Assessing the catalytic effect of coal ash constituents on the CO2 gasification rate of high ash, South African coal

The catalytic effect of inorganic species, within the ash, on the CO₂ gasification of three South African coals containing similar carbon-structural properties (elemental, structural and petrographical properties) was assessed. The reactivity of the coals with a particle size between 150 and 250 μm was determined in a thermo gravimetric analyser. The reactivity was measured at temperatures between 900 and 1000 °C, pressures between 1 and 10 bar, and fractions of CO₂ between 10 and 30%. For the selected coals, the reactivity decreased with ash content, and was found to be dependent on the composition of the ash. Specifically, the reactivity increased with calcium and magnesium content and alkali index.     

A FIXED BED BARRIER REACTOR WITH SEPARATE FEED OF REACTANTS

A new type of gas-solid reactor was developed and characterised in the series of reactor configurations with separate Teed of reactants studied by our group. The novelty in the proposed design lies in the use of a fixed bed of small catalytic particles instead of a porous catalytic membrane. The major advantages of this concept, as opposed to the catalytic membrane reactor, are: (i) the barrier activity and pore structure are more homogeneous (good properties for modelling purposes); (ii) an easier integration of the catalyst bed into the reactor is obtained (the fixed bed can be sealed more easily into metallic modules than a catalytic membrane).

A Pt catalyst supported on La-stabilised alumina pellets (d_p = 5 - 50 μm) was used and the catalytic oxidation of carbon monoxide was studied as a model reaction to characterise the reactor. A mathematical model based on the Dusty Gas Model approach was conceived and a good agreement between calculations and experiments was obtained. This fixed bed barrier reactor may thus represent a quicker and easier opportunity, compared to membrane reactors, to check the concept of the separate-feed of reactants with new reactions and catalysts.     

Reactor technology options for distributed hydrogen generation via ammonia decomposition: A review

Hydrogen (H₂) fuel obtained via thermo-catalytic ammonia (NH₃) decomposition is rapidly attracting considerable interest for portable and distributed power generation systems. Consequently, a variety of reactor technologies are being developed in view of the current lack of infrastructure to generate H₂ for proton exchange membrane (PEM) fuel cells. This paper provides an extensive review of the state-of-the-art reactor technology (also referred to as reactor infrastructure) for pure NH₃ decomposition. The review strategy is to survey the open literature and present reactor technology developments in a chronological order. The primary objective of this paper is to provide a condensed viewpoint and basis for future advances in reactor technology for generating H₂ via NH₃ decomposition. Also, this review highlights the prominent issues and prevailing challenges that are yet to be overcome for possible market entry and subsequent commercialization of various reactor technologies. To our knowledge, this work presents for the first time a review of reactor infrastructure for distributed H₂ generation via NH₃ decomposition. Despite commendable research and development progress, substantial effort is still required if commercialization of NH₃ decomposition reactor infrastructure is to be realized.     

Properties of high ash coal-char particles derived from inertinite-rich coal: II. Gasification kinetics with carbon dioxide

The reaction rate of carbon dioxide-nitrogen gas mixtures with a well-characterised high ash char derived from an inertinite-rich coal discard was investigated by experimentation and reaction rate modelling. Experimentation with a thermogravimetric analyzer at 87.5 kPa and 287.5 kPa between 850 °C and 900 °C and with 1mm diameter particles, similar to operating conditions used for bubbling fluidised bed gasification, was carried out. The char consisted of a large proportion of dense char formed from the inertinite in the parent coal, fine pores from the low concentration of reactive macerals and cracks formed as a result of thermal deflagration. The effects of carbon dioxide concentration, temperature and pressure on the carbon conversion with time were found to follow expected trends with long reaction times. The random pore model, which accounts for intraparticle structural changes, was examined to predict the overall reaction rate. For this evaluation, a new procedure was developed to determine the structural parameter which could not be calculated directly from initial characterisation results. This procedure consists of defining a reduced time parameter, which conveniently eliminates the effect of the intrinsic kinetics when conversion versus the reduced time results is used. Thus, the structural parameter, which characterises the pore growth and coalescence, can be evaluated by a regression procedure using experimental results obtained at all temperatures and pressures. Intrinsic reaction parameters based on the power rate law were also calculated from carbon conversion versus real time results using a stepwise regression procedure. It was found that the random pore model predictions for the carbon conversion with time using the determined parameters correlated very well with experimental results, thus confirming that the reaction rate is chemical-reaction controlled.     

A modelling evaluation of an ammonia-fuelled microchannel reformer for hydrogen generation

Hydrogen production from an ammonia-fuelled microchannel reactor is simulated in a three-dimensional (3D) model implemented via Comsol Multiphysics™. The work described in this paper endeavours to obtain a mathematical framework that provides an understanding of reaction-coupled transport phenomena within the microchannel reactor. The transport processes and reactor performance are elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction rate and NH₃ conversion profiles. The baseline case is first investigated to comprehend the behaviour of the microchannel reactor, then microstructural design and operating parameters are methodically altered around the baseline conditions to explore the optimum values. The simulation results show that an optimum NH₃ space velocity (GHSV) of 65,000 Nml g_cat⁻¹ h⁻¹ yields 99.1% NH₃ conversion and a power density of 32 kW_e L⁻¹ at the highest operating temperature of 973 K. It is also shown that a 40-μm-thick porous washcoat is most desirable at these optimum conditions. Finally, a low channel hydraulic diameter (225 μm) is observed to contribute to high NH₃ conversion. Mass transport limitations in the porous-washcoat and gas-phase are negligible as depicted by the Damköhler and Fourier numbers, respectively. The experimental microchannel reactor yields 98.2% NH₃ conversion and a power density of 30.8 kW_e L⁻¹ when tested at the optimum operating conditions established by the model. Good agreement with experimental data is observed, so the integrated experimental-modelling approach developed in this paper may well provide an incisive step toward the efficient design of ammonia-fuelled microchannel reformers.     

The modeling of the combustion of high-ash coal-char particles suitable for pressurised fluidized bed combustion: shrinking reacted core model

An investigation was undertaken involving the combustion of high-ash coal/char particles under conditions suitable for pressurised fluidised bed combustion, in order to evaluate an overall combustion model. The use of very poor quality feedstocks (greater than 40% ash, low calorific value and high sulphur content) in conventional pulverised fuel combustors (PFC) could be technically difficult and un-economical, and has the associated disadvantage of generating gaseous pollutants. Pressurised fluidised bed combustion (PFBC) which is an attractive alternative process and which uses millimetre-sized coal particles is increasing in use on a commercial scale and is the basis for several clean coal technology processes. A Thermogravimetic Analyser (TGA) was used for the experimentation, which was capable of handling relatively large coal/char particles at high pressures and temperatures. Experimentation with prepared coal/chars particles with a diameter of 3 mm at a pressure of 487 kPa and temperatures between 750 and 950 °C was carried out. For the determination of the overall kinetics of combustion it was found necessary to deviate from the established methods (surface-based reaction) and that it was essential to incorporate diffusion in the overall reaction model. Also, the concept of carbon concentration variation in the particle is introduced to account for the effect of high ash content (a mixture of carbon and minerals), instead of assuming pure carbon. This model, which consists essentially of a shrinking reactive core, was found to agree very well with experimental results and all relevant parameters required for an overall rate equation were evaluated. It is also shown that at high temperatures the shrinking reacted core model results approached the results obtained from the conventional shrinking unreacted core model.     

Salt rejection in nanofiltration for single and binary salt mixtures in view of sulphate removal

Three commercial membranes (NF70, NF90 and TFC-SR) were firstly characterized in terms of pure water flux and the rejection of uncharged (alcohols and sugars) compounds. Subsequently, the rejection of monovalent (sodium and chloride) and divalent (calcium and sulphate) ions in single (NaCl, CaCl, and Na₂SO₄) and binary (NaCI/Na₂,SO₄ CaCl₂/CaSO₄, NaCI/CaCl₂, and Na₂SO₄/CaSO₄) salt mixtures was studied. According to the pure water permeability the TFC-SR membrane is a loosely packed NF membrane (12.3 L.m ⁻².h⁻¹.bar⁻¹), while both NF70 and NF90 are tightly packed (2.6 and 3.6 Lm⁻².h⁻¹.bar-). According to the uncharged solute rejection, the MWCO_NF70 = 60, MWCO_NF90= 200 and MWCO_TFC-SR > 500. NF70 and NF90 were equally efficient in rejecting 1-2, 1-1 and 2-1 salts (>90%), while TFC-SR showed typical negatively charged surface behaviour, i.e., R (1-2) salt > R (11) salt > R (2-1). Sulphate rejection decreased in the presence of sodium chloride more significantly than in the presence of calcium chloride due to the more efficient retention of the bivalent calcium.     

Kinetic analysis of non-isothermal thermogravimetric analyser results using a new method for the evaluation of the temperature integral and multi-heating rates

A technique using non-isothermal thermogravimetric analyser results was developed for the validation of reaction rate models together with associated parameters suitable for chemically controlled gas-solid reactions. The solution of the temperature integral which occurs in the calculation is achieved by numerical integration with respect to a dimensionless activation energy variable, y=E/RT, following a transformation of the temperature integral equation. The evaluation of the validity of the kinetic model and determination of all the constants is accomplished with a two-step regression procedure with experimental results from several thermogrammes with different linear heating rates. The technique was validated by comparing results obtained for the combustion of two coal-chars with corresponding isothermal results using a shrinking core model with a nth order surface reaction.     

Spray drying absorption for desulphurization: a review of recent developments

Clean Technologies and Environmental Policy - Sulphur dioxide (SO2) abatement technologies, i.e. flue gas desulphurization (FGD), have proven effective in curtailing the harmful SO2 emissions...     

Properties of high ash char particles derived from inertinite-rich coal: 1. Chemical,structural and petrographic characteristics

An investigation was undertaken to determine the properties of high ash coal–chars derived from South African discards rich in inertinites, for the development of suitable overall reaction rate models at low temperatures (<900 °C). Detailed characterisation results of the parent coal and chars prepared at 700 °C and 900 °C obtained from standard coal analytical methods, petrographic techniques, CCSEM image analysis and a surface adsorption method are presented. The parent coal consisted of 32% by volume of inertite (“pure” inertinite), 7% of vitrite (pure “vitrinite”), and 13% of bi- and tri-macerite, 30% of maceral/mineral mixtures (carbominerite) with 18% of mineral-rich material. Reflectances obtained from measurements taken on vitrinites and total maceral reflectance scans increased dramatically on charring at 900 °C and were accompanied by an extension of vitrinite reflectance class distributions indicating higher molecular ordering. Volatiles were liberated essentially from the original parent vitrinites, creating fine gas pores. Inertinites increased in reflectance but not in porosity and were characterised as dense char fractions in the final charred product, according to a coal form analysis. Structural change due to low temperature thermal stress fracturing (passive deflagration) occurred early on in the temperature regimes, creating increased surface areas and porosity. The chars consist of a high proportion (52%) of extraneous rock fragments together with minerals mainly as fine inclusions in carbon rich particles (13%). The chars had very low porosities and surface areas. These were created by the devolatisation of reactive maceral associations and deflagration. Such materials could introduce intra-particle diffusional effects during gasification and combustion of millimetre size particles at low temperatures.