Edward J. Anthony

Sulfation phenomena in fluidized bed combustion systems

Fluidized bed combustors (FBCs) are noted for their ability to capture SO2 in situ via direct reaction with Ca-based sorbents. However, despite more than 30 years of intensive study of sulfation processes in atmospheric FBC boilers and numerous laboratory studies, there are still many uncertainties and disagreements on the subject. In particular, the mechanisms of the sulfation reaction are still not properly understood, and there is dispute over the explanation of the well-known temperature maximum for optimum sulfur capture found in FBC boilers. This paper discusses these points of contention and suggests the most probable mechanisms and explanations for the various phenomena seen with sulfur capture, based on current literature and personal experimentation.

Fluidized bed combustion of alternative solid fuels ; status, successes and problems of the technology

Abstract Fluidized bed combustion can be used for energy production or incineration for almost any material containing carbon, hydrogen and sulphur in a combustible form, whether it be in the form of a solid, liquid, slurry or gas. The technologys fuel flexibility arises from the fact that the fuel is present in the combustor at a low level and is burnt in the mass of a thermally inert bed material (typically this is limestone if sulphur capture is required, otherwise sand). However, fuel flexibility must either be built into the design of the combustor or alternatively the FBC system must be tailored for a specific fuel or combination of fuels. In addition, the designer must consider issues like heat release patterns, ash characteristics (particularly if the ash has any potential for agglomeration or fouling of heat transfer surfaces or blockage of the return valve in the case of a circulating FBC) and any special requirements of the fuel such as the need for sulphur or HCl capture. This paper surveys the literature on some of the more important alternative fuels and also makes specific recommendations about problems or major issues with those fuels. Particular attention is given to the use of FBC for petroleum coke, coal wastes, wood pulp sludges, and biomass residues. These fuels are emphasized because of their current economic importance, particularly in North America.

Influence of High-Temperature Steam on the Reactivity of CaO Sorbent for CO2 Capture

Calcium looping is a high-temperature CO(2) capture technology applicable to the postcombustion capture of CO(2) from power station flue gas, or integrated with fuel conversion in precombustion CO(2) capture schemes. The capture technology uses solid CaO sorbent derived from natural limestone and takes advantage of the reversible reaction between CaO and CO(2) to form CaCO(3); that is, to achieve the separation of CO(2) from flue or fuel gas, and produce a pure stream of CO(2) suitable for geological storage. An important characteristic of the sorbent, affecting the cost-efficiency of this technology, is the decay in reactivity of the sorbent over multiple CO(2) capture-and-release cycles. This work reports on the influence of high-temperature steam, which will be present in flue (about 5-10%) and fuel (∼20%) gases, on the reactivity of CaO sorbent derived from four natural limestones. A significant increase in the reactivity of these sorbents was found for 30 cycles in the presence of steam (from 1-20%). Steam influences the sorbent reactivity in two ways. Steam present during calcination promotes sintering that produces a sorbent morphology with most of the pore volume associated with larger pores of ∼50 nm in diameter, and which appears to be relatively more stable than the pore structure that evolves when no steam is present. The presence of steam during carbonation reduces the diffusion resistance during carbonation. We observed a synergistic effect, i.e., the highest reactivity was observed when steam was present for both calcination and carbonation.

An overview of advances in biomass gasification

Biomass gasification is a widely used thermochemical process for obtaining products with more value and potential applications than the raw material itself. Cutting-edge, innovative and economical gasification techniques with high efficiencies are a prerequisite for the development of this technology. This paper delivers an assessment on the fundamentals such as feedstock types, the impact of different operating parameters, tar formation and cracking, and modelling approaches for biomass gasification. Furthermore, the authors comparatively discuss various conventional mechanisms for gasification as well as recent advances in biomass gasification. Unique gasifiers along with multi-generation strategies are discussed as a means to promote this technology into alternative applications, which require higher flexibility and greater efficiency. A strategy to improve the feasibility and sustainability of biomass gasification is via technological advancement and the minimization of socio-environmental effects. This paper sheds light on diverse areas of biomass gasification as a potentially sustainable and environmentally friendly technology.

A review of developments in pilot-plant testing and modelling of calcium looping process for CO2 capture from power generation systems

A nearly complete decarbonisation of the power sector is essential to meet the European Union target for greenhouse gas emissions reduction. Carbon capture and storage technologies have been identified as a key measure in reducing the carbon-intensity of the power sector. However, no cost-effective technology has yet been developed on a commercial scale, which is mostly due to high capital cost. Moreover, the mature technologies, such as amine scrubbing or oxy-combustion technologies, impose a high projected efficiency penalty (8–12.5% points) upon integration to the power plant. The calcium looping process, which is currently being tested experimentally in bench- and pilot-scale plants worldwide, is regarded as a promising alternative to the chemical solvent scrubbing approach, as it leads to the projected efficiency penalty of 6–8% points. The calcium looping concept has been developing rapidly due to the introduction of new test facilities, new correlations for process modelling, and process configurations for improved performance. The first part of this review provides an overview of the bench- and pilot-plant test facilities available worldwide. The focus is put on summarising the characteristics and operating conditions of the test facilities, as well as extracting the key experimental findings. Additionally, the experimental data suitable for validation or verification of the process models are presented. In the second part, the approaches to the carbonator and the calciner reactor modelling are summarised and classified in five model complexity levels. Moreover, the model limitations are assessed and the needs for modelling baselines for further process analyses are identified. Finally, in the third part the approaches for the integration of calcium looping to the power generation systems and for the improvement of the process performance are identified and evaluated. This review indicates that calcium looping integration resulted in the projected efficiency penalty of 2.6–7.9% points for the coal-fired power plants and 9.1–11.4% points for the combined-cycle power plants. Also, it was found that the calcium looping process can be used to develop a novel high-efficiency (46.7%LHV) coal-fired power generation system, making this technology even more promising compared to the other CO2 capture technologies.

Lime-based sorbents for high-temperature CO2 capture--a review of sorbent modification methods.

This paper presents a review of the research on CO2 capture by lime-based looping cycles undertaken at CanmetENERGY’s (Ottawa, Canada) research laboratories. This is a new and very promising technology that may help in mitigation of global warming and climate change caused primarily by the use of fossil fuels. The intensity of the anticipated changes urgently requires solutions such as more cost-effective technologies for CO2 capture. This new technology is based on the use of lime-based sorbents in a dual fluidized bed combustion (FBC) reactor which contains a carbonator—a unit for CO2 capture, and a calciner—a unit for CaO regeneration. However, even though natural materials are cheap and abundant and very good candidates as solid CO2 carriers, their performance in a practical system still shows significant limitations. These limitations include rapid loss of activity during the capture cycles, which is a result of sintering, attrition, and consequent elutriation from FBC reactors. Therefore, research on sorbent performance is critical and this paper reviews some of the promising ways to overcome these shortcomings. It is shown that reactivation by steam/water, thermal pre-treatment, and doping simultaneously with sorbent reforming and pelletization are promising potential solutions to reduce the loss of activity of these sorbents over multiple cycles of use.

High-Purity Hydrogen via the Sorption-Enhanced Steam Methane Reforming Reaction over a Synthetic CaO-Based Sorbent and a Ni Catalyst

Sorbent-enhanced steam methane reforming (SE-SMR) is an emerging technology for the production of high-purity hydrogen from hydrocarbons with in situ CO2 capture. Here, SE-SMR was studied using a mixture containing a Ni-hydrotalcite-derived catalyst and a synthetic, Ca-based, calcium aluminate supported CO2 sorbent. The fresh and cycled materials were characterized using N2 physisorption, X-ray diffraction, and scanning and transmission electron microscopy. The combination of a Ni-hydrotalcite catalyst and the synthetic CO2 sorbent produced a stream of high-purity hydrogen, that is, 99 vol % (H2O- and N2-free basis). The CaO conversion of the synthetic CO2 sorbent was 0.58 mol CO2/mol CaO after 10 cycles, which was more than double the value achieved by limestone. The favorable CO2 capture characteristics of the synthetic CO2 sorbent were attributed to the uniform dispersion of CaO on a stable nanosized mayenite framework, thus retarding thermal sintering of the material. On the other hand, the cycled limestone lost its nanostructured morphology completely over 10 SE-SMR cycles due to its intrinsic lack of a support component.

Integration of calcium and chemical looping combustion using composite CaO/CuO-based materials.

Calcium looping cycles (CaL) and chemical looping combustion (CLC) are two new, developing technologies for reduction of CO(2) emissions from plants using fossil fuels for energy production, which are being intensively examined. Calcium looping is a two-stage process, which includes oxy-fuel combustion for sorbent regeneration, i.e., generation of a concentrated CO(2) stream. This paper discuss the development of composite materials which can use copper(II)-oxide (CuO) as an oxygen carrier to provide oxygen for the sorbent regeneration stage of calcium looping. In other words, the work presented here involves integration of calcium looping and chemical looping into a new class of postcombustion CO(2) capture processes designated as integrated CaL and CLC (CaL-CLC or Ca-Cu looping cycles) using composite pellets containing lime (CaO) and CuO together with the addition of calcium aluminate cement as a binder. Their activity was tested in a thermogravimetric analyzer (TGA) during calcination/reduction/oxidation/carbonation cycles. The calcination/reduction typically was performed in methane (CH(4)), and the oxidation/carbonation stage was carried out using a gas mixture containing both CO(2) and O(2). It was confirmed that the material synthesized is suitable for the proposed cycles; with the very favorable finding that reduction/oxidation of the oxygen carrier is complete. Various schemes for the Ca-Cu looping process have been explored here that would be compatible with these new composite materials, along with some different possibilities for flow directions among carbonator, calciner, and air reactor.

A study of thermal-cracking behavior of asphaltenes

Asphaltenes are problematic substances for heavy-oil upgrading processes. Recently interesting findings on thermal-cracking kinetics of an asphaltenic residue were reported, but a proposed model which considered parallel reactions for oil + gas and coke formation could not describe the behavior at higher temperatures. It was suggested that in such cases oils participated in secondary coke-forming reactions. Here we reexamine the data and give the expression for the oil + gas yield as a function of asphaltene conversion or residence time, which describes the data well. Further, we show that an empirical relation for coke formation and asphaltene conversion gives a reasonable description of the kinetics and prediction of the cracking behavior at high conversion level or long residence time, and that this method is much simpler. The maximum yield of oil + gas and the conversion level corresponding to the maximum yield can also be predicted easily. Further, our proposed approach is not dependent on assumed reaction orders of cracking.

Pressurized fluidized bed combustion

Introduction. Fluidization fundamentals. Pressurized combustion in FBC systems. General configuration of a PFBC plant. Solids preparation and handling. The pressurized combustor. High-temperature particulate control. Air emissions from pressurized fluidized bed combustors. The disposal and utilization of ash residues from pressurized fluidized bed combustion (PFBC). The combined cycle. Energy and exergy analysis of PFBC power plants. Process control outline. The demonstration units: Escatron and Tidd, four years of operation. Economics of pressurized fluidized bed combustion technology. Experimental and demonstration plants.