The esterification of palmitic acid in Jatropha Oil using 8wt% p-TSA catalyst was done at the 1:8 molar ratio of oil to methanol and 65℃. The conversion of palmitic acid appeared to be 95.3% in 60min. After that, the continuous transesterification of the oil using 0.5wt% KOH, 0.8wt% TMAH mixed catalyst[40vol% KOH(0.5wt%) + 60vol% TMAH(0.8wt%)] and 1.1wt% TMAH was conducted with the flow rates and the molar ratios at 65℃. The overall conversion of Jatropha Oil increased with the decrease of flow rate and showed 95.6% with 9ml/min of flow rate at the 1:8 molar ratio of oil to methanol and 65℃. But it showed 87% with 15ml/min of flow rate at the same conditions. The recovery of methanol(%) appeared to be 86% at the 1:8 molar ratio of oil to methanol, mixed catalyst and 65℃.
Fisher-Tropsch synthesis for the production of hydrocarbon from syngas was investigated on 20% cobalt-based catalysts (20% Co/HSA, 20% Co/Si-MMS), which were prepared by home-made supports with high surface areas such as high surface alumina (HSA) and silica mesopores molecular sieve (Si-MMS). In the gas phase reaction by syngas only, 20% Co/Si-MMS catalyst was shown in higher CO conversion and lower carbon dioxide formation than 20% Co/HSA, whereas the olefin selectivity was higher in 20% Co/HSA than in 20% Co/Si-MMS. In the effect of n-hexane added in syngas, the selectivities of C5+ and olefin were increased by comparing the supercritical phase reaction with the gas phase reaction in addition to reduce unexpected methane and carbon dioxide.
The esterification of the reactants of Jatropha oil and methanol added by propyleneglycol was done using p-TSA catalyst. And then the emulsification of triglyceride and methanol was conduced by 1.0vol% GMS. The emulsified reactants were transesterified at 65℃ using TMAH and mixed catalyst (50wt%-TMAH+50wt%-NaOH) respectively. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 80min. The overall conversion at the 1:8 molar ratio of mixed fat(50wt% Beef Tallow) to methanol and 65℃ using mixed catalyst was 95.4% The cloud point of Biodiesel decreased with the addition of petroleum diesel.
The fat of Tra and Basa catfish (Mekong Delta, Viet Nam) was evaluated for the first time as the potential feedstock for biodiesel production, due to its abundance, availability and cheap cost. The unsaturated fatty acid contents of Tra and Basa fat were 57.97% and 64.17%, respectively. Biodiesel was prepared from Tra and Basa fat by methanolysis reaction using alkali catalysts like sodium hydroxide and potassium hydroxide. Effects of various process parameters on biodiesel production, such as molar ratio of methanol to fat, catalyst concentration, temperature and time were investigated. As those results, the transesterification can be performed under moderate conditions, and the biodiesel yields were shown more than 90%. KOH catalyst was the best catalyst for biodiesel production from both Basa and Tra fat. As the feedstock aspect, Basa fat was indicated more efficiency than that of Tra fat. The maximum yield could be achieved by the transesterification from Basa fat with 5:1 molar ratio of methanol to fat, 0.8% KOH catalyst, 50℃, and 50 min. For Tra fat, the optimal condition were at 6:1 molar ratio of methanol to fat, 0.8% KOH catalyst, 50℃, and 45 min. Nowadays, due to cheaper cost and abundance, Tra fat is a promised resource for cheap biodiesel production in Viet Nam.
The esterification of free fatty acid in Jatropha oil added by propylene glycol using p-TSA catalyst was done, and then the transesterification of Jatropha oil added by 1.0vol% GMS as an emulsifier using TMAH, and mixed catalyst(60wt%-TMAH+ 40wt%-KOH) respectively was followed at 60℃. The esterification conversion at the 1:8 molar ratio of free fatty acid to methanol using 8.0wt% p-TSA was 94.7% within 60min. The overall conversion at the 1:8 molar ratio of Jatropha oil to methanol and 60℃ using mixed catalyst was 95.4%. The kinematic viscosity of Biodiesel using TMAH and mixed catalyst in 24h met the ASTM D-6751 above 30℃, and showed a little more than its criterion.
Pt-loaded carbon black for the catalyst of a PEM fuel cell was synthesized with different molar ratios of polyvinylpyrrolidone and H2PtCl6 solution to improve the dispersion of Pt nanoparticles on carbon black and decrease the size of Pt nanoparticles. From transmission electron microscopy results, Pt nanoparticles of a size of approximately 2 nm were highly dispersed when the polyvinylpyrrolidone concentration was 10mM. The electrochemical activity of the synthesized Pt/C catalysts was investigated by cyclic voltammetry, showing that the as-synthesized Pt-loaded carbon black catalyst had the best activity at a polyvinylpyrrolidone concentration of 10 mM.
Understanding the exact structure and surface characteristics of carbon materials is very important for design, synthesis, and utilization of the best carbon form with particular functions and high performance for practical applications such as selective adsorption adsorbents, energy storage materials, catalysts or catalyst supports, etc. This review paper focuses on carbon surface properties and the interaction between gaseous or liquid substances and carbon surface. Catalytic functions of carbon materials are reviewed including recent progress in synthesis and applications of nano-carbons.
Catalytic activity changes of perovskite catalysts were examined with their A-site substitution. For the preparation of catalysts, Mn was used for B-site component and La, Ce, Sr, Ba, Ca, Ag were used for A-site component of the perovskite catalysts(ABO3) The effect of calcination temperature on methane combustion and perovskite structure was also investigated. The surface area and adsorbed oxygen species were tested with BET apparatus and O2-TPD, respectively. Perovskite catalysts whose A-site was partially substituted needed higher calcination temperature than un-substituted one to form the perovskite structure. From O2-TPD experiment, it was found that methane combustion activity was directly related to the oxygen desorbing ability of the catalysts. The prepared catalyst(LM-7) was stable at 600℃ for 72 hours of reaction.
The transesterifications of beef tallow and the mixture of beef tallow and rapeseed oil were conducted at 65℃ respectively using TMAH, NaOH and their mixed catalysts. The reactants were emulsified with 1vol% emulsifier and propylene glycol. The overall conversion of beef tallow was 95% at such optimum conditions as the 1:8 of molar ratio and 0.8 wt% TMAH. The overall conversion of mixed fat at the 1:8 of molar ratio and mixed catalyst of 70 wt% TMAH 30 wt% NaOH was close to 97% which appeared at 0.8 wt% TMAH in 80min. And the kinematic viscosity of biodiesel mixture using the mixed catalyst was 6.5mm2/s at 40℃.
Carbon nanofiber (CNF) grown catalytically was chemically activated with KOH to attain structural change of CNF. The structural changes of CNF through KOH activation were investigated by using BET and SEM. From the results of BET, it was found that KOH activation was effective to develop particular sizes of pores on the CNF surface, increasing the surface area of CNF. Activated CNF was applied as an anode catalyst support of fuel cell. The effects of different activation conditions including the activation temperature and the activation time on the specific surface area of the CNF activated with KOH were investigated to obtain appropriate structure as a catalyst support. The 60 wt% Pt-Ru catalyst prepared was observed by using TEM and XRD.
Methane combustion over perovskite catalysts was investigated. For the preparation of catalysts, Co, Mn, Fe, and Ni were used as B-site components of the perovskite catalysts (ABO3) and La was used as A-site component. The effect of calcination temperature on methane combustion and perovskite structure was also investigated. The structure of perovskites, surface area, and adsorbed oxygen species were tested with XRD, BET apparatus, and O2-TPD, respectively. The formation of perovskite structure was affected by the calcination temperature. The catalyst desorbing oxygen at a lower temperature showed better activity for the methane combustion, therefore, the oxygen species desorbing at lower temperatures is responsible for the methane combustion.
The esterification of palmitic acid in rapeseed oil and methanol emulsified by propylene glycol with PTSA(p-toluene sulfonic acid) was followed by the transesterification of rapeseed oil into biodiesel with 1(w/v)% GMS(glycerol monostearate) as an emulsifier using TMAH(tetramethyl ammonium hydroxide) catalysts at 60℃. The former reaction was optimized at the 1:20 of molar ratio of oil to methanol and 5wt% PTSA, and the latter was optimized at the 1:8 of molar ratio of oil to methanol and 0.8wt% TMAH. The overall conversion into biodiesel was 98% after 60min of reaction time at the 1:8 of molar ratio, 0.8wt% TMAH and 60℃. TMAH was a good catalyst to control the viscosity of biodiesel mixture.
Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by O2-TPD and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the O2-TPD result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around 800℃.
Direct decomposition of methane over three types of carbon black (N330-p, N330-f, and HI-900L) was carried out in a fluidized bed quartz reactor. Properties of carbon black before and after reaction were measured and found to be related with surface structure and weight gain. For N330-p and N330-f, some carbon deposit on the surface was considered to be the reason for the increase of BET surface area and pore volume with weight gain. Carbon deposits on the surface and the conglutination of some aggregates may explain the slight increase of particle size. Properties of HI-900L changed much more significantly with weight gain. It is supposed that the increase of aggregate size of HI-900L were due to some unknown oily components. The corresponding agglomeration might be the reason for the decrease of BET surface area with weight gain, as compared with the increase of that for the case of N330 black.
It is interesting to discover the reaction kinetics of the newly developed molybdenum containing catalysts. The dissociation/adsorption of nitrogen on molybdenum surface is known to be structure sensitive, which is similar to that of nitrogen on iron surface. The rates over molybdenum nitride catalysts are increased with the increase of total pressure. This tendency is the same as that for iron catalyst, but is quite different from that for ruthenium catalyst. The activation energies of the molybdenum nitride catalysts are almost on the same level, although the activity is changed by the addition of the second component. The reaction rate is expressed as a function of the concentration of reactants and products. The surface nature of CO3Mo3N is drastically changed by the addition of alkali, changing the main adsorbed species from NH2 to NH on the surface. The strength of NHx adsorption is found to be changed by alkali dopping.
The copper oxide nano powders were synthesized by levitational gas condensation (LGC) method, and were applied to catalyst to fabricate 3,4-dihydropyrimidin-2-(1H)-one. Processes of adsorption of Biginelli reaction reagents on the copper nanooxide surface were studied by IR-spectroscopy. It was shown that benzaldehyde coordination, acetoacetic ether on the oxide surface is carried out with participation of carbonyl fragments, urea by N-H bonds which affects positively on the reagents reactivity.
The effect of La promoter on the carbon deposition and catalytic activity in the synthesis gas production with supported Ni catalysts was investigated. Active component was Ni and support was CeO2 and the promoter used was La. The reaction was carried out in a fixed bed reactor at 1 atm and 650~800℃. The catalysts were prepared by two methods, the impregnation method and urea method. The catalysts prepared by the urea method showed 10 times higher surface area than those of prepared by the impregnation method. By the introduction of La promoter in the catalyst system, carbon deposition was remarkably reduced from 16% to 2%. It appears that the promoter facilitates the formation of a stable fluoride-type phase, which reduces the carbon deposition. The best catalytic activity and CO and H2 selectivities were obtained with 2.5wt% Ni/Ce(La)Ox catalyst at 750℃, giving 90% methane conversion, 93 and.80% of CO and H2 selectivities, respectively.
Synthesis gas is produced commercially by a steam reforming process. However, the process is highly endothermic and energy intensive. Thus, this study was conducted to produce synthesis gas by the partial oxidation of methane to cut down the energy cost. Supported Ni catalysts were prepared by the impregnation method. To examine the activity of the catalysts, a differential fixed bed reactor was used, and the reaction was carried out at 750~850℃ and 1 atm. The fresh and used catalysts were characterized by XRD, XPS, TGA and AAS. The highest catalytic activity was obtained with the 13wt% Ni/MgO catalyst, with which methane conversion was 81%, and H2 and CO selectivities were 94% and 93%, respectively. 13wt% Ni/MgO catalyst showed the best MgNiO2 solid solution state, which can explain the highest catalytic activity of the 13wt% Ni/MgO catalyst.