A feasible and cost-effective process for utilization of toluene and heavy reformate is the conversion of its streams by transalkylation reaction into highly valuable xylenes. The process is usually catalysed by zeolites and the challenges to overcome in transalkylation of heavy reformate with toluene over zeolites are their selectivity, activity, long-term stability, and coke formation. Current study aimed to investigate xylenes production by transalkylation reaction on the synthesized metal-doped zeolite catalysts and to characterize prepared catalysts by FTIR, SEM, EDS and BET analysis. Toluene/heavy reformate modelled mixture was utilized as a feed. For the first time Beta and ZSM-5 catalysts with 10% (w/w) cerium and 0.1% (w/w) palladium were synthesized by calcination and wet impregnation method. Catalytic tests were performed by continuous-flow gas/solid catalytic fixed bed reactor at atmospheric pressure, 2 h-1 and 5 h-1 and 250, 300, 350 and 400 °C. Experimental results revealed that the highest heavy reformate conversion (98.94%) and toluene conversion (9.82%) were obtained over H-ZSM-5, at 400 °C and 2 h-1 WHSV. The highest xylene selectivity (11.53) was achieved over H-ZSM-5, and the highest p-xylene percentage (62.40%), using Ce-ZSM-5 catalyst. ZSM-5 catalysts showed more resistance to coke deposition than Beta zeolites. The present study delivers novel approach and catalysts, which have immense potential for developing safer and inexpensive transalkylation process in industry.
In this study, nickel-loaded perovskite oxides catalysts were synthesized via the impregnation of 10%Ni on XTiO3 (X = Ce, Sr, La, Ba, Ca, and Fe) supports and employed in the catalytic steam gasification of swine manure to produce H2-rich syngas for the first time. The synthesized catalysts were characterized using BET, H2-TPR, XRD, HR-TEM, and EDX analysis. Briefly, using perovskite supports resulted in the production of ultrafine catalyst nanoparticles with a uniform dispersion of Ni particles. According to the catalytic activity test, the gas yield showed the increment as 10% Ni/LaTiO3 < 10% Ni/FeTiO3 < 10% Ni/CeTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. Meanwhile, zero coke formation was achieved due to the oxygen mobility of prepared catalysts. Also, the increase in the H2 production for the applied catalysts was in the sequence as 10% Ni/CeTiO3 < 10% Ni/FeTiO3 < 10% Ni/LaTiO3 < 10% Ni/BaTiO3 < 10% Ni/SrTiO3 < 10% Ni/CaTiO3. The maximum H2 selectivity (∼48 vol%) obtained by10% Ni/CaTiO3 was probably due to the synergistic effect of Ni and Ti on enhancing the water-gas shift reaction, and Ca on creating the maximum oxygen mobility compared to other alkaline earth metals doped at the A place of perovskite. Overall, this study provides a suitable solution for enhanced H2 production through steam gasification of swine manure along with suggesting the appropriate supports to prevent Ni deactivation by lowering coke formation at the same time.
Due to their high lipid content, microalgae are one of the most significant sources of green hydrocarbons, which might help lessen the world's need for fossil fuels. Many zeolite-based catalysts are quickly deactivated by coke production and have a short lifetime. In this study, a bimetallic Lanthanum-Cerium (La-Ce)-modified HZSM-5 zeolite catalyst was synthesized through an impregnation method and was tested for the conversion of hydrolyzed oil into oxygen-free hydrocarbon fuels of high energy content. Initially, hydrolyzed oil (HO), the byproduct of the transesterification process, was obtained by the reaction of crude oil derived from Chlorella vulgaris microalgae and a methanol. Various catalysts were produced, screened, and evaluated for their ability to convert algal HO into hydrocarbons and other valuable compounds in a batch reactor. The performance of HZSM-5 was systematically tested in view of La-Ce loaded on conversion, yield, and selectivity. NH3-TPD analysis showed that the total acidity of the La-Ce-modified zeolites was lower than that of the pure HZSM-5 catalyst. TGA testing revealed that including the rare earth elements La and Ce in the HZSM-5 catalyst lowered the catalyst propensity for producing coke deposits. The acid sites necessary for algal HO conversion were improved by putting La and Ce into HZSM-5 zeolite at various loading percentages. The maximum hydrocarbon yield (42.963%), the highest HHV (34.362 MJ/Kg), and the highest DOD% (62.191%) were all achieved by the (7.5%La-2.5%Ce)/HZSM-5 catalyst, which was synthesized in this work. For comparison, the hydrocarbon yield for the parent HZSM-5 was 21.838%, the HHV was (33.230 MJ/Kg), and the DOD% was 44.235%. In conclusion, La and Ce-loading on the parent HZSM-5 may be responsible for the observed alterations in textural properties; nevertheless, there is no clear correlation between the physical features and the hydrocarbon yield (%). The principal effect of La and Ce modifying the parent HZSM-5 zeolite was to modify the acidic sites needed to enhance the conversion (%) of the algal HO during the catalytic deoxygenation process, which in turn raised the hydrocarbon yield (%) and increased the HHV and DOD%.
To replace the obsolete ponding system, palm oil mill effluent (POME) steam reforming (SR) over net-acidic LaNiO3 and net-basic LaCoO3 were proposed as the POME primary treatments, with promising H2-rich syngas production. Herein, the long-term evaluation of POME SR was scrutinized with both catalysts under the optimal conditions (600 °C, 0.09 mL POME/min, 0.3 g catalyst, & 74-105 μm catalyst particle size) to examine the catalyst microstructure changes, transient process stability, and final effluent evaluation. Extensive characterization proved the (i) adsorption of POME vapour on catalysts before SR, (ii) deposition of carbon and minerals on spent SR catalysts, and (iii) dominance of coking deactivation over sintering deactivation at 600 °C. Despite its longer run, spent LaCoO3 (50.54 wt%) had similar carbon deposition with spent LaNiO3 (50.44 wt%), concurring with its excellent coke resistance. Spent LaCoO3 (6.12 wt%; large protruding crystals) suffered a harsher mineral deposition than spent LaNiO3 (3.71 wt%; thin film coating), confirming that lower reactivity increased residence time of reactants. Transient syngas evolution of both SR catalysts was relatively steady up to 4 h but perturbed by coking deactivation thereafter. La2O2CO3 acted as an intermediate species that hastened the coke removal via reverse Boudouard reaction upon its decarbonation. La2O2CO3 decarbonation occurred continuously in LaCoO3 system but intermittently in LaNiO3 system. LaNiO3 system only lasted for 13 h as its compact ash blocked the gas flow. LaCoO3 system lasted longer (17 h) with its porous ash, but it eventually failed because KCl crystallites blocked its active sites. Relatively, LaCoO3 system offered greater net H2 production (72.78%) and POME treatment volume (30.77%) than LaNiO3 system. SR could attain appreciable POME degradation (>97% COD, BOD5, TSS, & colour intensity). Withal, SR-treated POME should be polished to further reduce its incompliant COD and BOD5.
Solid acid catalyzed cracking of waste oil-derived fatty acids is an attractive route to hydrocarbon fuels. HZSM-5 is an effective acid catalyst for fatty acid cracking; however, its microporous nature is susceptible to rapid deactivation by coking. We report the synthesis and application of hierarchical HZSM-5 (h-HZSM-5) in which silanization of pre-crystallized zeolite seeds is employed to introduce mesoporosity during the aggregation of growing crystallites. The resulting h-HZSM-5 comprises a disordered array of fused 10-20 nm crystallites and mesopores with a mean diameter of 13 nm, which maintain the high surface area and acidity of a conventional HZSM-5. Mesopores increase the yield of diesel range hydrocarbons obtained from oleic acid deoxygenation from ~20% to 65%, attributed to improved acid site accessibility within the hierarchical network.
A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.
Taguchi orthogonal array design, a statistical software is applied to n-hexane reforming. The purpose is to identify the most significant process variable in reforming conditions favouring n-hexane conversion to high aromatics and isomers and low cracked and coke precursor reformate products. Actual experimental data were used for this study. Three process variables i.e. temperature, contact time and hydrogen partial pressure were investigated. From the study it was found that the contact time was the most critical operating parameter for n-hexane conversion followed by reaction temperature and hydrogen partial pressure. It was also noted that enhanced n-hexane reforming conversion can be achieved by operating the process at reaction temperature 723 K and contact time 7.1 min with a H2 partial pressure 300 kPa. For selectivity to aromatics and isomers lower contact time of 1.07 min with intermediate hydrogen partial pressure of 300 to 500 kPa operating at a reaction temperature of 723 K is most favourable.
In this study, a binary mixture of petroleum coke and palm kernel shell had been investigated as potential starting materials for activated carbon production. Single-stage potassium carbonate (K2CO3) activation under nitrogen (N2) atmosphere was adopted in this research study. Effect of several operating parameters that included the impregnation ratio (1-3 wt./wt.), activation temperature (600-800 °C), and dwell time (1-2 hrs) were analyzed by using the Box-Behnken experimental design. Influence of these parameters towards activated carbon yield (Y1) and carbon dioxide (CO2) adsorption capacity at an atmospheric condition (Y2) were investigated. The optimum conditions for the activated carbon production were attained at impregnation ratio of 1.75:1, activation temperature of 680 °C, and dwell time of 1 h, with its corresponding Y1 and Y2 is 56.2 wt.% and 2.3991 mmol/g, respectively. Physicochemical properties of the pristine materials and synthesized activated carbon at the optimum conditions were analyzed in terms of their decomposition behavior, surface morphology, elemental composition, and textural characteristics. The study revealed that the blend of petroleum coke and palm kernel shell can be effectively used as the activated carbon precursors, and the experimental findings demonstrated comparable CO2 adsorption performance with commercial activated carbon as well as that in literatures.
Hydrocarbon-fueled solid oxide fuel cells (SOFCs) that can operate in the intermediate temperature range of 500-700 °C represent an attractive SOFC device for combined heat and power applications in the industrial market. One of the ways to realize such a device relies upon exploiting an in situ steam reforming process in the anode catalyzed by an anti-carbon coking catalyst. Here, we report a new Ni and Ru bimetal-doped perovskite catalyst, Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.9Ni0.05Ru0.05O3-δ (BZCYYbNRu), with enhanced catalytic hydrogen production activity on n-butane (C4H10), which can resist carbon coking over extended operation durations. Ru in the perovskite lattice inhibits Ni precipitation from perovskite, and the high water adsorption capacity of proton conducting perovskite improves the coking resistance of BZCYYbNRu. When BZCYYbNRu is used as a steam reforming catalyst layer on a Ni-YSZ-supported anode, the single fuel cell not only achieves a higher power density of 1113 mW cm-2 at 700 °C under a 10 mL min-1 C4H10 continuous feed stream at a steam to carbon (H2O/C) ratio of 0.5 but also shows a much better operational stability for 100 h at 600 °C compared with those reported in the literature.
In this study, the effect of beverages (Coke TM, Sprite™, Ribena™, Chrysanthemum tea and mineral water) on the demineralisation of the enamel surface was investigated. Demineralisation was determined by the rate of calcium released from the enamel surface on exposure to the beverages. Calcium was determined using the EDTA titration method. The pH of these beverages was measured using a pH meter and found to be in the acidic range (2.43 to 5.79) while mineral water which served as a control has a pH of 7.00. Ii was found that the rate of calcium released from Coke™(0.76 J..lg/min) showed a significant mean difference from Sprite™ (0.38 J..lg/min), Chrysanthemum tea (0.10 J..lg/min) and mineral water (0.00 J..lg/min)at p< .05, but was however not significantly different from Ribena™. Likewise, Chrysanthemum tea and mineral water also showed statistically no significant mean difference in the released of calcium during the study period. The results obtained in this study indicated that beverages with low pH may pose detrimental effect on the enamel surface which could have clinical implication, especially in people with salivary gland dysfunction or low salivary flow.
Energy has a significant influence on Malaysia's industry. It is used in electricity generation, refineries, gas processing plants and end-user applications such as transportation, residential, agriculture and fishing. These burning fossil fuel activities produce greenhouse gases (GHG) emissions. This article presents the emissions data of fuel used in power plants in Malaysia during the year of 1990 until 2017. The fuel used in power plants is coal and coke, natural gas, diesel oil and residual fuel oil. The energy data used in power plants were gathered from the Malaysia Energy Information Hub, published by the Malaysian Energy Commission. The GHG emissions data were calculated using the emission factors method. The climate impact of different GHGs in terms of CO2-equivalent (CO2-e) was also calculated using global warming potentials. The article also presents population data in Malaysia during the year. A correlation between the fuels, GHG emission and the population is also investigated using statistical analysis. The data presented here may facilitate the Malaysian government to identify the source of the pollutants and undertake a climate change mitigation plan.