Synthesis of a nano-crystalline solid acid catalyst from fly ash and its catalytic performance

The synthesis of nano-crystalline activated fly ash catalyst (AFAC) with crystallite size of 12 nm was carried out by chemical and thermal treatment of fly ash, a waste material generated from coal-burning power plants. Fly ash was chemically activated using sulfuric acid followed by thermal activation at 600 °C. The variation of surface and Physico-chemical properties of the fly ash by activation methods resulted in improved acidity and therefore, catalytic activity for acid catalyzed reactions. The AFAC was characterized by X-ray diffraction, FT-IR spectroscopy, N₂-adsorption–desorption isotherm, scanning electron microscopy, flame atomic absorption spectrophotometry and sulfur content by CHNS/O elemental analysis. It showed amorphous nature due to high silica content (81%) and possessed high BET surface area (120 m²/g). The catalyst was found to be highly active solid acid catalyst for liquid phase esterification of salicylic acid with acetic anhydride and methanol giving acetylsalicylic acid and methyl salicylate respectively. A maximum yield of 97% with high purity of acetylsalicylic acid (aspirin) and a very high conversion 87% of salicylic acid to methyl salicylate (oil of wintergreen) was obtained with AFAC. The surface acidity and therefore, catalytic activity in AFAC was originated by increased silica content, hydroxyl content and higher surface area as compared to fly ash. The study shows that coal generated fly ash can be converted into potential solid acid catalyst for acid catalyzed reactions. Furthermore, this catalyst may replace conventional environmentally hazardous homogeneous liquid acids making an ecofriendly; solvent free, atom efficient, solid acid based catalytic process. The application of fly ash to synthesize a solid acid catalyst finds a noble way to utilize this abundant waste material.     

Chemical modification of coal fly ash for the removal of phosphate from aqueous solution

This study investigated the chemical modifications of coal fly ash treated with HCl and NaOH. Sorption behavior of phosphate from water solution on treated fly ash was examined. Results showed that the HCl-treated fly ash (TFA-HCl) had a greater specific surface area (SSA) than the NaOH-treated fly ash (TFA-NaOH) and untreated fly ash (FA). The XRF, XRD patterns, and SEM images revealed the decreased CaO content in the TFA-HCl and observed the presence of NaP1 and sodalite zeolites in the TFA-NaOH. The P sorption capacity of all studied fly ashes increased with increasing initial P concentration and mechanisms of P sorption were influenced by the equilibrium pH. Maximum phosphate immobilization capacity obtained from Langmuir model was in the following manner, TFA-NaOH > FA > TFA-HCl (57.14, 23.20, and 6.90 mg P g⁻¹, respectively). The decreased CaO content and acidic pH in the TFA-HCl were responsible for the lowest capacity of phosphate immobilization, because of unfavorable condition for calcium phosphate precipitation. In contrast, due to alkaline condition and relatively high calcium content, the precipitation of calcium phosphate was a key mechanism for phosphate removal in the FA and TFA-NaOH. The TFA-NaOH had a greatest phosphate immobilization, due to high CaO content and an increased SSA after the conversion of fly ash to zeolite. Both Langmuir and Freundlich models were good fitted for the TFA-NaOH, while was only Langmuir model for the FA and Freundlich model for the TFA-HCl. Results suggested that treating fly ash with alkaline solution was a promising way to enhance phosphate immobilization.     

Fly ash-supported cerium triflate as an active recyclable solid acid catalyst for Friedel–Crafts acylation reaction

An efficient solid Lewis acid, has been synthesized by loading cerium triflate (7 wt%) on the acid activated fly ash with high silica content (81%). The physico-chemical properties of synthesized fly ash-supported cerium triflate catalyst (CFT) were monitored by XRD, FT-IR spectroscopy, FT-IR spectroscopy of the ammonia adsorbed catalyst, SEM-EDAX, TEM, Flame Atomic Absorption Spectrophotometer and TG-DTA study. The increased concentration of silica surface hydroxyl groups on activated fly ash have a major influence on the loading of cerium triflate. The catalytic activity of the catalyst CFT was tested in the acylation of veratrole using acetic anhydride as the acylating agent. The proposed model structure of CFT shows that the triflate species withdraws the electron density from the surface cerium making it electron deficit and generate Lewis acidity on the surface of fly ash as confirmed by NH₃ adsorbed FT-IR spectrum. The activity data indicate that this heterogeneous catalyst is very active, corresponding to high conversion (88%) of veratrole to 3,4-dimethoxyacetophenone. The catalyst could be easily recovered and reused giving similar conversion up to three reaction cycles indicating its stability under experimental conditions. Thus fly ash-supported cerium triflate is a novel and efficient catalyst and is a promising way of bulk utilization of waste fly ash by developing cost effective catalyst system for industrially important Friedel–Crafts acylation reactions.     

Synthesis and characterization of fly ash supported sulfated zirconia catalyst for benzylation reactions

Synthesis of highly active nano-crystalline, thermally stabilized solid acid catalyst has been reported by loading different weight fractions of sulfated zirconia on chemically activated fly ash through two step sol-gel technique. The catalysts were characterized using powder XRD, FT-IR, N₂-adsorption desorption study, CHNS elemental analysis, SEM-EDAX and their acidity were measured by pyridine adsorbed FTIR. Liquid phase benzylation of benzene and toluene with benzyl chloride was studied as test reaction for catalytic activity of SZF catalysts. A very high conversion of benzene (87%) and toluene (93%) were observed, which is attributed to significant amount of acid site on the catalyst surface. The FTIR study of the pyridine adsorbed samples reflects the presence of Brønsted as well as Lewis acid sites. The catalyst with 12 wt.% zirconia (SZF-12) was regenerated and reused up to four reaction cycles with equal efficiency as in the first run.     

Catalytic ammonia decomposition over CMK-3 supported Ru catalysts: Effects of surface treatments of supports

CMK-3 carbon was used as a catalyst support for Ru catalyst for ammonia decomposition. The supports were treated with acid, and the effects of treatment on the properties of CMK-3 supports were studied by N₂ adsorption, XRD, XPS and mass titration. The chemical treatment of carbon support cause significant changes in carbon surface chemistry and in turn had significant effects on both catalyst dispersion and catalytic activity. It is found that the as-synthesized CMK-3 carbon is not a good catalyst support for this reaction. However, surface functional groups produced by acid treatments led to larger Ru catalyst particles, while alkali treatments made the Ru catalyst dispersion even worse due to the residue alkali or earth alkali metals. Interestingly, relatively larger Ru catalyst particles but still well dispersed in the channel of the mesoporous structures of the carbon improves NH₃ conversion into H₂. This is determined by the chemical reaction rate-limiting step of ammonia decomposition. The catalytic activity follows the order: Ru-K/CMK-3 > Ru-Na/CMK-3 > Ru-Ca/CMK-3 > Ru-Cl/CMK-3 > Ru-SO₄/CMK-3 > Ru-PO₄/CMK-3 > Ru/CMK-3 > Ru-Li/CMK-3. CMK-3 is not a good carbon catalyst support due to its amorphous structure resulting in the poor electron conductivity.     

Calcium methoxide as a solid base catalyst for the transesterification of soybean oil to biodiesel with methanol

In this study, physical and chemical characterizations of calcium methoxide were investigated to assess its performance as an excellent solid base catalyst using some instrumental methods, such as BET surface area measurement, scanning electron micrographs and particle size distribution. Then, it was used to catalyze transesterification of soybean oil to biodiesel with methanol. The effects of various factors such as mass ratio of catalyst to oil, reaction temperature and volume ratio of methanol to oil were studied to optimize the reaction conditions. The results showed that calcium methoxide has strong basicity and high catalytic activity as a heterogeneous solid base catalyst and it was obtained a 98% biodiesel yield within 2 h in this reaction. Besides, the recycling experiment results showed it had a long catalyst lifetime and could maintain activity even after being reused for 20 cycles.     

Fly ash supported calcium oxide as recyclable solid base catalyst for Knoevenagel condensation reaction

A new type of solid base catalyst has been prepared by loading of CaO on thermally activated fly ash, with the aim of being used as heterogeneous catalyst for fine chemical production. The prepared fly ash supported calcium oxide catalyst (FAC) was characterized by FT-IR spectroscopy, X-ray diffraction analysis, Scanning Electron Microscopy and atomic absorption spectroscopy. The catalytic activity of FAC was evaluated by Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate as model test reaction under optimized conditions. The catalyst gave very high conversion (87%) of benzaldehyde to desired product ethyl (E)-α-cyanocinnamate with high purity. The catalyst was completely recyclable without significant loss in activity up to three reaction cycles, which confers its stability during reaction unlike commercial catalysts. Moreover this catalyst shows a promising future in providing environmentally clean process for the industrial sector.     

Role of active sites in the steam activation of high unburned carbon fly ashes

Previous studies on carbon gasification have not included high unburned carbon content fly ashes, and therefore it remains unclear why not all fly ash carbon samples are equally suitable for activation. The concentration of active sites is well known to influence carbon gasification reactions. Therefore, the objective of this work was to investigate the effect of the concentration of active sites on the behavior of fly ash carbon samples upon steam activation. Six fly ash carbons were selected to produce activated carbons using steam at 850 °C. The concentration of active sites was determined by non-dispersive infrared analysis (NDIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). XRD analyses were also conducted to determine the crystallite size. It was observed that the concentration of active sites played a more significant effect on the surface areas of activated carbons in the carbon burn-off zone of >60%. Statistical analysis was used to relate the surface areas of activated carbon variances with carbon burn-off levels.     

Carbon nanotube growth mechanism switches from tip- to base-growth with decreasing catalyst particle size

The growth of carbon nanotubes by a plasma assisted catalytic chemical vapor deposition was investigated using cobalt, nickel and iron catalyst particles of different sizes. For the three catalysts examined, it was shown that the growth mode switches from “tip-growth” for large particles (>>5 nm) to “base-growth” for smaller ones (<5 nm). While single-walled nanotubes and those with few walls (typically <7 walls) grow from their base, larger multi-walled nanotubes are fed with carbon via their tips which support the catalyst particle. A growth scenario involving two different pathways for carbon diffusion is proposed in order to explain the change in growth mode.     

Nickel catalyst supported on magnesium oxide with high surface area and plate-like shape: A highly stable and active catalyst in methane reforming with carbon dioxide

Nanocrystalline magnesium oxide with a high surface area and a highly defective surface structure with plate-like shape was synthesized by a facile method using polyvinyl alcohol as a surfactant. The prepared MgO was employed as support for nickel catalysts with various nickel loadings in methane reforming with carbon dioxide. The results showed high catalytic activity and stability for the prepared catalysts due to the formation of NiO–MgO solid solution and high basicity of support. The 5% Ni/MgO catalyst was very effective in this process and exhibited stable catalytic performance for 50 h of reaction as well as a high resistance against carbon formation.     

Transesterification of vegetable oils over a phosphazenium hydroxide catalyst incorporated onto silica

The catalytic activity of a phosphazenium hydroxide (PzOH) catalyst incorporated onto silica (PzOH/SiO₂) was investigated in the transesterification of vegetable oils with methanol. The PzOH stably incorporated onto silica (SiO₂) maintained its basicity and converted methanol molecules to methoxide ions. The PzOH/SiO₂ catalyst exhibited high activity in the transesterification of palm, corn, grape seed, and soybean oils (S-oil) with methanol, achieving ~ 90% conversion at 75 °C with a catalyst loading of 0.2 g per 4.8 ml of S-oil. Although the accumulation of organic materials on PzOH/SiO₂ reduced its activity, this accumulation was effectively removed by washing with methanol. The high activity of PzOH/SiO₂ was responsible for its strong basicity and for the free mobility of the PzOH moiety.     

An efficient catalyst Co(salophen) for synthesis of diethyl carbonate by oxidative carbonylation of ethanol

The oxidative carbonylation of ethanol to diethyl carbonate (DEC) was investigated by an efficient catalyst system comprising of Co-Schiff base complexes. Effects of Schiff base ligands, reaction time, catalyst concentration, temperature and pressure on the catalytic activity were studied. Co(salophen) [N,N′-bis(salicylidene) o-phenylenediamine cobalt] catalyst exhibited better catalytic activity compared with other Co complexes. When the oxidative carbonylation was carried out at the reaction conditions: 0.12 mol/L Co(salophen), P(CO)/P(O₂) = 2:1, 3.0 MPa, 140 °C, 2.5 h, the conversion of ethanol is 15.8%, the selectivity to DEC is 99.5% and the turnover number (TON) is 22.2. The corrosion behavior of Co(salophen) catalyst to the stainless steel reactor was also examined. The corrosion rate to the stainless steel by Co(salophen) catalyst is below 0.005 mm/a. SEM images demonstrated that the pitting corrosion was not observed on the surface of the stainless steel.     

Mechanical activation of fly ash: Effect on reaction, structure and properties of resulting geopolymer

Geopolymerisation of mechanically activated fly ash was studied at ambient (27 °C) and elevated (60 °C) temperatures by isothermal conduction calorimeter. Under both the conditions, mechanical activation enhanced the rate and decreased time of reaction. It was interesting to observe that in the samples milled for 45 min (median size ∼5 μm), a broad peak corresponding to geopolymerisation initiated at 27 °C after 32 h. The rate maxima at 60 °C, a measure of fly ash reactivity, showed a non-linear dependence on particle size and increased rapidly when the median size was reduced to less than 5-7 μm. Improvement in strength properties is correlated with median particle size, and reactivity of fly ash. The characterisation of the geopolymer samples by SEM-EDS, XRD and FTIR revealed that mechanical activation leads to microstructure and structural variations which can be invoked to explain the variation in the properties.     

Synthesis and characterization of calcium–alumino-silicate hydrates from oil shale ash – Towards industrial applications

The influence of the alkaline medium on the hydrothermal activation of the oil shale fly ash with NaOH and KOH was studied using SEM/EDX, XRD, ²⁹Si and ²⁷Al high-resolution MAS-NMR spectra. In the presence of NaOH the silicon in the original fly ash was completely converted into calcium–aluminum–silicate–hydrates, mainly into 1.1 nm tobermorite structure during 24-h treatment at 160 °C. At similar reaction conditions, the activation with KOH resulted only to the formation of amorphous calcium–silica-hydrate gel on the surface of ash particles at temperature. The results obtained in this study indicate that the oil shale fly ash can be used for production of Al-substituted tobermorites when strongly alkaline media (NaOH) is applied. The synthesized product was used in a catalytic d-lactose isomerization reaction.     

Effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample

The effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample has been investigated. The samples were tested for mercury adsorption using a fixed‐bed with a simulated flue gas. The activated fly ash carbon sample has lower mercury capacity than its precursor fly ash carbon (0.23 vs. 1.85 mg/g), although its surface area is around 15 times larger, 863 vs. 53 m²/g. It was found that oxygen functionality and the presence of halogen species on the surface of fly ash carbons may promote mercury adsorption, while the surface area does not seem to have a significant effect on their mercury capacity.     

Selective catalytic reduction of NO by ammonia with fly ash catalyst

This paper investigates the selective catalytic reduction (SCR) of NO with NH₃ using fly ash catalyst. The catalytically active elements investigated here included Fe, Cu, Ni and V. The results indicated that fly ash, after pre-treatment, can be reasonably used as the SCR catalyst support to remove NO from flue gas. Cu gave the highest catalytic activity and NO conversion, compared with Fe, Ni and V. In the pre-treatment process, the nitric acid treatment and drying temperatures for the fly ash particles had little effect on the NO conversion. However, the calcination temperature had an important effect on the catalyst preparation process.     

Sulphur dioxide removal using South African limestone/siliceous materials

This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO₂ removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 °C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 °C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 °C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe₂O₃ and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO₂ absorption capacity in terms of mol of SO₂ per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents.     

Study of the preasphaltenes of coal liquefaction and its hydro-conversion kinetics catalyzed by SO4/ZrO2

The investigation of hydro-conversion behavior of the heavy intermediate products derived from coal direct liquefaction is advantageous to optimize the technological conditions of direct coal liquefaction and improve the oil yield. In this paper, the hydro-conversion of preasphaltenes catalyzed by SO₄²⁻/ZrO₂ solid acid was investigated based on the structural characterization of preasphaltenes and its hydro-conversion products, and the determination of products distribution and the kinetics of preasphaltenes hydro-conversion. The results indicated that the content of condensed aromatic rings increased, and the contents of hydrogen, oxygen and aliphatic side chains of preasphaltenes decreased with the increase of coal liquefaction temperature. The preasphaltenes showed higher hydro-conversion reactivity while SO₄²⁻/ZrO₂ solid acid was used as catalyst. Higher temperature and longer time were in favor of increasing the conversion and the oil + gas yield. The conversion of preasphaltenes hydro-conversion under 425 °C, for 40 min reached 81.3% with 51.2% oil + gas yield. SO₄²⁻/ZrO₂ solid acid was in favor of the catalytic cracking rather than the catalytic hydrogenation in the hydro-conversion of preasphaltenes. The activation energy of preasphaltenes conversion into asphaltenes was 72 kJ/mol. The regressive reactions were only observed at a higher temperature.     

Electrochemical promotion of YSZ monolith honeycomb for deep oxidation of methane

A honeycomb monolith of YSZ (yttria stabilized zirconia) was used, for the first time, as a solid electrolyte to perform electrochemical promotion of the deep oxidation of methane. The goal of this study was to validate the concept of Electrochemical Promotion of Catalysis (EPOC) by using Pd particles dispersed on the channels surface of a YSZ dense honeycomb monolith. The Pd catalyst was an effective material as methane conversion reached 20% at about 320 °C. The catalytic properties of the monolithic electrochemical catalyst were investigated upon electrical polarization at 400 °C. Non faradaic effects were observed both under positive and negative polarizations with a maximum of the faradaic efficiency of 47.     

Catalytic performance of porous carbons obtained by chemical activation

Porous carbons were prepared by the pyrolysis of pinewood in nitrogen at 773 K, followed by chemical activation using different concentrations of KOH in nitrogen at 973 K. Both water-washed and acid-washed samples exhibited much higher specific surface areas than unactivated carbon. The water-washed sample showed strong basicity and a high catalytic performance in the decomposition of isopropanol, even higher than superbase 26%KNO₃/γ-Al₂O₃. Moreover, these porous carbons can act as water-resistant solid bases. The formation of the insoluble basic sites is most possibly related to the intercalation of potassium in the carbon during the chemical activation.