Steam reforming of ethanol with zirconia incorporated mesoporous silicate supported catalysts

Steam reforming of ethanol is a promising route for the production of high purity hydrogen. Ni impregnated zirconia, with high chemical and thermal stability and high water adsorption-dissociation capability is an attractive catalyst for this reaction. In the present study, mesoporous zirconia and high surface area zirconia/silicate structured materials, such as Zr-SBA-15 and Zr-MCM-41, were synthesized following hydrothermal routes, using different surfactants as the structure directing templates. Surface area values of Ni impregnated mesoporous Zr-SBA-15 and Zr-MCM-41 catalysts with molar Zr/Si ratios of 0.13 and 0.45 were 515 and 338 m²/g, respectively. Ethanol reforming tests performed with these catalysts, in the temperature range of 550–650 °C, proved the potential of these materials to achieve very high hydrogen yields, over 90% of the maximum yield value of 6 mol per mole of ethanol reacted. Type of support material, Ni distribution and cluster size over the catalyst, reaction temperature and steam to ethanol ratio were found to have strong influence on coke formation and stability of hydrogen yield.     

Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel production

This paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 °C and 700 °C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60–65 °C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production.     

Biodiesel from palm oil via loading KF/Ca–Al hydrotalcite catalyst

The solid base catalyst KF/Ca–Al hydrotalcite was obtained from Ca–Al layered double hydroxides and successfully used in the transesterification of methanol with palm oil to produce biodiesel. With the load of KF, the activity of Ca–Al mixed-oxides had been improved much. For the mass ratio 80 wt.%(KF·6H₂O to Ca–Al mixed-oxides) catalyst, under the optimal condition: 338 K, catalyst amount 5%(wt./wt. oil) and methanol/oil molar ratio 12:1, after 5 h reaction, the fatty acid methyl esters yield could reach 97.98%; for the mass ratio 100 wt.%(KF·6H₂O to Ca–Al mixed-oxides) ones, under the same reaction condition, only needed 3 h to get the FAME yield of 99.74%, and even only reacted 1 h, the FAME yield could obtain 97.14%.     

Effects of water on the esterification of free fatty acids by acid catalysts

To maximize the production of biodiesel from soybean soapstock, the effects of water on the esterification of high-FFA (free fatty acid) oils were investigated. Oleic acid and high acid acid oil (HAAO) were esterified by reaction with methanol in the presence of Amberlyst-15 as a heterogeneous catalyst or sulfuric acid as a homogeneous catalyst. The yield of fatty acid methyl ester (FAME) was studied at oil to methanol molar ratios of 1:3 and 1:6 and reaction temperatures of 60 and 80 °C. The rate of esterification of oleic acid significantly decreased as the initial water content increased to 20% of the oil. The activity of Amberlyst-15 decreased more rapidly than that of sulfuric acid, due to the direct poisoning of acid sites by water. Esterification using sulfuric acid was not affected by water until there was a 5% water addition at a 1:6 molar ratio of oil to methanol. FAME content of HAAO prepared from soapstock rapidly increased for the first 30 min of esterification. Following the 30-min mark, the rate of FAME production decreased significantly due to the accumulation of water. When methanol and Amberlyst-15 were removed from the HAAO after 30 min of esterification and fresh methanol and a catalyst were added, the time required to reach 85% FAME content was reduced from 6 h to 1.8 h.     

Structural effect of Ni/SBA-15 by Zr promoter for H2 production via methane dry reforming

5 wt% of Ni/SBA-15 supported with numerous Zr loading (1–7 wt%) were produced using sol-gel technique at 60 °C. The influence of Zr promoter on the physiochemical properties of Ni/SBA-15 catalysts for methane dry reforming were examined in a fixed-bed reactor at 800 °C. Analytical characterizations including XRD, BET, FTIR, N₂ adsorption desorption, TEM and TGA were conducted to study the physiochemical properties of Zr/Ni/SBA-15 catalysts for the sake of identification of the amount of coke deposition formed on the spent catalyst. Increasing the amount of Zr loading from 1 to 7 wt% supported on Ni/SBA-15 reduced the catalyst's surface area as was proven from the physiochemical properties of Zr/Ni/SBA-15 catalyst. The catalytic activity test revealed that the optimum Zr loading was 1 wt% at which CH₄ and CO₂ conversions were 87.07% and 4.01%, meanwhile H₂:CO ratios was 0.42. This result was owing to the existence of the Zr species in promoting a good dispersion of Nickel (Ni) active sites on the catalyst surface as affirmed from XRD and FTIR results. The latest discovery indicates that promotion of 1 wt% Zr onto Ni/SBA-15 can prompt excellent catalytic performance in CRM.     

Biodiesel production from mixed soybean oil and rapeseed oil

The biodiesel (fatty acid methyl esters, FAME) was prepared by transesterification of the mixed oil (soybean oil and rapeseed oil) with sodium hydroxide (NaOH) as catalyst. The effects of mole ratio of methanol to oil, reaction temperature, catalyst amount and reaction time on the yield were studied. In order to decrease the operational temperature, a co-solvent (hexane) was added into the reactants and the conversion efficiency of the reaction was improved. The optimal reaction conditions were obtained by this experiment: methanol/oil mole ratio 5.0:1, reaction temperature 55 °C, catalyst amount 0.8 wt.% and reaction time 2.0 h. Under the optimum conditions, a 94% yield of methyl esters was reached ∼94%. The structure of the biodiesel was characterized by FT-IR spectroscopy. The sulfur content of biodiesel was determined by Inductively Coupled Plasma emission spectrometer (ICP), and the satisfied result was obtained. The properties of obtained biodiesel from mixed oil are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel. Production of biodiesel has positive impact on the utilization of agricultural and forestry products.     

Optimization of biodiesel production from waste fish oil

The present study deals with the production of biodiesel using waste fish oil. The research assesses the effect of the transesterification parameters on the biodiesel yield and its properties, including temperature (40–60 °C), molar ratio methanol to oil (3:1–9:1) and reaction time (30–90 min). The experimental results were fitted to complete quadratic models and optimized by response surface methodology. All the biodiesel samples presented a FAME content higher than 93 wt.% with a maximum, 95.39 wt.%, at 60 °C, 9:1 of methanol to oil ratio and 90 min. On the other hand, a maximum biodiesel yield was found at the same methanol to oil ratio and reaction time conditions but at lower temperature, 40 °C, which reduced the saponification of triglycerides by the alkaline catalyst employed. Adequate values of kinematic viscosity (measured at 30 °C) were obtained, with a minimum of 6.30 mm²/s obtained at 60 °C, 5.15:1 of methanol to oil ratio and 55.52 min. However, the oxidative stability of the biodiesels produced must be further improved by adding antioxidants because low values of IP, below 2.22 h, were obtained. Finally, satisfactory values of completion of melt onset temperature, ranging from 3.31 °C to 3.83 °C, were measured.     

Screening,optimization and kinetics of Jatropha curcas oil transesterification with heterogeneous catalysts

This work investigates the production of fatty acid methyl esters (FAME) from Jatropha curcas oil using a variety of heterogeneous catalysts: resins, zeolites, clays, hydrotalcites, aluminas and niobium oxide. For this purpose, a catalyst screening was first conducted in a batch reactor at the following operating conditions: oil to methanol molar ratio of 1:9, 6 h of reaction, 5 wt% catalyst, at 333 and 393 K. From the screening step, KSF clay and Amberlyst 15 catalysts were selected to carry out a 2³ full factorial central composite rotatable design so as to elucidate the effects of process variables on FAME yield. The optimum reaction conditions for both catalysts were found to be oil to methanol molar ratio of 1:12, 5 wt% of catalyst, 433 K and 6 h of reaction with a FAME yield of about 70 wt%. A kinetic study was then experimentally performed and a semi-empirical model was built to represent the experimental data. Finally, catalyst re-utilization in five successive batch experiments was evaluated at the optimized conditions.     

Structural/texture evolution of CaO/MCM‐41 nanocatalyst by doping various amounts of cerium for active and stable catalyst: Biodiesel production from waste vegetable cooking oil

In present work, the aim of producing biodiesel from waste cooking oil was pursued by doping the cerium element into the MCM‐41 framework as catalyst with various Si/Ce molar ratio (5, 10, 25, 50, and Ce = 0). The catalytic performance and stability improved by employing the ultrasound irradiation in active phase loading step of catalyst preparation. The physicochemical characteristics of synthesized samples were investigated using various techniques as follows: Brunauer‐Emmett‐Teller (BET), X‐ray powder diffraction (XRD), Fourier transfer infrared (FTIR), energy‐dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). The XRD patterns along with the results of FTIR and BET analysis revealed the MCM‐41 framework destruction while increasing the Ce content. The FESEM images of the nanocatalysts illustrated a well distribution and uniform morphology for the Ca/CeM (Si/Ce = 25). The particle size and size distribution of the Ca/CeM (Si/Ce = 25) were subsequently determined by TEM and FESEM images. The activity of fabricated nanocatalysts was evaluated by measuring the free acid methyl ester (FAME) content of produced biodiesel. The tests were carried out at constant operational conditions: T = 60°C, catalyst loading = 5 wt%, methanol/oil molar ratio = 9, and 6‐hour reaction time. A superior activity was observed for Ca/CeM (Si/Ce = 25) among other nanocatalysts with 96.8% conversion of triglycerides to biodiesel. The mentioned sample was utilized in five reaction cycles, and at the end of the fifth cycle, the conversion reached to 91.5% which demonstrated its significant stability.     

Parametric study and optimization of in situ transesterification of Jatropha curcas L assisted by benzyltrimethylammonium hydroxide as a phase transfer catalyst via response surface methodology

In the present work, non-edible oil source, Jatropha curcas oil was used with base catalyzed methanol and ethanol to produce biodiesel using in situ transesterification assisted by Benzyltrimethylammonium hydroxide (BTMAOH) as a phase transfer catalyst (PTC). Experimental investigation showed that base catalyzed in situ transesterification reaction rate was enhanced with the use of BTMAOH as a PTC. During the experiment fast formation of biodiesel was observed in relatively shorter time for PTC assisted reaction as compared to the reaction in the absence of PTC. The effect of individual reaction parameters was investigated using response surface methodology (RSM). Optimum operating conditions were also found statistically. Weight fractions of 89 ± 0.7% fatty acid methyl esters (FAME) yield and 99.4 ± 0.4% fatty acid ethyl esters (FAEE) yield were produced at optimum reaction condition. The fuel quality of FAME and FAEE was investigated against the fuel quality specification set by ASTM D6751 and EN-14214 standards.     

A green catalyst for biodiesel production from jatropha oil: Optimization study

In this study, a simple and solvent-free method was used to prepare sulfated zirconia-alumina (SZA) catalyst. Its catalytic activity was subsequently investigated for the transesterification of Jatropha curcas L. oil to fatty acid methyl ester (FAME). The effects of catalyst preparation parameters on the yield of FAME were investigated using Design of Experiment (DOE). Results revealed that calcination temperature has a quadratic effect while calcination duration has a linear effect on the yield of FAME. Apart from that, interaction between both variables was also found to significantly affect the yield of FAME. At optimum condition; calcination temperature and calcination duration at 490 °C and 4 h, respectively, an optimum FAME yield of 78.2 wt% was obtained. Characterization with XRD, IR and BET were then used to verify the characteristic of SZA catalyst with those prepared using well established method and also to describe the catalyst characteristic with its activity.     

Acid-catalyzed production of biodiesel from waste frying oil

The reaction kinetics of acid-catalyzed transesterification of waste frying oil in excess methanol to form fatty acid methyl esters (FAME), for possible use as biodiesel, was studied. Rate of mixing, feed composition (molar ratio oil:methanol:acid) and temperature were independent variables. There was no significant difference in the yield of FAME when the rate of mixing was in the turbulent range 100 to 600 rpm. The oil:methanol:acid molar ratios and the temperature were the most significant factors affecting the yield of FAME. At 70 °C with oil:methanol:acid molar ratios of 1:245:3.8, and at 80 °C with oil:methanol:acid molar ratios in the range 1:74:1.9–1:245:3.8, the transesterification was essentially a pseudo-first-order reaction as a result of the large excess of methanol which drove the reaction to completion (99±1% at 4 h). In the presence of the large excess of methanol, free fatty acids present in the waste oil were very rapidly converted to methyl esters in the first few minutes under the above conditions. Little or no monoglycerides were detected during the course of the reaction, and diglycerides present in the initial waste oil were rapidly converted to FAME.     

Synthesis of fatty acid methyl esters via the methanolysis of palm oil over Ca3.5xZr0.5yAlxO3 mixed oxide catalyst

Novel mixed metal oxide catalyst Ca_3.5xZr_0.5yAl_xO₃ was synthesized through the coprecipitation of metal hydroxides. The textural, morphological, and surface properties of the synthesized catalysts were characterized via Brunauer–Emmett–Teller method, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy. The catalytic performance of the as-synthesized catalyst series was evaluated during the transesterification of cooking palm oil with methanol to produce fatty acid methyl esters (FAME). The influence of different parameters, including the calcination temperature (300–700 °C), methanol to oil molar ratio (6:1–25:1), catalyst amount (0.5–6.5 wt%), reaction time (0.5–12 h) and temperature (70–180 °C), on the process was thoroughly investigated. The metal oxide composite catalyst with a Ca:Zr ratio of 7:1 showed good catalytic activity toward methyl esters. Over 87% of FAME content was obtained when the methanol to oil molar ratio was 12:1, reaction temperature 150 °C, reaction time 5 h and 2.5 wt% of catalyst loading. The catalyst could also be reused for over four cycles.     

Synthesis of fatty acid methyl esters via the transesterification of waste cooking oil by methanol with a barium-modified montmorillonite K10 catalyst

The transesterification of waste cooking oil (WCO) with methanol to produce fatty acid methyl esters (FAMEs) in the presence of barium-modified montmorillonite K10 (BMK10) catalyst was investigated in a batch reactor. The influence of the reaction parameters on the yield of FAME was investigated. The highest value of 83.38% was obtained with 3.5 wt% catalyst loading at 150 °C with a methanol: oil molar ratio of 12:1 during a reaction time of 5 h. BMK10 is a promising low-cost catalyst for the transesterification of WCO to produce FAME.     

Kinetics of biofuel generation from deodorizer distillates derived from the physical refining of olive oil and squalene recovery

The recovery of squalene from deodorizer distillate derived from the physical refining of olive oil was evaluated by combining pressurized acidic esterification in a closed system with vacuum distillation. Esterification was carried out at 341, 359, 366, 391 and 395 K. The reaction at 395 K was found to be satisfactory as it decreased the acid value by 99.21% and generated a FAME concentration of 67.53% within 1 h. In order to demonstrate that the generation of FAME from deodorizer distillate was mainly due to the transformation of FFA, the reaction extent, which characterizes the reaction and simplifies calculations, was evaluated for FFA removal and the generation of FAME. Subsequent vacuum distillation allowed the separation of one fraction rich in FAME (94%), which can be used as a biofuel and accounted for 85% of the initial mass, and another fraction that was rich in squalene (78%) and may be used for manufacturing pharmaceutical products. The global squalene yield was 117 g kg⁻¹ initial deodorizer distillate.     

Biodiesel production by esterification of palm fatty acid distillate

Production of fatty acid methyl ester (FAME) from palm fatty acid distillate (PFAD) having high free fatty acids (FFA) was investigated in this work. Batch esterifications of PFAD were carried out to study the influence of: including reaction temperatures of 70–100 °C, molar ratios of methanol to PFAD of 0.4:1–12:1, quantity of catalysts of 0–5.502% (wt of sulfuric acid/wt of PFAD) and reaction times of 15–240 min. The optimum condition for the continuous esterification process (CSTR) was molar ratio of methanol to PFAD at 8:1 with 1.834 wt% of H₂SO₄ at 70 °C under its own pressure with a retention time of 60 min. The amount of FFA was reduced from 93 wt% to less than 2 wt% at the end of the esterification process. The FAME was purified by neutralization with 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 15 min followed by transesterification process with 0.396 M sodium hydroxide in methanol solution at a reaction temperature of 65 °C for 15 min. The final FAME product met with the Thai biodiesel quality standard, and ASTM D6751-02.     

Characterization of Ti-based hydrogen absorbing alloys

In this paper, Ti-x wt.% Zr (x = 25, 30, 35) alloys were developed and their hydrogen absorption properties were characterized systematically. Phase structure investigation indicates that experimental Ti-x wt.% Zr (x = 25, 30, 35) alloys are solid solutions with HCP (hexagonal close-packed) structure. And the X-ray diffraction patterns of hydrided alloys showed that the main phase composition is FCC (face-centered cubic) structure, the minority FCC Ti₂ZrH₄ phase was also observed in hydrided Ti-30 wt.% Zr alloy. Besides, the hydrogen absorption thermodynamic and kinetic properties were characterized, thermodynamic calculation was combined with experiments for the first time, thermodynamic model of the Ti–Zr–H ternary system was developed by using first-principles calculations combined with CALPHAD (CALculation of PHase Diagrams) method, the predicted PCT curves agree well with experimental data. Properties of Ti-x wt.% Zr (x = 0–50) alloys at 573 K were also predicted.     

Synthesis of biodiesel from vegetable oils wastewater sludge by in-situ subcritical methanol transesterification: Process evaluation and optimization

Biodiesel are gaining increased public and scientific attention as an alternative to petroleum diesel fuel, driven by factors such as oil price spikes, energy security and environmental concerns. In this study, low grade wastewater sludge originated from wastewater treatment unit of vegetable oil factory as a viable alternative lipid source for biodiesel production was evaluated. The lipid mass fraction of the dry and ash-free sludge was 12.44 ± 0.87%, which mainly comprised of C16–C18 fatty acids. The in-situ transesterification process under subcritical water and methanol conditions was applied as a green pathway to convert lipids into fatty acid methyl esters (FAMEs). The reaction parameters investigated were temperatures (155–215 °C), pressures (5.5–6.5 MPa) and methanol to lipid mass ratios (1:1, 5:1 and 9:1). The highest FAME yield of 92.67 ± 3.23% was obtained at 215 °C, 6.5 MPa and methanol to lipid mass ratio of 5:1. Statistical analysis based on response surface methodology in 3-factor-3-level central composite designed experiments and analysis of variance were applied to examine the relation between input parameters and the response and to locate the optimum condition. Results showed that 98% of the variability in the response could be adequately explained by the second-order polynomial model. The optimum FAME yield (90.37%) was obtained at 215 °C, 6.5 MPa and methanol to lipid mass ratio of 5.12:1. Experimental validation (N = 3) demonstrated satisfactory agreement between the observed and predicted values with an error of at most 3.3%.     

Biodiesel production from refined sunflower vegetable oil over KOH/ZSM5 catalysts

ZSM5 zeolite was impregnated with different KOH loadings (15 wt.%, 25 wt.% and 35 wt.%) to prepare a series of KOH/ZSM5 catalysts. The catalysts were calcined at 500 °C for 3 h and then characterized by N₂ adsorption–desorption and X-ray diffraction (XRD) techniques. The catalysts were tested in the transesterification reaction in a batch reactor at 60 °C and under atmospheric pressure. It was found that KOH/ZSM5 with 35 wt.% loading showed the best catalytic performance. The best reaction conditions in the presence of KOH/ZSM5 (35 wt.%) were determined while modifying the catalyst to oil ratio and the reaction time. The highest methyl ester yield (>95%) was obtained for a reaction time of 24 h, a catalyst to oil ratio of 18 wt.%, and a methanol to oil molar ratio of 12:1. The properties of produced biodiesel complied with the ASTM specifications. The catalytic stability test showed that 35KOH/ZSM5 was stable for 3 consecutive runs. Characterization of the spent catalyst indicated that a slight deactivation might be due to the leaching of potassium oxides active sites.     

Muskmelon (Cucumis melo) seed oil: A potential non-food oil source for biodiesel production

Methanolysis of muskmelon seed oil was optimized employing RSM (response surface methodology). Four process variables were evaluated at two levels: methanol/oil molar ratio (3:1–12:1), catalyst concentration in relation to oil mass (0.25–1.25 wt % KOH), reaction temperature (25–65 °C) and methanolysis reaction time (20–90 min). Multiple regression analysis was employed to get the quadratic polynomial equation for predicting transesterification using RSM. The result indicated that catalyst concentration and reaction temperature were the important factors that significantly affect the yield of MMOMEs (muskmelon oil methyl esters)/biodiesel. The RSM methodology was used to obtain methyl esters yield (89.5%) were found at following reaction conditions; 5.8:1 methanol-to-oil ratio, 0.79% catalyst concentration, 55 °C reaction temperature and 72.5-min reaction time. There was a linear correlation between observed and predicted values. The biodiesel was analyzed using GC/MS (gas chromatography/mass spectrometry) which indicated four FAMEs (fatty acid methyl esters) (linoleic-, oleic-, palmitic- and stearic acids) as its major components. The FT-IR (fourier transform infraRed) spectrum of MMOMEs was also acquired to ensure the confirmation of methyl esters formation. Fuel properties of MMOMEs were determined and found to satisfy the ASTM D 6751 and EU 14214 specifications.