Development of iron oxide sorbents for Hg removal from coal derived fuel gas: Sulfidation characteristics of iron oxide sorbents and activity for COS formation during Hg removal

The aim of this study is to develop a process for the removal of Hg⁰ using H₂S over iron oxides sorbents, which will be located just before the wet desulfurization unit and catalytic COS converter of a coal gasification system. It is necessary to understand the reactions between the iron oxide sorbent and other components of the fuel gas such as H₂S, CO, H₂, H₂O, etc. In this study, the sulfidation behavior and activity for COS formation during Hg⁰ removal from coal derived fuel gas over iron oxides prepared by precipitation and supported iron oxide (1 wt% Fe₂O₃/TiO₂) prepared by conventional impregnation were investigated. The iron oxide samples were dried at 110 °C (designated as Fe₂O₃-110) and calcined at 300 and 550 °C (Fe₂O₃-300 and Fe₂O₃-550). The sulfidation behavior of iron oxide sorbents in coal derived fuel gas was investigated by thermo-gravimetric analysis (TGA). COS formation during Hg⁰ removal over iron oxide sorbents was also investigated using a laboratory-scale fixed-bed reactor. It was seen that the Hg⁰ removal activity of the sorbents increased with the decrease of calcinations temperature of iron oxide and extent of sulfidation of the sorbents also increased with the decrease of calcination temperature. The presence of CO suppressed the weight gain of iron oxide due to sulfidation. COS was formed during the Hg⁰ removal experiments over Fe₂O₃-110. However, in the cases of calcined iron oxides (Fe₂O₃-300, Fe₂O₃-550) and 1 wt% Fe₂O₃/TiO₂, formation of COS was not observed but the Hg⁰ removal activity of 1 wt% Fe₂O₃/TiO₂ was high. Both FeS and FeS₂ were active for Hg⁰ removal in coal derived fuel gas without forming any COS.     

Development of iron-based sorbents for Hg0 removal from coal derived fuel gas: Effect of hydrogen chloride

Laboratory studies were conducted to develop an elemental mercury (Hg⁰) removal process based on the reaction of H₂S and Hg⁰ using iron-based sorbents for coal derived fuel gas. It is well known that hydrogen chloride (HCl) is present in fuel gases derived from some types of coal, but the effect of HCl on the Hg⁰ removal performance of iron-based sorbents in coal derived fuel gas is not yet well understood. In this study, the effects of HCl on the removal of Hg⁰ from coal derived fuel gases over iron-based sorbents such as iron oxide (Fe₂O₃), supported iron oxides on TiO₂, iron oxide–Ca(OH)₂, and iron sulfides were investigated. The Hg⁰ removal experiments were carried out in a laboratory-scale fixed-bed reactor at 80 °C using simulated fuel gas. In the case of iron oxide (Fe₂O₃), the presence of HCl suppressed the Hg⁰ removal rate. In the case of Fe₂O₃ (2 or 5 wt%)/TiO₂, the presence of HCl did not suppress the Hg⁰ removal rate and the activity was stable. The Hg⁰ removal performance of reagent FeS₂ was higher than that of the iron oxide, and not affected by the presence of HCl. The Hg⁰ removal rate of iron oxide–Ca(OH)₂ was not effected by the presence of HCl, because HCl was captured by Ca(OH)₂. The reagent FeS₂ showed higher Hg⁰ removal activity than that of FeS₂ ore. However, the Hg⁰ removal performance of ground and kneaded FeS₂ ore was comparable to that of reagent FeS₂ probably due to the increase in porosity of the FeS₂ ore by grinding and kneading.     

Removal of sulfur at high temperatures using iron-based sorbents supported on fine coal ash

This paper deals with the simultaneous removal of H₂S and COS in the temperature range of 400-650 °C at 1 bar by using iron-based sorbents. The iron-based sorbents were prepared using iron oxide and cerium oxide with coal fine ash as the support. Simulated coal gas was used in the sulfidation experiments and 5% O₂ in N₂ gas was used for regeneration of sorbents. Both sulfidation and regeneration experiments have been carried out using a fixed-bed quartz reactor. The product gases were analyzed using a GC equipped with a TCD and a FPD. The results demonstrated that both H₂S and COS can be effectively reduced using the iron-based sorbents supported on fine coal ash. XRD analysis shows that Fe_1−xS phase has formed during sulfidation indicating a high sulfur capacity of the sorbent. The mechanism of the removal of COS simultaneously with H₂S is also discussed.     

Palladium based sorbents for high temperature arsine removal from fuel gas

The use of Pd-based sorbents for high temperature removal of AsH₃ from gasified coal was investigated using a simulated gas feed. A sorbent consisting of 5 wt% Pd on alumina beads has been tested for AsH₃ removal from synthetic fuel gas (CO, CO₂, H₂) at 204 and 288 °C. Arsenic uptake was found to be essentially linear with exposure time and considerably higher than that for unpromoted alumina beads. Arsenic loadings in excess of 7 wt% were achieved, though the sorbent is unlikely to be saturated at this loading. As the arsenic loading on the sorbent increased a PdAs₂ phase was identified in the XRD pattern. The adsorption of arsine on palladium has potential implications for catalysts, electrodes, and membranes for the separation of hydrogen from fuel gas.     

Sorption-enhanced water gas shift reaction by sodium-promoted calcium oxides

The water gas shift reaction was evaluated in the presence of novel carbon dioxide (CO₂) capture sorbents, both alone and with catalyst, at moderate reaction conditions (i.e., 300-600 °C and 1-11.2 atm). Experimental results showed significant improvements to carbon monoxide (CO) conversions and production of hydrogen (H₂) when CO₂ sorbents are incorporated into the water gas shift reaction. Results suggested that the performance of the sorbent is linked to the presence of a Ca(OH)₂ phase within the sorbent. Promoting calcium oxide (CaO) sorbents with sodium hydroxide (NaOH) as well as pre-treating the CaO sorbent with steam appeared to lead to formation of Ca(OH)₂, which improved CO₂ sorption capacity and WGS performance. Results suggest that an optimum amount of NaOH exists as too much leads to a lower capture capacity of the resultant sorbent. During capture, the NaOH-promoted sorbents displayed a high capture efficiency (nearly 100%) at temperatures of 300-600 °C. Results also suggest that the CaO sorbents possess catalytic properties which may augment the WGS reactivity even post-breakthrough. Furthermore, promotion of CaO by NaOH significantly reduces the regeneration temperature of the former.     

Mercury control testing in a pulverized lignite-fired system

The Energy & Environmental Research Center (EERC) is evaluating and developing advanced and innovative concepts for controlling Hg emissions from North Dakota lignite-fired power plants with the goal of achieving 50%–90% Hg removal at one-half to three-fourths the current estimated costs. Pilot-scale tests were performed to evaluate potential sorbents and fuel additives for removing Hg from North Dakota lignite (Freedom and Center Mines) combustion flue gases. The Hg sorbents and Hg⁰ oxidation and sorbent enhancement additives were evaluated separately, and most were also tested in combination. A 580 MJ/h (550,000 Btu/h) pulverized coal combustion system was used to conduct sorbent injections and/or lignite additive additions upstream of three particulate control devices (PCDs): 1) an electrostatic precipitator (ESP), 2) a spray dryer and fabric filter, and 3) a retrofit advanced hybrid particulate collector (AHPC) filter (an ESP followed by an AHPC filter). ASTM International Method D6784-02 (Ontario Hydro method) and continuous Hg monitors were used to measure Hg species concentrations across the control devices. The effects of sorbent injection and coal additive addition rates on Hg removal were evaluated for each PCD option. The effects of continuous injection and batch addition of sorbents on the Hg removal performance of the ESP/AHPC filter system were also investigated. Increasing injection and additive rates and improving contact between the sorbents and flue gases generally promoted Hg capture. Most of the coal additives tested significantly enhanced PCD Hg removal, especially in the presence of a sorbent.     

Reactivity of Metal Oxide Sorbents for Removal of Sulfur Compounds from Coal Gases at High Temperature and Pressure

Abstract

Hot-gas desulfurization for the integrated gasification combined cycle (IGCC) process has been investigated to effectively remove hydrogen sulfide with various metal oxide sorbents at high temperatures and pressures. Metal oxide sorbents such as zinc titanate oxide, zinc ferrite oxide, copper oxide, manganese oxide, and calcium oxide were found to be promising sorbents in comparison with other removal methods such as membrane separation and reactive membrane separation. The removal reaction of H₂S from coal gas mixtures with zinc titanate oxide sorbents was conducted in a batch reactor. The main objectives of this research are to formulate promising metal oxide sorbents for removal of hydrogen sulfide from coal gas mixtures, to compare reactivity of a formulated sorbent with a sorbent supplied by the Research Triangle Institute at high temperatures and pressures, and to determine effects of concentrations of moisture contained in coal gas mixtures, and to determine effects of concentrations of moisture contained in coal gas mixtures on equilibrium absorption of H₂S into metal oxide sorbents. Promising durable metal oxide sorbents with high-sulfur-absorbing capacity were formulated by mixing active metal oxide powders with inert metal oxide powders and calcining these powder mixtures.     

Research progress of hot gas filtration,desulphurization and HCl removal in coal-derived fuel gas: A review

The present review paper highlighted on the recent progress of hot gas filtration, desulphurization and HCl removal in coal-derived fuel gas for combined cycle power generation (IGCC) or molten carbonate fuel cells (MCFC) technologies. As a critical process in the gasification system, hot gas filtration in the particulate control device (PCD) was introduced with enhanced understanding of equipment and operation, filter element and failsafe material properties, and gasification ash characteristics. The issues associated with the commercialization of hot gas filtration were also addressed, and some novel systems and methods were also discussed. The hot gas desulphurization in coal-derived fuel gas has concentrated on developing regenerable sorbents including the single and composite oxides of Zn, Fe, Cu, Mn and other species, and the reduction of metal oxides in the highly reducing atmosphere followed by vaporization of elements can be a problem for reactivity and regeneration. With regard to the removal of HCl, the studies have indicated sorbents prepared by pelletizing the powders of naturally available alkali metal and alkali earth metal substances can rapidly react with HCl vapor and reduce the HCl vapor concentration to less than 1 ppmv, and some sorbents lab-made have very high chlorine capacity. The sorbents based hot gas cleaning also has some challenges. Kinetics studies showed that unreacted shrinking core (USC) can be applied to the modeling of H₂S and HCl removal by sorbents at high temperature, and the surface chemical reaction and reactant diffusion by product layers between solid sorbents and gases were very important mechanisms. The paper also proposed and discussed a rational concept for the simultaneous removal of multiple contaminants including ash, H₂S and HCl, which will offer a possible cost reduction by two or more processes in a single vessel for hot gas cleaning.     

Characteristics of the mercury vapor removal from coal combustion flue gas by activated carbon using H2S

Removal of Hg⁰ vapor from the simulated coal combustion flue gases with a commercial activated carbon was investigated using H₂S. This method is based on the reaction of H₂S and Hg over the adsorbents. The Hg⁰ removal experiments were carried out in a conventional flow type packed bed reactor system in the temperature range of 80–150 °C using simulated flue gases having the composition of Hg⁰ (4.9 ppb), H₂S (0–20 ppm), SO₂ (0–487 ppm), CO₂ (10%), H₂O (0–15%), O₂ (0–5%), N₂ (balance gas). The following results were obtained: in the presence of both H₂S and SO₂, Hg removal was favored at lower temperatures (80–100 °C). At 150 °C, presence of O₂ was indispensable for Hg⁰ removal from H₂S–SO₂ flue gas system. It is suggested that the partial oxidation of H₂S with O₂ to elemental sulfur (H₂S+1/2O₂=S_ad+H₂O) and the Clause reaction (SO₂+2H₂S=3S_ad+2H₂O) may contribute to the Hg⁰ removal over activated carbon by the following reaction: S_ad+Hg=HgS. The formation of elemental sulfur on the activated carbon was confirmed by a visual observation.     

锰系可再生高温脱硫剂的制备及其性能测试

煤气的高温脱硫净化是 IGCC 和 DRI 生产的瓶颈,直接影响整个过程的热效率。在50℃、pH值约为9的条件下采用硝酸锰、硝酸铝混合溶液与氨水进行共沉淀,制备了锰含量不同的脱硫剂,在固定床反应器中考察了脱硫剂的硫化及再生性能,并利用XRD、SEM、BET等手段表征了脱硫剂在硫化/再生过程中的物相和结构变化。共沉淀法制备的脱硫剂Mn/Al分散性好,在850℃高温下进行脱硫反应可以定量快速进行。脱硫硫容与脱硫剂锰含量呈正比,Mn-S/Mn-O交换原子比在0.90~0.95之间,改变空速和进口H₂S含量并不改变脱硫硫容。采用O₂浓度为3%的稀释空气在850℃下再生,再生后的硫容稳定,说明所制备的脱硫剂可用于高温可再生脱硫。     

NH3 and HCN formation during the gasification of three rank-ordered coals in steam and oxygen

A Victorian brown coal (68.5% C), a Chinese high-volatile Shenmu bituminous coal (82.3% C) and a Chinese low-volatile Dongshan bituminous coal (90% C) were gasified in a fluidised-bed/fixed-bed reactor at 800 °C in atmospheres containing 15% H₂O, 2000 ppm O₂ or 15% H₂O + 2000 ppm O₂. While the gasification of these coals in 2000 ppm O₂ converted less than 27% of coal-N into NH₃, the introduction of steam played a vital role in converting a large proportion of coal-N into NH₃ by providing H on char surface. The importance of the roles of steam in the formation of NH₃ in atmospheres containing 15% H₂O + 2000 ppm O₂ decreased with increasing coal rank. This is largely due to the slow gasification of high-rank coal chars, resulting in low availability of H on char surface. The gasification of chars from the high-rank coal appears to produce higher yields of HCN than that of lower rank coals, probably as a result of the decomposition of partially hydrogenated/broken/activated char-N structures during gasification at high temperature. The alkali and alkaline earth metallic species in brown coal tend to favour the release of coal-N as tar-N but have limited effects on char-N conversion during gasification.     

Oxygen reduction by Fe-based catalysts in PEM fuel cell conditions: Activity and selectivity of the catalysts obtained with two Fe precursors and various carbon supports

Fe-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cell conditions have been prepared by adsorbing two Fe precursors on various commercial and developmental carbon supports. The resulting materials have been pyrolyzed at 900 °C in an atmosphere rich in NH₃. The Fe precursors were: iron acetate (FeAc) and iron tetramethoxy phenylporphyrin chloride (ClFeTMPP). The nominal Fe content was 2000 ppm (0.2 wt.%). The carbon supports were HS300, Printex XE-2, Norit SX-Ultra, Ketjenblack, EC-600JD, Acetylene Black, Vulcan XC-72R, Black Pearls 2000, and two developmental carbon black powders, RC1 and RC2 from Sid Richardson Carbon Corporation. The catalyst activity for ORR has been analyzed in fuel cell tests at 80 °C as well as by cyclic voltammetry in O₂ saturated H₂SO₄ at pH 1 and 25 °C, while their selectivity was determined by rotating ring-disk electrode in the same electrolyte. A large effect of the carbon support was found on the activity and on the selectivity of the catalysts made with both Fe precursors. The most important parameter in both cases is the nitrogen content of the catalyst surface. High nitrogen content improves both activity towards ORR and selectivity towards the reduction of oxygen to water (4e⁻ reaction). A possible interpretation of the activity and selectivity results is to explain them in terms of two Fe-based catalytic sites: FeN₂/C and FeN₄/C. Increasing the relative amount of FeN₂/C improves both activity and selectivity of the catalysts towards the 4e⁻ reaction, while most of the peroxide formation may be attributed to FeN₄/C. When FeAc is used as Fe precursor, iron oxide and/or hydroxide are also formed. The latter materials have low catalytic activity for ORR and reduce O₂ mainly to H₂O₂.     

Corrosion behavior of SM 80SS tube steel in stimulant solution containing H2S and CO2

Scanning electron microscopy, X-ray diffraction and electrochemical measurement technique were applied to investigate the corrosion of SM 80SS tube steel in stimulant solution with carbon dioxide (CO₂) and hydrogen sulfide (H₂S) at variable conditions of PCO₂/PH₂S and temperature. The results suggest that there exists a synergism of sweet corrosion and sour corrosion on the steel surface, corrosion attack increases in the initial stage and then decrease with the increase of PCO₂ or PH₂S; serious corrosion occurs in the PCO₂/PH₂S ranged from 31 to 520. In addition, the fitted parabola function equation Y = 0.47873 + 0.04014X - (3.23788E−5)X² is established, and the most serious corrosion is 600 for PCO₂/PH₂S. Under the moderate contents of PCO₂ and PH₂S, the corrosion scale consists of FeS_0.9 and FeCO₃; for relatively high PH₂S, additive product FeS comes into being at high temperature such as T = 150 °C, product FeO(OH) is found in the corrosion scale. The H₂S corrosion has a significant effect on the whole reaction process and iron sulfide is superior to precipitating on the steel surface compared with iron carbonate. In addition, the surface scales of iron sulfide almost act as a diffusion barrier and inhibit the corrosion by a coverage effect strongly depending on H₂S concentration by EIS measurement.     

Desulfurization matching with coal poly-generation system based on dual gas resources

The coal poly-generation system for the production of alcohol and ether fuels as well as power is one of advanced coal utilization techniques. The team leaded by Professor Xie Kechang is carrying out the research on the poly-generation system to produce the syngas from the combination of gasified and pyrolyzed coal gas (dual gas resources) for the alcohol ether synthesis. Gas desulfurization is one of the key technologies for this system. The desulfurization matching with dual gas resources based poly-generation system for the production of alcohol and ether fuels as well as power is presented according to gas components, sulfur content, sulfur species and desulfurization accuracy in this technology. This matching desulfurization is classified into hot gas desulfurization, normal gas desulfurization, warm gas desulfurization and organic sulfur catalytic conversion. The preparation of H₂S removal sorbents, organic sulfur hydrolysis catalyst and the evaluation of their activities involved in the system were investigated. The H₂S removal efficiencies of the crude and fine desulfurization sorbents prepared for hot gas desulfurization are 90% and 99% at 500 °C in simulating coal gas, and their sulfur capacities are 21.85 wt.% and 24.91 wt.%, respectively. The organic sulfur catalyst shows the high hydrolysis activity, and the hydrolysis conversion of COS is more than that of CS₂ on the same catalyst. The research will provide necessary information for the matching desulfurization technology in the demonstration project on dual gas resources coal poly-generation system.     

Effects of reduction of metal oxide sorbents on reactivity and physical properties during hot gas desulphurization in IGCC

In this study, the changes of physical properties and reactivity of the metal oxide sorbents were investigated under the reducing conditions of coal gas. Metal oxide sorbents are converted into metal sulphides as a result of reaction with H₂S in synthesis gas. This could cause the reduced reactivity of sorbents if the metal oxides were converted into metallic elements due to the reduction by either hydrogen or carbon monoxide. In this experiment, the changes of physical properties and reactivity of the metal oxides were investigated over the temperature range 480-700 °C. It is confirmed that the reactivity of sulphidation and the reduction of metal oxide increased with increasing temperature. Even though the sulphur capacity of the sorbents in the early stage was high, it reduced rapidly due to the progressive reduction of metal oxides as the sulphidation/regeneration process was repeated. The reduction of metal oxide and the extent of reduction were verified by measuring the amount of oxygen consumed and the amount of SO₂ produced during the regeneration of sulphidated sorbents with the aids of a gas analyser. It was concluded that the reactivity of the metal oxide sorbents was influenced by reduction with coal gas at high temperature.     

Iron oxide supported sulfated TiO2 nanotube catalysts for NO reduction with propane

Sulfated TiO₂ nanotubes and a series of iron oxide loaded sulfated TiO₂ nanotubes catalysts with different iron oxide loadings (1 wt%, 3 wt%, 5 wt% and 7 wt%) were prepared and calcined at 400 °C. The physico-chemical properties of the catalysts were studied by using XRD, N₂-physisorption, Raman spectroscopy, SEM-EDX, TEM, XPS, and pyridine adsorption using FTIR and H₂-TPR techniques. It was observed that iron oxide was highly dispersed on the sulfated TiO₂ nanotube support due to its strong interaction. The activity of these catalysts in the catalytic removal of NO with propane was also studied in the temperature range of 300–500 °C. Highest activity (90% NO conversion) was observed with 5 wt% iron oxide supported on sulfated TiO₂ catalyst at 450 °C. Selective catalytic reduction of NO activity of the catalysts was correlated with iron oxide loading, reducibility, and the Brönsted and Lewis acid sites of the catalysts. The catalyst also showed good stability under studied reaction conditions that no deactivation was observed during the 50 h of reaction.     

Kinetic behaviour of iron oxide sorbent in hot gas desulfurization

Although a number of reports on sorbents containing ZnO for H₂S removal from coal-derived gases can be found in the literature, it is shown in our study that a special sorbent containing Fe₂O₃·FeO (SFO) with minor promoters (Al₂O₃, K₂O, and CaO) as the main active species is more attractive for both sulfidation and regeneration stages, also under economic considerations. This paper presents the kinetic behaviour of SFO in a hot gas desulfurization process using a thermogravimetric analysis under isothermal condition in the operating range between 500 and 800 °C. The gas stream was N₂ with a 2% wt of H₂S. Experiences carried out on sorbent sulfidation with SFO (particle sizes in the range of 0.042-0.12 mm) indicate that the sorbent sulfidation capacity sharply increases with temperature in the range of 500-600 °C. It is also shown that the sample weight reaches its maximum absorption capacity, near saturation, at 600 °C so that it makes no sense to increase the sulfidation temperature from this point. To make a comparison between SFO and a zinc titanate based sorbent, a set of sulfidation tests was carried out at 600 °C during 7200 s using the same sieve range for both sorbents between 42 and 90 μm. Results show that the sulfidation capacity of SFO is 1.9 times higher than that of zinc titanate.     

Efficient oxidative desulfurization (ODS) of model fuel with H2O2 catalyzed by MoO3/γ-Al2O3 under mild and solvent free conditions

An efficient process to remove organic sulfur compounds from model fuel has been explored. Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) can be completely oxidized into their corresponding sulfones by H₂O₂ over 14 wt.% MoO₃/γ-Al₂O₃ catalyst under mild conditions in 15 min. The effects of solvent, initial sulfide concentration, loading of MoO₃ and amount of catalyst on oxidative removal of DBT were studied. The employments of solvents have decreased the reaction rate of DBT, which can be attributed to the competitive adsorption between the sulfide and solvent. The oxidative reactivity increases in the order of thiophene (Th) < benzothiophene (BT) < DBT < 4, 6-DMDBT. The catalyst can be regenerated by methanol washing at 333 K.     

Processing and performance of solid oxide fuel cell with Gd-doped ceria electrolyte

Fuel Cell performance was measured at 792-1095 K for Ni-GDC (Gd-doped ceria) anode-supported GDC film (60 μm thickness) with a (La_0.8Sr_0.2)(Co_0.8Fe_0.2)O₃ cathode using H₂ fuel containing 3 vol% H₂O. A maximum power density, 436 mW/cm², was obtained at 1095 K. The electrical conductivity of GDC electrolyte in N₂ atmosphere of 10⁻¹⁵-10⁰ Pa oxygen partial pressures (Po₂) at 773-1073 K was independent of Po₂, which indicated the diffusion of oxide ions. The conductivity of GDC in H₂O/H₂ atmosphere increased because of the further formation of electrons due to the dissociation of hydrogen in GDC (H₂ → 2H⁺ + 2e⁻). The hole conductivity was observed at 873 K in Po₂ = 10⁰-10⁴ Pa. The key factors in increasing power density are the increase of open circuit voltage and the suppression of H₂ fuel dissolution in GDC electrolyte. These are controlled by the cathode material and Gd-dopant composition.     

In situ gasification of a lignite coal and CO2 separation using chemical looping with a Cu-based oxygen carrier

Chemical looping combustion (CLC) has the inherent property of separating CO₂ from flue gases. This paper is concerned with the application of chemical looping to the combustion of a solid fossil fuel (a lignite and its char) in a technique whereby the fuel is gasified in situ using CO₂ in the presence of a batch of supported copper oxide (the “oxygen carrier”) in a single reactor. As the metal oxide becomes depleted, the feed of fuel is discontinued, the inventory of fuel is reduced by further gasification and then the contents are re-oxidised by the admission of air to the reactor, to begin the cycle again. The choice of oxides is restricted because it requires an oxide which is exothermic during reduction to balance the endothermic gasification reactions. Copper has such oxides, but a key question is whether or not it can withstand temperatures at which gasification rates are significant (∼1173 K), particularly from the point of view of avoiding sintering and deactivation of the carrier in its reduced form. It was found that an impregnated carrier, made by impregnating a θ-alumina catalyst support (BET area 157 m²/g) with a saturated solution of copper and aluminium nitrates, acted as a durable carrier over 20 cycles of reduction and oxidation, using both Hambach lignite coal, and its char, and with air as the oxidising agent. During the course of the experiments, the BET surface area of the support fell from ∼60 m²/g, just after preparation, to around 6 m²/g after 20 cycles. However, this fall did not appear to affect the overall capacity of the oxygen carrier to react with fuels and its effect on the kinetics of the reaction with CO did not influence the outcome of the experiments, since the overall performance of the looping scheme is dominated by the much slower kinetics of the gasification reaction. The apparent kinetics of the gasification are faster in the presence of the looping agent: this is because the bulk concentration of CO in the presence of the looping agent is lower, and partly because the destruction of CO in the vicinity of a gasifying particle enhances the rate of removal of CO by mass transfer (and increases the local concentration of CO₂). There was little evidence to suggest a direct reaction between carbonaceous and carrier solids, other than via a gaseous intermediate. However, the observation of finite rates of conversion in a bed of active carrier, fluidised by nitrogen, is a scientific curiosity, which we have not been able to explain satisfactorily. At 1173 K, as used here, rates of gasification of Hambach lignite, and its char, are significant. The CuO in the carrier decomposes at 1173 K to produce gas-phase O₂ and Cu₂O: both can react with CO produced by gasification, whilst the O₂ can react directly with the char.