Studies of the effect of retorting factors on the yield of shale oil for a new comprehensive utilization technology of oil shale

The comprehensive utilization of oil shale is a new promising technology achieving high utilization-factors for both oil shale’s chemical and energy potentials, and avoiding serious environmental impacts. For this technology, it is an urgent issue how to obtain shale oil with a high yield and as well as treat shale char efficiently and economically. In this present work, retorting experiments of three type I oil shales were performed using an aluminum retort, and the effect of retorting temperature, residence time, particle size and heating rate on the yield of shale oil was studied at low retorting temperatures ranging from 400 °C to 520 °C, respectively, at which shale char obtained has good combustion properties. The experimental data show that an increase in the retorting temperature, the residence time and the heating time has positive significant effect on improving the yield of shale oil, and a middle particle size is helpful for increasing the oil yield as well. The grey system method was applied to evaluate the effect of retorting factors on the yield of shale oil, showing that the retorting temperature is the most marked factor influencing the yield of shale oil.     

Gasification of oil shale dust in a counterflow moving bed filtration combustion reactor

Experimental investigation of gasification of oil shale dust in a counterflow moving bed filtration combustion reactor was carried out. The process was implemented similar to filtration combustion of gases: pulverized solid fuel supplied simultaneously with oxidizer. For a controlled supply of fuel dust a new rotating dispenser was used. Characteristics of process depending on the equivalence ratio were obtained. The absence of a rise in pressure drop over time indicates the lack of fuel accumulation and ash inside the porous bed, all ash was carried out from the reactor with a gas stream. It is shown that an increase in the flow rate of a gaseous oxidizer leads to an increase in both temperature and the inert velocity. The inert velocity, the calorific value of gaseous products, and the efficiency of gasification increase almost linearly with the equivalence ratio. Proposed method allows producing combustible gaseous products without a noticeable concentration of pyrolysis tars and calorific value up to 4 MJ/m³, gasification efficiency was ~85%.     

Kinetic modeling and simulation: Pyrolysis of Jatropha residue de-oiled cake

An improved kinetic model based on thermal decomposition of biomass constituents, i.e. cellulose, hemicellulose and lignin, is developed in the present study. The model considers the independent parallel reactions of order n producing volatiles and charcoal from each biomass constituent. While estimating the kinetic parameters, the order of degradation of biomass constituents is also checked and found to be matching with the order of degradation reported in the literature. The results of thermo-gravimetric analysis of Jatropha de-oiled cakes are used to find the kinetic parameters. The experimental runs are carried out using a thermo-gravimetric analyzer (TGA 4000, Perkin Elmer). TGA study is performed in a nitrogen atmosphere under non-isothermal conditions at different heating rates and the thermal decomposition profiles are used. The model is simulated using finite difference method to predict the pyrolysis rate. The corresponding parameters of the model are estimated by minimizing the square of the error between the model predicted values of residual weight fraction and the experimental data of thermogravimetry. The minimization of square of the error is performed using non-traditional optimization technique logarithmic differential evolution (LDE).     

Gasification of biomass: comparison of fixed bed and fluidized bed gasifier

Gasification as a thermochemical process is defined and limited to combustion and pyrolysis. A systematic overview of reactor designs categorizes fixed bed and fluidized bed reactors. Criteria for a comparison of these reactors are worked out, i.e. technology, use of material, use of energy, environment and economy. A utility analysis for thermochemical processes is suggested. It shows that the advantages of one of the reactor types are marginal. An advantage mainly depends on the physical consistency of the input. As a result there is no significant advantage for the fixed bed or the fluidized bed reactor.     

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.     

Progress and recent utilization trends in combustion of Chinese oil shale

The gradual decrease in conventional energy resources, and the growth of heavy industry, have placed great pressure on China's energy supplies. As a result of technological development, clean and diverse energy utilization facilities have become available in the energy market. Oil shale with combustible organic materials is widespread throughout the earth; many researchers have been motivated to investigate efficient means to use oil shale as an alternative energy as soon as possible.

In China, the conventional utilization of oil shale is concentrated mainly on oil shale retorting, and burning oil shale in pulverized furnaces, or bubbling fluidized beds. To improve the availability of oil shale, many specialists have advocated burning oil shale in a circulating fluidized bed (CFB), which has a satisfactory combustion efficiency, low NO_X and SO₂ emission, adaptability to low-grade coal, etc. In Huadian, China, a plant incorporating three units of 65 t h⁻¹ oil shale-fired CFB began successful commercial operation in 1996, proving that burning oil shale in a CFB produces both high combustion efficiency and environmental protection. For effective utilization of oil shale, its pyrolysis and combustion characteristics, emission performance of gaseous pollutants from an oil shale-fired CFB pilot setup, co-combustion characteristics of oil shale and high sulfur coal—as well as the operating performance of the Huadian CFB boiler—were further studied. The resulting experimental data and theoretical analysis prove that oil shale resources have significant potential use in the combustion field.

This paper introduces these fundamental characteristics and the industrial application of oil shale in combustion. Three projects are recommended for the future use of oil shale, based on the current status of energy and the characteristics of oil shale: (1) co-combustion of oil shale and high sulfur fuel for furnace desulfurization; (2) large-scale development of oil shale-fired CFBs; (3) a comprehensive oil shale utilization project to produce shale oil, burn oil-shale semicoke in a CFB boiler to generate electricity and supply heat, and produce building materials with oil shale ash.     

Flash pyrolysis of jatropha oil cake in electrically heated fluidized bed reactor

Fluidized bed flash pyrolysis experiments have been conducted on a sample of jatropha oil cake to determine particularly the effects of particle size, pyrolysis temperature and nitrogen gas flow rate on the pyrolysis yields. The particle size, nitrogen gas flow rate and temperature of jatropha oil cake were varied from 0.3 to 1.18 mm, 1.25 to 2.4 m³/h and 350 to 550 °C. The maximum oil yield of 64.25 wt% was obtained at a nitrogen gas flow rate of 1.75 m³/h, particle size of 0.7–1.0 mm and pyrolysis temperature of 500 °C. The calorific value of pyrolysis oil was found to be 19.66 MJ/kg. The pyrolysis gas can be used as a gaseous fuel.     

The effect of acid treatment on pyrolysis of Longkou oil shale

The effect of acid treatment on mineral removal and pyrolysis of Longkou oil shale were investigated. X-ray diffraction (XRD) and X-ray fluorescence (XRF) indicated that the HCl treatment can remove the calcite, the H₂SO₄ treatment can convert the calcite to CaSO₄, and the HF treatment can remove the quartz and convert the calcite to CaF₂; moreover, all three treatments cannot remove the pyrite in the oil shale. Oil shale was individually treated with HCl, H₂SO₄, and HF before conducted the pyrolysis experiment. The pyrolysis results showed that oil shale treated with H₂SO₄ or HF almost equally enhanced the oil yield, while HCl treatment had a negative effect on the oil yield. Thermogravimetry (TG) analysis indicated that the carbonates had a catalytic effect, sulfates may also had a catalytic effect and the silicates had an inhibitive effect on the decomposition of kerogen. Combining the TG analysis, oil yield and the price of every acid, the H₂SO₄ treatment was considered to be the best method to treat oil shale.Moreover, the carbonate minerals can be removed after H₂SO₄ treatment, so it would reduce the amount of pyrolysis feed to increase production efficiency.     

Interactions and kinetic analysis of oil shale semi-coke with cornstalk during co-combustion

The combustion experiments of oil shale semi-coke from Wang Qing retorts, cornstalk as well as their mixture were conducted under different heating rates using the thermogravimetric analyzer. The results showed that the advance ignition and burnout can be achieved when semi-coke was mixed with cornstalk. Derivative thermogravimetric curve of the experiment was compared with that of the calculated. The values of interaction index were solved. The interaction of mixture in the combustion process occurred mainly in 400–600 °C. It can be explained that the combustion of fixed carbon in cornstalk was delayed. The kinetics of combustion was studied for samples. The activation enthalpy, activation entropy and free energy of activation were analyzed by Kissinger–Akahira–Sunose equation and distributed activation energy model based on Eyring rate constant. The free energy of activation decreased with the addition of cornstalk proportion in the mixture. The results showed the feasibility using Johnson–Mehl–Avrami equation to simulate thermogravimetric curve. The representation of free energy of activation simulated agrees with that solved by Kissinger–Akahira–Sunose equation.     

Two-dimensional numerical modeling of combustion of Jordanian oil shale

A two-dimensional (2-D) modeling of the burning process of Jordanian oil shale in a circulating fluidized bed (CFB) burner was done in this study. The governing equations of continuity, momentum, energy, mass diffusion, and chemical combustion reactions kinetics were solved numerically using the finite volume method. The numerical solution was carried out using a high-resolution 2-D mesh to account for the solid and gaseous phases, k-ε turbulence, non-premixed combustion, and reacting CFD model with the same dimensions and materials of the experimental combustion burner used in this work. The temperature distribution and evolution of species were also computed.

Proximate and ultimate analyses were also performed to evaluate the air–fuel ratio and ash content. The required thermophysical properties, such as heating value, density, and porosity were obtained experimentally, while the activation energy was obtained from published literature.

It was found that the temperature contours of the combustion process showed that the adiabatic flame temperature was 1080 K in a vertical burner, while the obtained experimental results of maximum temperature at various locations of the burner in actual, non-adiabatic, non-stoichiometric combustion reached 950 K, showing good agreement with the model.     

Theoretical and experimental investigation of biomass gasification process in a fixed bed gasifier

This investigation concerns the process of air biomass gasification in a fixed bed gasifier. Theoretical equilibrium calculations and experimental investigation of the composition of syngas were carried out and compared with findings of other researchers. The influence of excess air ratio (λ) and parameters of biomass on the composition of syngas were investigated. A theoretical model is proposed, based on the equilibrium and thermodynamic balance of the gasification zone.The experimental investigation was carried out at a setup that consists of a gasifier connected by a pipe with a water boiler fired with coal (50 kWth). Syngas obtained in the gasifier is supplied into the coal firing zone of the boiler, and co-combusted with coal. The moisture content in biomass and excess air ratio of the gasification process are crucial parameters, determining the composition of syngas. Another important parameter is the kind of applied biomass. Despite similar compositions and dimensions of the two investigated feedstocks (wood pellets and oats husk pellets), compositions of syngas obtained in the case of these fuels were different. On the basis of tests it may be stated that oats husk pellets are not a suitable fuel for the purpose of gasification.     

Reducing CO2 emissions from oil shale semicoke smoldering combustion by varying the carbonate and fixed carbon contents

One technique used to recover oil from ground oil shale, or to burn oil shale semicoke, consists of propagating a smoldering front through a packed bed. One drawback of this technique is that the mineral structure of the shale is decarbonated due to the high temperature of the front. This phenomenon causes 70% of the CO₂ emissions released during such processes. The remaining 30% result from the fixed carbon oxidation. With the aim of decreasing the front temperature and thus avoiding decarbonation at the front passage, the impact of two parameters was experimentally tested in this work: first, increasing the amount of carbonates, as they may play the role of a heat sink, and second, decreasing the amount of fixed carbon in the medium. It is shown that increasing the amount of carbonates can only decrease the front temperature to 800 °C but not lower, which is still too high to avoid decarbonation. On the other hand, the front temperature can be decreased enough for decarbonation to be almost completely avoided by reducing the amount of fixed carbon. At the low temperatures reached, almost all the fixed carbon is oxidized, but not all the oxygen transported in the air is consumed by the chemical front. The velocity of the front is consequently decreased.     

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.     

Kinetic and diffusive data from batch combustion of wood chars in fluidized bed

In this work it is studied the combustion of batches of wood char particles in a shallow fluidized bed at laboratory scale. Commercial and recarbonized chars from nut pine and cork oak parent woods were burned for bed temperatures of 600-750 °C and particle sizes range of 1.8-3.6 mm. A combustion model based on the two-phase theory of fluidization is presented to evaluate the global combustion resistance. Sherwood numbers and kinetic constants for the heterogeneous phase reaction are also assessed. Through the comparison among theoretical and experimental results, conclusions are drawn on the combustion mechanism as well as on the combustion controlling resistance. The Arrhenius law is proposed to predict the kinetic constants for the studied chars.     

Utilization of grinding aids in oil shale milling

Grinding aids (GAs) effectively reduce the energy requirements of the grinding process and improve grinding productivity. Two GAs (sodium silicate and triethanolamine (TEA)) were selected and their mechanisms of action were explored. The effect of the different grinding parameters on oil shale grinding efficiency was determined. The adsorption characteristics of the GAs were investigated using scanning electron microscopy (SEM), pulp viscosity, surface potential, and Fourier transform infra-red spectroscopy (FTIR). The results indicate that compared to grinding without GAs, the addition of sodium silicate and triethanolamine (TEA), increases the yield of ?0.075 mm particles by ?2.97% and 14.05%, respectively. The optimal grinding parameters were determined for a pulp concentration 40%, a steel ball weight ratio of Φ32 mm: Φ25 mm: Φ22 mm: Φ18 mm (50:24:17:9), and a grinding time of 20 min. The flotation test results indicate that compared to sodium silicate, TEA is the more suitable GA. The addition of sodium silicate reduced the sharp edges of the particles, increased the pulp viscosity and reduced the surface potential. It was not conducive to pulp dispersion. Conversely, TEA reduced the pulp viscosity and increased the surface potential, which enhanced the repulsive force between the particles, increasing the particle spacing, and the dispersion of the pulp. Sodium silicate and TEA both formed hydrogen bonds or chemical bonds on the surface of the mineral particles, strengthened the steric-hinderance effect, and enhanced the repulsive force between the particles.     

Prediction of some performance characteristics of shale oil in the gas turbine combustor

Measurements of radiation, smoke and temperature in a developed experimental combustor at various air pressures, inlet temperatures and air-fuel ratios have shown the effects of such fuel properties as volatility, boiling range and H percentage mass content on ignition, lean blow-out, liner temperature and exhaust smoke. This study has been extended to cover some of these performance characteristics for shale oil.     

Carbonisation of bagasse in a fixed bed reactor: influence of process variables on char yield and characteristics

Carbonisation experiments on samples of sugar cane bagasse were conducted in a static fixed bed reactor to determine the effect of process variables such as temperature, heating rate, inert sweep gas flow rate and particle size on the yield and composition of solid product char. Experiments were performed to the final temperatures of 250–700°C with heating rates from 5 to 30°C/min with nitrogen sweep gas flow rate of 350 cc/min. Additional tests were aimed at studying the effect of different flow rates of nitrogen sweep gas from 0 to 700 cc/min during carbonization and different particle size fractions of bagasse. The results showed that as the carbonisation temperature was increased, the yield of char decreased. The reduction in yield was rapid up to a final temperature of 500°C and was slower thereafter. The yield of char was relatively insensitive to the changes in heating rate and particle size. Increasing the sweep gas flow rate to 350 cc/min reduced the yield of char. It appears the presence of inert sweep gas reduced secondary reactions which promoted char formation. The proximate analysis of the char suggests that fixed carbon and ash content increased with temperature. The char obtained at temperatures higher than 500°C have high carbon content and is suitable as renewable fuel and for other applications. The carbonization of bagasse has the potential to produce environmental friendly fuels and can assist in reducing deforestation for the production of charcoal.     

CO2 gasification characteristics of nascent pyrolyzed particles from coals and oil shale

In this work, the co‐pyrolysis characteristics of oil shale with two typical coals, bitumite and lignite, and the co‐gasification characteristics of the mixture pyrolyzed fuels were studied via thermo‐gravimetric analysis. The individual fuels and mixture fuels were first pyrolysis in N₂ atmosphere to specified temperature (450, 550, and 620 °C) at the heating rate of 20, 30 and 40 °C/min, respectively, and then maintained at the given temperature for 20 min before converted to CO₂ ambient to conduct the CO₂ gasification tests. The kinetic behavior and effects of both fuel types and pyrolysis temperature were investigated. The shoulder peak at around 550 °C observed in the derivative of weight loss derivative thermogravimetry analysis (DTG) curve during the pyrolysis of oil shale has confirmed the existence of specific reactions of oil shale at around 550 °C that leads to a sharp trough in the differential curves of co‐pyrolysis with coals and the unusual change in activation energies of gasification. In isothermal pyrolysis stage, oil shale lost its vast majority of organic matters at the temperature lower than 550 °C. The escape of pyrolysis gas and liquids in the coals is much harder than that in oil shale. The interaction between oil shale and bitumite was too weak to discriminate both in the pyrolysis and CO₂ gasification process. The variation of the particle surface structure caused by the releasing of volatile gases is strongly affected by the reaction rate and temperature. Quick volatile decomposition and gas releasing lead to the increase of surface area, decrease of the average pore diameter as well as the uniformization of the pore structure, while the higher temperature results in the blockade and merging of fine pores. The two factors lead to the greatest mass loss rate in the pyrolyzed particles obtained at 550 °C in temperature programmed CO₂ gasification stage. Two model‐free methods, Friedman method and Flynn–Wall–Ozawa method, were used to extract kinetic parameters from the experimentally determined pyrolyzed fuel conversions. The volatile contend has a significant influence on the fixed carbon conversion during the partially pyrolyzed particles' CO₂ gasification. In this study, significant interactions existed in co‐thermal utilization, both pyrolysis and CO₂ gasification, of oil shale and lignite. It is therefore surmised that co‐gasification of pyrolyzed lignite and oil shale may represent a feasible, practical route to high‐efficiency utilization of these fuels. Copyright © 2017 John Wiley & Sons, Ltd.     

Comparison of green waste gasification performance in updraft and downdraft fixed bed gasifiers

This study aimed to investigate the gasification potential of municipal green waste in different fixed-bed gasifier configurations as updraft and downdraft. Both reactor systems were constructed from stainless-steel with a cyclone separator to increase synthesis gas yield and reduce tar production. Green waste collected from parks and gardens by Manisa Metropolitan Municipality, Turkey, was used in the experiments. After full-characterization of green waste, gasification experiments were performed above 700 °C to produce syngas with more than 40% (volumetric) H₂ and heating value around 12.54 MJ/Nm³. Dry air (DA) and pure oxygen (PO) were used as gasification agents. DA was applied with the flow-rates ranged between 0.4 and 0.05 L/min while the flow-rate of PO was 0.01 L/min. The maximum H₂ production as 45 vol% was obtained in downdraft reactor while it was about 51 vol% in updraft system. CH₄ production was obtained as higher value (app. 19 vol%) in downdraft reactor than that (13 vol%) in the updraft one. In the experiments with DA above 700 °C, the H₂/CO ratio varied between 1 and 3, and in the experiments with PO, it increased up to a maximum value of 4. The study has found a suitable set of gasification process parameters for two reactor systems. Therefore, the findings have been compared and discussed in detail.     

Platinum group elements in terrestrial oil shale from the Lunpola Basin,northern Tibet,China

The Lunpola oil shale is the largest oil shale resource in Tibet. Twenty-four samples were collected from this deposition to determine the platinum group element (PGE) characteristics. The total PGE contents in terrestrial oil shale are low (average 2.386 ng/g). The PGEs are enriched in the oil shale samples near the boundary between the oil shale and its underlying strata. The PGE enrichment may be the result of a change of oxic–anoxic conditions. The individual PGEs of oil shale samples from the Lunpola oil shale exhibit similar modes of occurrence, and their distributions are controlled mainly by Fe-bearing minerals (pyrite). The source of PGEs in the Lunpola oil shale is probably related to water chemistry and terrigenous supply.