Syngas Production from Lignite Coal Using K2CO3 Catalytic Steam Gasification with Controlled Heating Rate in Pyrolysis Step

Gasification uses steam increases H2 content in the syngas. Kinetics of gasification process can be improved by using K₂CO₃ catalyst. Controlled heating rate in pyrolysis step determines the pore size of charcoal that affects yield gas and H₂ and CO content in the syngas. In previous research, pyrolisis step was performed without considering heating rate in pyrolysis step. This experiment was performed by catalytic steam gasification using lignite char from pyrolysis with controlled heating rate intended to produce maximum yield of syngas with mole ratio of H₂/CO ≈ 2. Slow heating rate (3 °C/min) until 850 °C in the pyrolysis step has resulted in largest surface area of char. This study was performed by feeding Indonesian lignite char particles and K₂CO₃ catalyst into a fixed bed reactor with variation of steam/char mole ratio (2.2; 2.9; 4.0) and gasification temperature (750 °C, 825 °C, and 900 °C). Highest ratio of H₂/CO (1.682) was obtained at 750 °C and steam/char ratio 2.2. Largest gas yield obtained from this study was 0.504 mol/g of char at 900 °C and steam/char ratio 2.9. Optimum condition for syngas production was at 750 °C and steam/char mole ratio 2.2 with gas yield 0.353 mol/g of char and H₂/CO ratio 1.682.     

Effects of calcination and activation temperature on dry reforming catalysts

The effect of calcination temperatures on dry reforming catalysts supported on high surface area alumina Ni/γ-Al₂O₃ (SA-6175) was studied experimentally. In this study, the prepared catalyst was tested in a micro tubular reactor using temperature ranges of 500, 600, 700 and 800 °C at atmospheric pressure, using a total flow rate of 33 ml/min consisting of 3 ml/min of N₂, 15 ml/min of CO₂ and 15 ml/min of CH₄. The calcination was carried out in the range of 500–900 °C. The catalyst is activated inside the reactor at 500–800 °C using hydrogen gas. It was observed that calcination enhances catalyst activity which increases as calcination and reaction temperatures were increased. The highest conversion was obtained at 800 °C reaction temperature by using catalyst calcined at 900 °C and activation at 700 °C. The catalyst characterization conducted supported the observed experimental results.     

Effects of pyrolysis conditions on the physical characteristics of oil-palm-shell activated carbons used in aqueous phase phenol adsorption

Oil-palm shells, a biomass by-product from palm-oil mills, were converted into activated carbons by vacuum or nitrogen pyrolysis, followed by steam activation. The effects of pyrolysis environment, temperature and hold time on the physical characteristics of the activated carbons were studied. The optimum pyrolysis conditions for preparing activated carbons for obtaining high pore surface area are vacuum pyrolysis at a pyrolysis temperature of 675 °C and 2 h hold time. The activation conditions were fixed at a temperature of 900 °C and 1 h hold time. The activated carbons thus obtained possessed well-developed porosities, predominantly microporosities. For the pyrolysis atmosphere, it was found that significant improvement in the surface characteristics of the activated carbons was obtained for those pyrolysed under vacuum. Adsorption capacities of activated carbons were determined using phenol solution. For the activated carbons pyrolysed under optimum vacuum conditions, a maximum phenol adsorption capacity of 166 mg/g of carbon was obtained. A linear relationship between the BET surface area and the adsorptive capacity was shown.     

Preparation of carbon molecular sieves from palm shell: effect of benzene deposition conditions

Application of carbon molecular sieve (CMS) for gas separation has been found much attention recently. In this work, CMS was prepared from locally available palm shell through carbonization, steam activation and carbon vapour deposition (CVD) technique. After carbonization step, the char produced was subjected to steam activation at various activation times. The activated carbon obtained at 53.2% burn-off, which contain the highest amount of micropore volume was further used in CVD step by using benzene vapour at various deposition conditions. The performance of CMSs produced was examined by assessing the adsorption kinetics of O₂, N₂, CO₂ and CH₄ gases. All CMS samples showed a small N₂ and CH₄ uptake compared to the O₂ and CO₂. The suitable conditions for CVD were found at 800°C, 30 min and 30 vol% benzene of deposition temperature, time and benzene concentration, respectively. At this point the O₂/N₂ and CO₂/CH₄ uptake ratios arrived 7.1 and 16.0, respectively.     

Ni–Al hydrotalcite-like material as the catalyst precursors for the dry reforming of methane at low temperature

Nickel–aluminium and magnesium–aluminium hydrotalcites were prepared by co-precipitation and subsequently submitted to calcination. The mixed oxides obtained from the thermal decomposition of the synthesized materials were characterized by XRD, H₂-TPR, N₂ sorption and elemental analysis and subsequently tested in the reaction of methane dry reforming (DRM) in the presence of excess of methane (CH₄/CO₂/Ar = 2/1/7). DMR in the presence of the nickel-containing hydrotalcite-derived material showed CH₄ and CO₂ conversions of ca. 50% at 550 °C. The high values of the H₂/CO molar ratio indicate that at 550 °C methane decomposition was strongly influencing the DRM process. The sample reduced at 900 °C showed better catalytic performance than the sample activated at 550 °C. The catalytic performance in isothermal conditions from 550 °C to 750 °C was also determined.     

Oxygen selective ceramic hollow fiber membranes

Oxygen ion conducting Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ hollow fiber membranes with o.d. 1.15 mm and i.d. 0.71 mm were fabricated using a sequence of extrusion, gelation, coating and sintering steps. The starting ceramic powder was synthesized by combined EDTA–citrate complexing followed by thermal treatment at 900 °C. The powder was then dispersed in a polymer solution, and extruded through a spinerette. After gelation, an additional thin coating of the ceramic powder was applied on the fiber, and sintering was carried out at 1190 °C to obtain the final ceramic membrane. The fibers were characterized by SEM, and tested for air separation at ambient pressure and at temperatures between 700 and 950 °C. The maximum oxygen flux measured was 5.1 mL/min/cm² at 950 °C.     

Effect of heating on speciation of copper in Si/Al/Ca-based environmental matrices

X-ray absorption spectroscopy is used to investigate the speciation of sorbed copper in heated fly ash. CuO and Cu(OH)₂ are determined to be the principal copper species in the Cu-sorbing fly ash heated at 500 °C for 2 h. Heating the Cu-sorbing fly ash to 900 °C or 1100 °C can result in the formation of CuSO₄, representing 41% and 32% of the total copper, respectively. Ash sintering and/or co-melting at 900 and 1100 °C occur, thereby triggering chemical reaction between CuO/Cu(OH)₂ and sulfur compounds.     

Electrochemical characterisation of MBaCo3ZnO7+δ (M = Y,Er, Tb) as SOFC cathode material with low thermal expansion coefficient

The electrochemical oxygen activation at high temperature was studied on a new class of oxygen-store material based on the system YBaCo₄O_7+δ. Three different porous layers made of YBaCo₃ZnO_7+δ, ErBaCo₃ZnO_7+δ and TbBaCo₃ZnO_7+δ were electrochemically tested as oxygen activation coatings and showed a very promising activity. The envisaged applications for these materials are principally as SOFC cathodes and as catalytic layer on oxygen membranes. The electrochemical performance followed the order Tb ? Y > Er at any tested temperature. Area specific resistance for the best performing material (TbBaCo₃ZnO_7+δ) ranges from 30 mΩ cm² at 850 °C to 0.46 Ω cm² at 650 °C. High temperature XRD showed that the thermal expansion coefficient (25–900 °C) in air of TbBaCo₃ZnO₇ is 9.45 × 10^?6 K^?1, which evidences the good thermochemical compatibility of this cobalt-rich electrocatalyst with YSZ/GDC electrolytes.     

Preparation of activated carbon from cherry stones by physical activation in air. Influence of the chemical carbonisation with H2SO4

In the preparation of activated carbon (AC) by the method of physical activation, the carbonisation stage is usually carried out by heat treatment of a precursor at a given temperature in an inert atmosphere, whereas the activation stage is performed in air, carbon dioxide or steam atmosphere. Here, the use of a chemical carbonisation-based method with H₂SO₄ in aqueous solution as an alternative to the physical carbonisation method is studied. Using cherry stones (CS), AC was prepared by physical activation in air, as usual, and by carbonising with H₂SO₄ prior to activating in air. CS was carbonised at 600 °C in nitrogen atmosphere or with H₂SO₄ solutions of various concentrations and the resulting products were activated at 350–550 °C in air. Characterisation was undertaken by proximate analysis, TG–DTG analysis, N₂ adsorption at −196 °C, mercury porosimetry, density measurements and FT-IR spectroscopy. By the H₂SO₄-chemical carbonisation, AC with a lower inorganic matter content, wider pore size distribution in the meso- and macropore ranges, higher mesopore volume and carboxylic acid groups are prepared. The development of microporosity is similar regardless of the carbonisation method provided that the activation of the chemically carbonised product is effected at higher temperature. Physical carbonisation results in AC with an homogeneous macroporosity and with quinone type functional groups. Yield is also slightly higher by this carbonisation method.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

Study of immobilized candida rugosa lipase for biodiesel fuel production from palm oil by flow microcalorimetry

Enzymatic transesterification of palm oil with methanol and ethanol was studied. Of the four lipases that were tested in the initial screening, lipase Candida Rugosa (CR) resulted in the highest yield of mono alkyl esters. Lipase CR was further investigated in immobilized form within an activated carbon as support. The activated carbon was prepared by activation physical. Using the immobilized lipase CR, the effects of water and alcohol concentration, enzyme loading and enzyme thermal stability in the transesterification reaction were investigated. The optimal conditions for processing 50 g of palm oil were: 37 °C, 1:14.5 oil/methanol molar ratio, 1.0 g water and 500 mg lipase for the reactions with methanol, 35 °C, 1:15.0 oil/ethanol molar ratio, 1.0 g water, 500 mg lipase for the reactions with ethanol, and 35 °C, 1:10.0 oil/n-butanol molar ratio, 1.0 g water, 500 mg lipase for the reactions with ethanol. Subject to the optimal conditions, methyl and ethyl esters formation of 70 and 85 mol% in 1 h of reaction were obtained for the immobilized enzyme reactions. The flow microcalorimetry is an important and novel techniques is used in evaluation of biodiesel production.     

High oxygen-reduction activity of silk-derived activated carbon

Activated carbon prepared from silk fibroin, which is free of metal elements, showed a high catalytic activity for the oxygen-reduction reaction (ORR). The activated carbon had a very high onset potential of E_onset = 0.83 V (vs. RHE) in oxygen-saturated 0.5 M H₂SO₄ at 60 °C. The ORR on the activated carbon proceeded by a four-electron process in the high-electrode-potential region; this gradually decreased to a 3.5-electron reaction below about 0.6 V (vs. RHE). Only about 1% of nitrogen atoms (mostly quaternary) remained in the activated carbon by heat-treatment at up to 1200 °C are responsible for the high catalytic activity. The open circuit voltage of a polymer electrolyte fuel cell using the activated carbon as the cathode and a platinum/carbon black anode under pure oxygen and hydrogen gases, respectively, both at one atmosphere, was 0.96 V at 27 °C.     

A cobalt-free electrode material La0.5Sr0.5Fe0.8Cu0.2O3 − δ for symmetrical solid oxide fuel cells

Cobalt-free perovskite oxide La_0.5Sr_0.5Fe_0.8Cu_0.2O_3 − δ (LSFC) was applied as both anode and cathode for symmetrical solid oxide fuel cells (SSOFCs). The LSFC shows a reversible transition between a cubic perovskite phase in air and a mixture of SrFeLaO₄, a K₂NiF₄-type layered perovskite oxide, metallic Cu and LaFeO₃ in reducing atmosphere at elevated temperature. The average thermal expansion coefficient of LSFC in air is 17.7 × 10^− 6 K^− 1 at 25 °C to 900 °C. By adopting LSFC as initial electrodes to fabricate electrolyte supported SSOFCs, the cells generate maximum power output of 1054, 795 and 577 mW cm^− 2 with humidified H₂ fuel (~ 3% H₂O) and 895, 721 and 482 mW cm^− 2 with humidified syngas fuel (H₂:CO = 1:1) at 900, 850 and 800 °C, respectively. Moreover, the cell with humidified H₂ fuel demonstrates a reasonable stability at 800 °C under 0.7 V for 100 h.     

Highly efficient CdSe quantum-dot-sensitized TiO2 photoelectrodes for solar cell applications

With 4.2 nm quantum-dots (QDs) as seeds on TiO₂ film, a highly efficient TiO₂ photoelectrode was prepared by a seed-growing process using chemical bath deposition technique, followed by a covering process with ZnS layer, and a post-sintering process at 400 °C. The assembled solar cells presented IPCE peak values of 73% and power conversion efficiency of 3.21% under AM 1.5 G irradiation.     

An investigation on the solid state pyrolytic decomposition of bimetallic oxalate precursors of Ca,Sr and Ba with cobalt: A mechanistic approach

The mixed metal oxalate precursors, calcium(II)bis(oxalato)cobaltate(II)hydrate (COC), strontium(II)bis(oxalato)cobaltate(II)pentahydrate (SOC) and barium(II)bis(oxalato)cobaltate(II)octahydrate (BOC) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR spectral and X-ray powder diffraction studies. Thermal decomposition studies (TG, DTG and DTA) in air showed that the compound COC decomposed mainly to CaC₂O₄ and Co₃O₄ at 340 °C, and a mixture of CaCO₃ and Co₃O₄ identified at 510 °C. A mixture of CaCO₃ and Ca₃Co₂O₆ along with the oxides and carbides of both the cobalt and calcium were attributed at 1000 °C as end products. DSC study in nitrogen ascertained the formation of a mixture of CaO and CoO along with a trace of carbon at 550 °C. The mixture species, SrC₂O₄, CoC₂O₄ and Co₃O₄ were generated at 255 °C in case of SOC in air, which ultimately changed to CoSrO₃, SrCO₃ and oxides of strontium and cobalt at 1000 °C. The several mixture species also generated as intermediate at 332 and 532 °C. The DSC study in nitrogen indicated the formation of CoSrO_x (0.5 < x < 1) as end product. In case of BOC in air, a mixture of BaCoO₂, BaO, CoO and carbides are identified as end product at 1000 °C through the generation of several intermediate species at 350 and 530 °C. A mixture of BaO and CoO is identified as end product in DSC study in nitrogen. The kinetic parameters have been evaluated for all the dehydration and decomposition steps of all the three compounds using four non-mechanistic equations. Using seven mechanistic equations, the kind of dominance of kinetic control mechanism of the dehydration and decomposition steps are also inferred. The kinetic parameters, ΔH and ΔS of all the steps are explored from the DSC studies. Some of the decomposition products are identified by IR and X-ray powder diffraction studies.     

Low temperature synthesis of highly ion conductive Li7La3Zr2O12–Li3BO3 composites

Highly lithium ion conductive composites with Al-doped Li₇La₃Zr₂O₁₂ (LLZ) and amorphous Li₃BO₃ were prepared from sol–gel derived precursor powders of LLZ and Li₃BO₃. Precursor LLZ powders with cubic phase were obtained by a heat treatment of the precursor dried gel at 600 °C. Pellets of the mixture of the obtained LLZ and Li₃BO₃ were first held at 700 °C, and then successively sintered at 900 °C. Density of the sintered pellet with Li₃BO₃ was larger than that of the pellet without Li₃BO₃. From the TEM observation, the pellets were found to consist of cubic LLZ and amorphous Li₃BO₃. Total electrical conductivity of the obtained LLZ–Li₃BO₃ composite was 1 × 10^− 4 Scm^− 1 at 30 °C.     

Optimization of preparation conditions for activated carbon from palm oil fronds using response surface methodology on removal of pesticides from aqueous solution

Palm oil fronds were used to prepare activated carbon using the physiochemical activation method, which consisted of potassium hydroxide (KOH) treatment and carbon dioxide (CO₂) gasification. The effects of variable parameters activation temperature, activation time and chemical impregnation ratios (KOH: char by weight) on the preparation of the activated carbon and for the removal of pesticides: bentazon, carbofuran and 2,4-Dichlorophenoxyacetic acid (2,4-D) were investigated. Based on the central composite design (CCD), two factor interaction (2FI) and quadratic models were respectively employed to correlate the effect of variable parameters on the preparation of activated carbon used for the removal of pesticides with carbon yield. From the analysis of variance (ANOVA), the most influential factor on each experimental design response was identified. The optimum conditions for preparing the activated carbon from oil palm fronds were found as follows: activation temperature of 750 °C, activation time of 2 h and chemical impregnation ratio of 2.38. The percentage error between predicted and experimental results for the removal of bentazon, carbofuran and 2,4-D were 8.2, 1.3 and 9.2%, respectively and for the yield of the palm oil frond activated carbon was 5.6.     

Synthesis and characterization of LiCo3/5Mn2/5VO4 ceramics

Dielectric and a.c. conductivity properties of LiCo_3/5Mn_2/5VO₄ ceramic are investigated. This compound is prepared by solution-based chemical method and the formation is checked by X-ray diffraction (XRD) study. XRD analysis at room temperature shows an orthorhombic phase. Frequency dependence of dielectric constant (?_r) at different temperatures shows a dispersive behavior at low frequencies. Temperature dependence of ?_r at different frequencies indicates the transition temperature (T_c) = 235 °C, 245 °C, 257 °C and 265 °C with (?_r)_max. ～3689, 1373, 750 and 386 for 10, 50, 100 and 200 kHz respectively. A.c. conductivity analysis indicates that electrical conduction in the material is a thermally activated process.     

Physico–chemical properties of CdO–Al2O3 catalysts. I – Structural characteristics

Alumina gels AN6 and AN7 were prepared by precipitation with NaOH from hydrated aluminum sulfate at pH 6 and 7, respectively. A third alumina gel AA7 was similarly prepared, but by precipitation with 30% ammonia. Pure cadmia C8 and C9 were precipitated from cadmium sulfate at pH 8 and 9 using NaOH. Five mechanically mixed gels ACM (1:0.25), ACM (1:0.5), ACM (1:1), ACM (0.5:1) and ACM (0.25:1) were prepared by thoroughly mixing the appropriate molar ratios of AN7 and C8. Also, five coprecipitated gels ACC (1:0.25), ACC (1:0.5), ACC (1:1), ACC (0.5:1) and ACC (0.25:1) were coprecipitated by dropping simultaneously the appropriate volumes of 1 M aluminum sulfate, 1 M cadmium sulfate and 3 M NaOH. Calcination products at 400, 500, 600, 800 and 1000 °C were obtained from each preparation.TG–DTA patterns of uncalcined samples were analyzed and the XRD of all 1000 °C-products and some selected samples calcined at 400–800 °C were investigated. The thermal behaviors of pure and mixed gels depend on the precipitating agent, pH of precipitation, chemical composition and method of preparation. Generally, calcination at temperatures below 800 °C gave poorly crystalline phases. Well crystalline phases are obtained at 800 and 1000 °C. For pure alumina γ-Al₂O₃ was shown as 400 °C-calcination product that transforms into the δ form around 900 °C and later to θ-Al₂O₃ as a major phase and α-Al₂O₃ as a minor phase at 1000 °C. CdO was shown by 500 °C-calcined cadmia gel that showed color changes with rise of calcination temperature. The most stable black cadmium oxide phase (Monteponite) is obtained upon calcination at 1000 °C. Thousand degree celsius- calcined mixed oxides showed θ-Al₂O₃, α-Al₂O₃, CdAl₂O₄ and monteponite which dominate depending on the chemical composition.     

Kinetic and equilibrium adsorption of methylene blue and remazol dyes onto steam-activated carbons developed from date pits

Steam-activated carbons DS2 and DS5 were prepared by gasifying 600 °C-date pits carbonization products with steam at 950 °C to burn-off = 20 and 50%, respectively. The textural properties of these carbons were determined from the nitrogen adsorption at ?196 °C. The chemistry of the carbon surface was determined from the surface pH and from neutralization of the surface carbon–oxygen groups of basic and acidic type. The kinetic and equilibrium adsorption of MB and RY on DS2 and DS5 was determined at 27 and 37 °C and at initial sorption solution pH 3–7.DS2 and DS5 have expanded surface area, large total pore volume and contain both micro and mesoporosity. They have on their surface basic and acidic groups of different strength and functionality. This enhanced the sorption of the cationic dye (MB) and of the anionic dye (RY). The adsorption of MB and RY on DS2 and DS5 involves intraparticle diffusion and followed pseudo-second order kinetics. The adsorption isotherms were applicable to the Langmuir isotherm and high monolayer capacities for MB and RY dyes were evaluated indicating the high efficiencies of the carbons for dye adsorption.