Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.     

Evaluating the potential of CNT-supported Co catalyst used for gas pollution removal in the incineration flue gas

This study investigated the use of Cu/Al₂O₃, Co/Al₂O₃, Fe/Al₂O₃, and Ni/Al₂O₃ catalysts for the growth of carbon nanotubes (CNTs). These CNTs were used as support for Co catalyst preparation and Co/CNT catalysts were applied to a catalytic reaction to remove BTEX, PAHs, SO₂, NO, and CO simultaneously in a pilot-scale incineration system. The analyzed results of EDS and XRD showed low metal content and good dispersion characteristics of the Al₂O₃-supported catalysts by excess-solution impregnation. FESEM analyzed results showed that the CNTs that were synthesized from Co, Fe, and Ni catalysts had a diameter of 20 nm, whereas those synthesized from Cu/Al₂O₃ had a diameter of 50 nm. Pilot-scale test results demonstrated that the Co/CNT catalyst effectively removed air pollutants in the catalytic reaction and that there was no obvious deactivation by Pb, water vapor, and coke deposited in the process. The thermal stabilization at 250 °C and hydrophobicity properties of CNTs enhanced the application of CNT catalysts in flue gas.     

Selective dissolution of critical metals from diesel and naptha spent hydrodesulphurization catalysts

The petroleum refining industry makes extensive use of catalysts, containing critical metals, such as, Mo, Co and Ni, for the desulphurization of various oil fractions. The selective recovery of these metals from two uncrushed and at low temperature calcined industrial hydrodesulphurization (Mo---Co/Al₂O₃ and Mo---Ni/Al₂O₃---SiO₂) catalysts was studied, applying a two-step alkali-acid procedure. Fundamental kinetic aspects of the process, such as, reaction time, leaching reagents concentration and reaction temperature, were studied. Recoveries up to 97% for Mo and up to 92% for Co or Ni in separate solutions were achieved, using low cost and easily available reagents, such as sodium hydroxide and sulphuric acid.     

Fuel cell system with sodium borohydride hydrogen generator for small unmanned aerial vehicles

A 100 W proton exchange membrane fuel cell (PEMFC) system with a sodium borohydride (NaBH₄) hydrogen generator was investigated for small unmanned aerial vehicles (UAVs). The performance of a cobalt–phosphorous/nickel foam catalyst was evaluated to determine the change in catalytic activity under real operating conditions. The response time increased owing to oxidation of the metals and accumulation of sodium; however, the catalyst remained active at high reaction temperatures. A NaBH₄ hydrogen generator with the catalyst was developed for a 100 W PEMFC system. The hydrogen generation rate was stable for 3 h, and the conversion efficiency was 97.8%. Finally, a 100 W PEMFC system with the NaBH₄ hydrogen generator was investigated for small UAVs. The maximum power and energy density of the PEMFC system were 95.96 W and 185.2 Wh/kg, respectively.     

Nanocatalyzed biodiesel synthesis from the oily contents of Marine brown alga Dictyota dichotoma

This research article demonstrates biodiesel synthesis through the methanolysis of the oily contents (4.02 ± 0.27% w/w on dried basis) of Dictyota dichotoma collected from the coast of Hawksbay, Pakistan. The metal oxides (CaO, MgO, ZnO, and TiO₂) used as nanocatalysts were refluxed (5% K₂SO₄), calcinated (850 °C) and characterized by Atomic Force Microscopy (AFM) which produced 93.2% w/w FAME (biodiesel) at relatively mild condition (5% catalyst, 65 °C, 3 h, 18:1 molar ratio) using CaO. Whereas, MgO, ZnO, and TiO₂ produced 92.4%, 72.5%, and 31.8% w/w FAME, respectively at elevated condition (225 °C). Thus, CaO was considered to be the best catalyst among the others. This tri-phase reaction require continuous fast mixing and the yield depends on the reaction parameters like catalyst amount, temperature, reaction time and molar ratio (methanol: oil). The reusability of these heterogeneous catalysts simplified the purification step, reduced the waste generation and make the final product technically and economically viable.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce CO_x-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr_0.8Mg_0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg_1.0 and Co/Zr_1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.     

Combined steam-dry reforming of toluene in syngas over CaNiRu/Al2O3 catalysts

Cracking, steam reforming, dry reforming, and combined steam and dry reforming of toluene in model syngas were performed using catalysts to simulate tar removal produced during biomass gasification. The catalysts were prepared by adding Ru, Ca, and Mn to Ni-based catalysts, and their properties were measured using BET, pulse CO chemisorption, XRD and TG. In steam and dry reforming of toluene, a high toluene conversion was observed with increasing Ca content in the catalyst and catalysts containing Ca showed a higher activity than those containing Mn. In combined steam-dry reforming with syngas, 1%CaNiRu/Al₂O₃ indicated a conversion of 93.9% at 800°C.     

Effect of calcination temperature on the application of sodium zirconate solid base catalyst for biodiesel production from Jatropha curcas oil

Influence of catalyst calcination temperature on the catalyst characteristics and catalytic transesterification of Jatropha curcas oil for biodiesel production was studied by using sodium zirconate (Na₂ZrO₃) solid base catalyst. Na₂ZrO₃ catalysts were prepared by impregnation method followed by calcination at temperatures of 700, 800, and 900°C. The prepared catalysts were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, and field emission scanning electron microscopy. Important parameters influencing the catalytic activity and fatty acid methyl ester yield were investigated. It was found that the increase in calcination temperature showed marked increase in activity due to the increased porosity and presence of tetragonal zirconia. Investigation of the reusability of the catalysts showed that the catalytic activity was retained even after five cycles of reaction.     

Producing biodiesel from waste animal oil by modified ZnO

Biodiesel produced by transesterification of waste animal oil is a promising green fuel in the future. ZnO-Al₂O₃ and ZnO/Zn₂Al composition oxides were prepared by co-precipitation method and impregnation method, respectively. The above catalysts were characterized by X-ray diffraction (XRD), Brunauer--Emmett--Teller (BET) and CO₂ adsorption and temperature-programmed desorption (CO₂-TPD) and show that the high activity for the catalyst is attributed to its high alkalinity. The reaction parameters were optimized and the results show that the transesterification ratio of waste animal oil can reach 98.7% with 10% ZnO/Zn₂Al catalyst after 2 h. Moreover, 10%ZnO/Zn₂Al compound oxides can be active for the successive cycles. The glycerol as a predominant by-product after transesterification is of high purity with high use value.     

Chemical-looping with oxygen uncoupling for combustion of solid fuels

Chemical-looping with oxygen uncoupling (CLOU) is a novel method to burn solid fuels in gas-phase oxygen without the need for an energy intensive air separation unit. The carbon dioxide from the combustion is inherently separated from the rest of the flue gases. CLOU is based on chemical-looping combustion (CLC) and involves three steps in two reactors, one air reactor where a metal oxide captures oxygen from the combustion air (step 1), and a fuel reactor where the metal oxide releases oxygen in the gas-phase (step 2) and where this gas-phase oxygen reacts with a fuel (step 3). In other proposed schemes for using chemical-looping combustion of solid fuels there is a need for an intermediate gasification step of the char with steam or carbon dioxide to form reactive gaseous compounds which then react with the oxygen carrier particles. The gasification of char with H₂O and CO₂ is inherently slow, resulting in slow overall rates of reaction. This slow gasification is avoided in the proposed process, since there is no intermediate gasification step needed and the char reacts directly with gas-phase oxygen. The process demands an oxygen carrier which has the ability to react with the oxygen in the combustion air in the air reactor but which decomposes to a reduced metal oxide and gas-phase oxygen in the fuel reactor. Three metal oxide systems with suitable thermodynamic properties have been identified, and a thermal analysis has shown that Mn₂O₃/Mn₃O₄ and CuO/Cu₂O have suitable thermodynamic properties, although Co₃O₄/CoO may also be a possibility. However, the latter system has the disadvantage of an overall endothermic reaction in the fuel reactor. Results from batch laboratory fluidized bed tests with CuO and a gaseous and solid fuel are presented. The reaction rate of petroleum coke is approximately a factor 50 higher using CLOU in comparison to the reaction rate of the same fuel with an iron-based oxygen carrier in normal CLC.     

Catalytic degradation of toxic organic dye using an aluminum-doped Cu0.4Zn0.6-xAlxFe2O4 (x = 0.0, 0.2, 0.4, 0.6) spinel ferrite in a photo-Fenton system

Catalytic activity of spinel ferrite in breaking down toxic dye materials are promising due to their uniqueness. In this study, aluminum-doped copper zinc ferrite, Cu_0.4Zn_0.6-xAl_xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6), a catalyst for toxic dye degradation is synthesized through chemical co-precipitation route. The formation of the spinel ferrite catalyst is initially confirmed by Fourier transform infrared spectra, which shows the frequency of metal-oxygen bond vibration at 539 and 427 cm⁻¹ attributed to the tetrahedral and octahedral sites respectively. Higher intensity sharp peak of X-ray diffraction for (311) plane is the evidence for the phase purity and the formation of spinel ferrite. The crystallite size is found to decrease with the increase of Al³⁺ ion. The surface structure of the obtained particles is investigated using a scanning electron microscope. Analyses of the material's magnetic characteristics using a vibrating sample magnetometer (VSM) revealed that it is, in fact, a soft magnet, as evidenced by the loop of its hysteresis, which is narrow. The catalytic degradation of methylene blue dye under the mechanism of the photo-Fenton process is studied with the obtained spinel ferrites and the result is found to be as high as 96.5%. The process follows pseudo-second order kinetics and the Langmuir isotherm.     

Design and optimization of new La1−xCexNi1−yFeyO3 (x,y = 0–0.4) nano catalysts in dry reforming of methane

The paper reports the production of syngas from dry reforming of methane (DRM) over La_1?xCe_xNi_1?yFe_yO₃ (x, y = 0–0.4) perovskites. A series of La_1?xCe_xNi_1?yFe_yO₃ were designed by central composite design (CCD) and synthesized by a sol–gel auto combustion method. Artificial neural network (ANN) approach was used to determine the relationship between preparation and operational parameters on the performance of the catalysts in the DRM process. Nickel mole fraction, lanthanum mole fraction, calcination temperature, and reaction temperature were considered as input variables, and conversion of methane was considered as the output variable. An ANN model with nine neurons in the hidden layer was the suitable in predicting conversion of methane. The genetic algorithm (GA) was subsequently used to determine the optimal preparation condition for enhancing the conversion of methane. La_0.6Ce_0.4Ni_0.99Fe_0.01O₃ catalyst, calcined at 756°C was obtained to be the most active catalyst owing to the optimal composition of nickel and lanthanum in the catalyst formulation.     

Heterostructure CdS/ZnS nanoparticles as a visible light-driven photocatalyst for hydrogen generation from water

(CdS)_x/(ZnS)_1–x nanoparticles were synthesized as a visible light-driven photocatalyst using the stepped microemulsion technique with a series of the ratio factors (x). The photocatalytic test results showed that (CdS)_x/(ZnS)_1-x with x = 0.8 had the highest photo-reactivity for H₂ production from water under visible light. The composite (CdS)_0.8/(ZnS)_0.2 catalyst had a heterogeneous structure that exhibited a much greater photocatalytic hydrogen production activity than either pure CdS or the homogeneous Cd_0.8Zn_0.2S solid solution. ZnS deposition also was shown to largely improve the stability of CdS in the heterostructured CdS/ZnS catalyst. Thermal treatment of the catalyst, i.e., annealing (CdS)_0.8/(ZnS)_0.2 at 723 K, improved the crystallinity of the catalyst and increased its photocatalytic H₂ production rate by more than 36 times. Deposition of Ru on the surface of the catalyst particles by in situ photo-deposition further increased the photo-H₂ generation rate by 3 times. The photocatalyst of 0.5%Ru/CdS/ZnS achieved the highest H₂ production activity, at a rate of 12650 μmol/g-h and with a light to hydrogen energy conversion efficiency of 6.5%.     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

Production of Fe2O3 from FeSO4·xH2O formed in galvanizing works

FeSO₄·xH₂O is generated in large amounts in galvanizing workshops. It can be reutilized by conversion to Fe₂O₃. In this study, the recovery of Fe₂O₃ from FeSO₄·xH₂O formed in the galvanizing process has been examined. The experimental work was carried out at various temperatures and times in the oxidizing medium. The reaction temperatures and times were selected as 450, 500, 550, 600, 650, 700, 800 and 900°C, and 15, 30, 45, 60, 90 and 120 minutes, respectively. In order to determine the amount of Fe₂O₃, a titrimetric method was applied. The reaction products were characterized by means of IR and XRD techniques.The extent of conversion is low at temperatures below 650°C. Almost all of the iron (II) sulfate in the original sample was converted to iron(III) oxide at 650°C (120 min), 700°C (90 min), 800°C (60 min) and 900°C (45 min).     

Energy conversion from electrolyte concentration gradient using charged nano-pores

Power generation based on the reversed electro-dialysis (RED) cell is studied both numerically and experimentally in this work. The membrane that separates the concentrated and dilute electrolytes is treated as a charged nano-pore array. Both numerical and experimental results show that the RED cell performance is similar to the typical electrochemical cell having a linearly varied current–voltage relation. The open circuit voltage and short-circuit current depend on the ion selectivity of the nano-pore membrane, which is related to the concentration ratio, pore surface charge density, and pore size. The highest energy conversion efficiencies are approximately 48% and 24% from numerical predictions and experimental measurements, respectively. The reason for this discrepancy is attributed to the inhomogenous pore size and surface charge density distributions of the Al₂O₃ membrane used in these experiments.     

Solid fuels in chemical-looping combustion

The feasibility of using a number of different solid fuels in chemical-looping combustion (CLC) has been investigated. A laboratory fluidized bed reactor system for solid fuel, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions, was used. In each reducing phase 0.2 g of fuel in the size range 180–250 μm was added to the reactor containing 40 g oxygen carrier of size 125–180 μm. Two different oxygen carriers were tested, a synthetic particle of 60% active material of Fe₂O₃ and 40% MgAl₂O₄ and a particle consisting of the natural mineral ilmenite. Effect of steam content in the fluidizing gas of the reactor was investigated as well as effect of temperature. A number of experiments were also made to investigate the rate of conversion of the different fuels in a CLC system. A high dependency on steam content in the fluidizing gas as well as temperature was shown. The fraction of volatiles in the fuel was also found to be important. Furthermore the presence of an oxygen carrier was shown to enhance the conversion rate of the intermediate gasification reaction. At 950 °C and with 50% steam the time needed to achieve 95% conversion of fuel particles with a diameter of 0.125–0.18 mm ranged between 4 and 15 min depending on the fuel, while 80% conversion was reached within 2–10 min. In almost all cases the synthetic Fe₂O₃ particle with 40% MgAl₂O₄ and the mineral ilmenite showed similar results with the different fuels.     

Purification of oxyfuel-derived CO2

Oxyfuel combustion in a pulverised fuel coal-fired power station produces a raw CO₂ product containing contaminants such as water vapour plus oxygen, nitrogen and argon derived from the excess oxygen for combustion, impurities in the oxygen used, and any air leakage into the system. There are also acid gases present, such as SO₃, SO₂, HCl and NO_x produced as byproducts of combustion. At GHGT8 (White and Allam, 2006) we presented reactions that gave a path-way for SO₂ to be removed as H₂SO₄ and NO and NO₂ to be removed as HNO₃. In this paper we present initial results from the OxyCoal-UK project in which these reactions are being studied experimentally to provide the important reaction kinetic information that is so far missing from the literature. This experimental work is being carried out at Imperial College London with synthetic flue gas and then using actual flue gas via a sidestream at Doosan Babcock's 160 kW coal-fired oxyfuel rig. The results produced support the theory that SO_x and NO_x components can be removed during compression of raw oxyfuel-derived CO₂ and therefore, for emissions control and CO₂ product purity, traditional FGD and deNO_x systems should not be required in an oxyfuel-fired coal power plant.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.