kerogen is a solid mixture of organic compounds that is found in certain sedimentary rocks. The kerogen can be pyrolyzed and distilled into petroleum-like oil. Oil shale and bituminous materials are suitable for obtaining petroleum-like products. The process designed in this study has the ability to control unwanted volatile materials. The mineral matter is removed from oil shale before pyrolysis. The pyrolysis of the oil shale is performed in a retort. The temperature at which the kerogen decomposes into usable hydrocarbons begins at 300°C, but the decomposition proceeds more rapidly and completely at higher temperatures. Decomposition takes place most quickly at a temperature between 475 and 525°C. Shale oil from oil shale consists of the hydrocarbons: paraffins, olefins, isoparaffins and naphthenes, isoolefins and cycloolefins, monocyclic aromatics, and poly-cyclic aromatics. The nonhydrocarbons are nitrogen, sulfur, and oxygen (NSO) compounds.     

Pyrolysis of waste pomegranate peels for bio-oil production

In order to obtain bio-oil from the pomegranate peel which is a by-product of juice production process, the dried pomegranate peel was pyrolyzed at a heating rate of 10°C/min and different temperatures between 400 and 550°C. The highest pyrolytic oil yield of 40.47 wt% was obtained at the final temperature of 550°C. The oil product was characterized by various analysis techniques. The results showed that the oil product mostly contained fine chemicals with oxygen like phenols, furfural, and its derivatives with the carbon number in a range of C₃-C₁₀. The oil product had the potential for producing fine chemicals.     

Hybrid clean energy technologies for power generation from sub-bituminous coals: a case of 250 MW unit

Major re-thinking is required on the conventional pulverized fuel conversion route of power generation wherein the ash and mineral burden in coals is transported through the entire flow passage of the boiler. For high-ash fuels, this has to be contained and the boiler must be clear of all mineral matter. The two independent clean coal candidate technologies for efficiency enhancement and emission controls – ultra-supercritical cycle (USC) and integrated gasification with combined cycle (IGCC) – both have limitations in adaptation to high-ash coals. While the USC is limited by the steam temperature up to 600°C (commercial scale) (700°C pilot scale) and boiler tube failure risks, IGCC is limited to high-quality fuels like diesel, naphtha, etc. (commercial scale) and high-grade coals (pre-commercial scale). The hybridization of the two technologies in their current form (ultra-supercritical cycle with gasification conversion) and carbon capture and storage (CCS) together with solar energy (solar thermal and solar photovoltaic) integration presents possibilities for immediate application to low-grade sub-bituminous coals to achieve the clean technology goals. The energy efficiency of the hybrid system is around 44.45%, which is of the order of the USC with pulverized coal combustion. But the predominant benefits of a clean operation override. The benefits are reduction in CO₂ generation from 0.86 to 0.70 kg/kWh and reduction in ash expelled from 0.20–0.24 to 0.12–0.18 kg/kWh besides elimination of dispersion of ash around the power station and facilitating CCS.     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.