Search results for: catalytic pyrolysis

Authors: Anushree, Chhaya Sharma, Satish Kumar

Abstract:

Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO₂ nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO₂ nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce₄₀Ni₆₀ catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: Nano-materials, NiO-CeO2, wastewater, wet air oxidation.

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Authors: V. Georgiev

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Catalytic oxidation of benzene assisted by ozone, on alumina, silica, and boehmite-supported Ni/Pd catalysts was investigated at 353 K to assess the influence of the support on the reaction. Three bimetallic Ni/Pd nanosized samples with loading 4.7% of Ni and 0.17% of Pd supported on SiO₂, AlOOH and Al₂O₃ were synthesized by the extractive-pyrolytic method. The phase composition was characterized by means of XRD and the surface area and pore size were estimated using Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) methods. At the beginning of the reaction, catalysts were significantly deactivated due to the accumulation of intermediates on the catalyst surface and after 60 minutes it turned stable. Ni/Pd/AlOOH catalyst showed the highest steady-state activity in comparison with the Ni/Pd/SiO₂ and Ni/Pd/Al₂O₃ catalysts. Their activity depends on the ozone decomposition potential of the catalysts because of generating oxidizing active species. The sample with the highest ozone decomposition ability which correlated to the surface area of the support oxidizes benzene to the highest extent.

Keywords: Ozone, catalysts, oxidation, Volatile organic compounds, VOCs.

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Authors: Javier Rivas, Olga Gimeno, Maria Carbajo, Teresa Borralho

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Potassium monopersulfate has been decomposed in aqueous solution in the presence of Co(II). The effect of the main operating variables has been assessed. Minimum variations in pH exert a considerable influence on the process kinetics. Thus, when no pH adjustment is considered, the actual effect of variables like initial monopersulfate and/or catalyst concentration may be hindered. As expected, temperature enhances the monopersulfate decomposition rate by following the Arrhenius law. The activation energy in the proximity of 85 kJ/mol has been obtained. Amongst the different solids tested in the monopersulfate decomposition, only the perovskite LaTi0.15Cu0.85O3 has shown a significant catalytic activity.

Keywords: Monopersulfate, Oxone®, Sulfate radicals, Watertreatment.

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Authors: Jian Huang, Weixin Qian, Haitao Zhang, Weiyong Ying

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Cobalt-gadolinium catalyst for Fischer-Tropsch synthesis was prepared by impregnation method with commercial silica gel, and its texture properties were characterized by BET, XRD, and TPR. The catalytic performance of the catalyst was tested in a fixed bed reactor. The results showed that the addition of gadolinium to the cobalt catalyst might decrease the size of cobalt particles, and increased the dispersion of catalytic active cobalt phases. The carbon number distributions for the catalysts was calculated by ASF equation.

Keywords: Fischer-Tropsch synthesis, cobalt-based catalysts, gadolinium, carbon number distributions.

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Authors: Ramlan Zailani, Halim Ghafar, Mohamad Sofian So'aib

Abstract:

Air infiltration in mass scale industrial applications of bio char production is inevitable. The presence of oxygen during the carbonization process is detrimental to the production of biochar yield and properties. The experiment was carried out on several wood species in a fixed-bed pyrolyser under various fractions of oxygen ranging from 0% to 11% by varying nitrogen and oxygen composition in the pyrolysing gas mixtures at desired compositions. The bed temperature and holding time were also varied. Process optimization was carried out by Response Surface Methodology (RSM) by employing Central Composite Design (CCD) using Design Expert 6.0 Software. The effect of oxygen ratio and holding time on biochar yield within the range studied were statistically significant. From the analysis result, optimum condition of 15.2% biochar yield of mangrove wood was predicted at pyrolysis temperature of 403 oC, oxygen percentage of 2.3% and holding time of two hours. This prediction agreed well with the experiment finding of 15.1% biochar yield.

Keywords: Mangrove wood, slow pyrolysis, oxygen infiltration.

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Authors: Yan Zeng, Hongfang Ma, Haitao Zhang, Weiyong Ying

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Ni-based catalysts with different amounts of Na as promoter from 2 to 6 wt % were prepared by solution combustion method. The catalytic activity was investigated in syngas methanation reaction. Carbon oxides conversion and methane selectivity are greatly influenced by sodium loading. Adding 2 wt% Na remarkably improves catalytic activity and long-term stability, attributed to its smaller mean NiO particle size, better distribution, and milder metal-support interaction. However, excess addition of Na results in deactivation distinctly due to the blockage of active sites.

Keywords: Nickel catalysts, Syngas methanation, Sodium, Solution combustion method.

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Authors: H. Ganji, H. R. Mahdipoor, J. Ahmadpanah, H. Naderi

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The modified Claus process is the major technology for the recovery of elemental sulfur from hydrogen sulfide. The chemical reactions that can occur in the reaction furnace are numerous and many byproducts such as carbon disulfide and carbon carbonyl sulfide are produced. These compounds can often contribute from 20 to 50% of the pollutants and therefore, should be hydrolyzed in the catalytic converter. The inlet temperature of the first catalytic reactor should be maintained over than 250 °C, to hydrolyze COS and CS2. In this paper, the various configurations for the first converter reheating of sulfur recovery unit are investigated. As a result, the performance of each method is presented for a typical clause unit. The results show that the hot gas method seems to be better than the other methods.

Keywords: Sulfur recovery unit, reaction converter.

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

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The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, ceria, gold catalysts.

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Authors: Prathap S. Raghavendra, Mohamed S. Z. Shamshuddin, Thimmaraju N., Venkatesh

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The transesterification of dimethyl malonate (DMM) with phenol has been studied in vapour phase over cordierite honeycomb coated with solid acid catalysts such as ZrO2, Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared honeycomb coated, powder forms, and characterized for their total surface acidity by NH3-TPD and crystalinity by powder XRD methods. Phenyl methyl malonate (PMM) and diphenyl malonate (DPM) were obtained as the reaction products. A good conversion of DMM (up to 82%) of MPM with 95% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 °C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. However, over SO4^2-/ZrO2 catalyst, the yield of DPM was found to be higher. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or SO42– ions. Transesterification reactions were also carried out over powder forms of the catalytic materials and the yield of the desired phenyl ester products were compared with that of the HC coated catalytic materials. The solid acids were found to be reusable when used for at least 5 reaction cycles.

Keywords: Cordierite honeycomb, methyl phenyl malonate, vapour phase transesterification, zirconia.

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Authors: H. Wasag

Abstract:

The removal of hydrogen sulphide is required for reasons of health, odour problems, safety and corrosivity problems. The means of removing hydrogen sulphide mainly depend on its concentration and kind of medium to be purified. The paper deals with a method of hydrogen sulphide removal from the air by its catalytic oxidation to elemental sulphur with the use of Fe-EDTA complex. The possibility of obtaining fibrous filtering materials able to remove small concentrations of H2S from the air were described. The base of these materials is fibrous ion exchanger with Fe(III)- EDTA complex immobilized on their functional groups. The complex of trivalent iron converts hydrogen sulphide to elemental sulphur. Bivalent iron formed in the reaction is oxidized by the atmospheric oxygen, so complex of trivalent iron is continuously regenerated and the overall process can be accounted as pseudocatalytic. In the present paper properties of several fibrous catalysts based on ion exchangers with different chemical nature (weak acid,weak base and strong base) were described. It was shown that the main parameters affecting the process of catalytic oxidation are:concentration of hydrogen sulphide in the air, relative humidity of the purified air, the process time and the content of Fe-EDTA complex in the fibres. The data presented show that the filtering layers with anion exchange package are much more active in the catalytic processes of hydrogen sulphide removal than cation exchanger and inert materials. In the addition to the nature of the fibres relative air humidity is a critical factor determining efficiency of the material in the air purification from H2S. It was proved that the most promising carrier of the Fe-EDTA catalyst for hydrogen sulphide oxidation are Fiban A-6 and Fiban AK-22 fibres.

Keywords: hydrogen sulphide, catalytic oxidation, odour control, ion exchange, fibrous ion exchangers, air deodorization

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Authors: Tae Hyun Ahn, Gyo Woo Lee, Man Young Kim

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Because of high thermal efficiency and low CO2 emission, diesel engines are being used widely in many industrial fields although it makes many PM and NOx which give both human health and environment a negative effect. NOx regulations for diesel engines, however, are being strengthened and it is impossible to meet the emission standard without NOx reduction devices such as SCR (Selective Catalytic Reduction), LNC (Lean NOx Catalyst), and LNT (Lean NOx Trap). Among the NOx reduction devices, urea-SCR system is known as the most stable and efficient method to solve the problem of NOx emission. But this device has some issues associated with the ammonia slip phenomenon which is occurred by shortage of evaporation and thermolysis time, and that makes it difficult to achieve uniform distribution of the injected urea in front of monolith. Therefore, this study has focused on the mixing enhancement between urea and exhaust gases to enhance the efficiency of the SCR catalyst equipped in catalytic muffler by changing inlet gas temperature and spray conditions to improve the spray uniformity of the urea water solution. Finally, it can be found that various parameters such as inlet gas temperature and injector and injection angles significantly affect the evaporation and mixing of the urea water solution with exhaust gases, and therefore, optimization of these parameters are required.

Keywords: Evaporation, Injection, Selective Catalytic Reduction (SCR), Thermolysis, UWS (Urea-Water-Solution).

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Authors: Algirdas Jasinskas, Egidijus Šarauskis, Raimondas Šarauskis, Antanas Sakalauskas

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This paper presents the new results of energy plant – rye and triticale at yellow ripeness and ripe, pre-treatment in high pressure steam reactor and monosaccharide extraction. There were investigated the influence of steam pressure (20 to 22 bar), retention duration (180 to 240 s) and catalytic sulphuric acid concentration strength (0 to 0.5 %) on the pre-treatment process, contents of monosaccharides (glucose, arabinose, xylose, mannose) and undesirable by-compounds (furfural and HMF) in the reactor. The study has determined that the largest amount of monosaccharides (37.2 % of glucose, 2.7 % of arabinose, 8.4 % of xylose, and 1.3 % of mannose) was received in the rye at ripe, the samples of which were mixed with 0.5 % concentration of catalytic sulphuric acid, and hydrolysed in the reactor, where the pressure was 20 bar, whereas the reaction time – 240 s.

Keywords: Bioethanol, Pre-treatment, Rye, Triticale.

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Authors: S.Fardindoost, A. Iraji Zad, S.M.Mahdavi

Abstract:

Tungsten trioxide has been prepared by using P-PTA as a precursor on alumina substrates by spin coating method. Palladium introduced on WO3 film via electrolysis deposition by using palladium chloride as catalytic precursor. The catalytic precursor was introduced on the series of films with different morphologies. X-ray diffractometry (XRD), Scanning electron microscopy (SEM) and XPS were applied to analyze structure and morphology of the fabricated thin films. Then we measured variation of samples- electrical conductivity of pure and Pd added films in air and diluted hydrogen. Addition of Pd resulted in a remarkable improvement of the hydrogen sensing properties of WO3 by detection of Hydrogen below 1% at room temperature. Also variation of the electrical conductivity in the presence of diluted hydrogen revealed that response of samples depends rather strongly on the palladium configuration on the surface.

Keywords: Electrolysis, Hydrogen sensing, Palladium, WO3

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Authors: M.F. Mohamad, Anita Ramli, S.E.E Misi, S. Yusup

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This work presents the hydrogen production from steam gasification of palm kernel shell (PKS) at 700 oC in the presence of 5% Ni/BEA and 5% Fe/BEA as catalysts. The steam gasification was performed in two-staged reactors to evaluate the effect of calcinations temperature and the steam to biomass ratio on the product gas composition. The catalytic activity of Ni/BEA catalyst decreases with increasing calcinations temperatures from 500 to 700 oC. The highest H2 concentration is produced by Fe/BEA (600) with more than 71 vol%. The catalytic activity of the catalysts tested is found to correspond to its physicochemical properties. The optimum range for steam to biomass ratio if found to be between 2 to 4. Excess steam content results in temperature drop in the gasifier which is undesirable for the gasification reactions.

Keywords: Hydrogen, Palm Kernel Shell, Steam gasification, Ni/BEA, Fe/BEA

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Authors: M. Wannaborworn, B. Jongsomjit, T. Shiono

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Copolymerization of ethylene with 1-hexene was carried out using two ansa-fluorenyl titanium derivative complexes. The substituent effect on the catalytic activity, monomer reactivity ratio and polymer property was investigated. It was found that the presence of t-Bu groups on fluorenyl ring exhibited remarkable catalytic activity and produced polymer with high molecular weight. However, these catalysts produce polymer with narrow molecular weight distribution, indicating the characteristic of single-site metallocene catalyst. Based on 13C NMR, we can observe that monomer reactivity ratio was affected by catalyst structure. The rH values of complex 2 were lower than that of complex 1 which might be result from the higher steric hindrance leading to a reduction of 1- hexene insertion step.

Keywords: Constrained geometry catalyst, linear low density polyethylene, copolymerization, reactivity ratio

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Authors: Xiangjun Li, Huaiyuan Tian, Wujie Zhang, Dianhua Liu

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Polyoxymethylene dimethyl ethers (PODE_n) as clean diesel additive can improve the combustion efficiency and quality of diesel fuel and alleviate the problem of atmospheric pollution. Considering synthetic routes, PODE production from methanol and formaldehyde is regarded as the most economical and promising synthetic route. However, methanol used for synthesizing PODE can produce water, which causes the loss of active center of catalyst and hydrolysis of PODE_n in the production process. Macroporous strong acidic cation exchange resin catalyst was prepared, which has comparative advantages over other common solid acid catalysts in terms of stability and catalytic efficiency for synthesizing PODE. Catalytic reactions were carried out under 353 K, 1 MPa and 3mL·g_cat^-1·h^-1 in a fixed bed reactor. Methanol conversion and PODE_3-6 selectivity reached 49.91% and 23.43%, respectively. Catalyst lifetime evaluation showed that resin catalyst retained its catalytic activity for 20 days without significant changes and catalytic activity of completely deactivated resin catalyst can basically return to previous level by simple acid regeneration. The acid exchange capacities of original and deactivated catalyst were 2.5191 and 0.0979 mmol·g^-1, respectively, while regenerated catalyst reached 2.0430 mmol·g^-1, indicating that the main reason for resin catalyst deactivation is that Brønsted acid sites of original resin catalyst were temporarily replaced by non-hydrogen ion cations. A separation process consisting of extraction and distillation for PODE_3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE_3-6, respectively. The concentration of PODE_3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE_3-6 from methanol and formaldehyde solution is feasible.

Keywords: Inactivation, polyoxymethylene dimethyl ethers, separation process, sulfonic cation exchange resin.

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Authors: Junjie Chen, Deguang Xu

Abstract:

Transient simulation of the hydrogen-assisted self-ignition of propane-air mixtures were carried out in platinum-coated micro-channels from ambient cold-start conditions, using a two-dimensional model with reduced-order reaction schemes, heat conduction in the solid walls, convection and surface radiation heat transfer. The self-ignition behavior of hydrogen-propane mixed fuel is analyzed and compared with the heated feed case. Simulations indicate that hydrogen can successfully cause self-ignition of propane-air mixtures in catalytic micro-channels with a 0.2 mm gap size, eliminating the need for startup devices. The minimum hydrogen composition for propane self-ignition is found to be in the range of 0.8-2.8% (on a molar basis), and increases with increasing wall thermal conductivity, and decreasing inlet velocity or propane composition. Higher propane-air ratio results in earlier ignition. The ignition characteristics of hydrogen-assisted propane qualitatively resemble the selectively inlet feed preheating mode. Transient response of the mixed hydrogen- propane fuel reveals sequential ignition of propane followed by hydrogen. Front-end propane ignition is observed in all cases. Low wall thermal conductivities cause earlier ignition of the mixed hydrogen-propane fuel, subsequently resulting in low exit temperatures. The transient-state behavior of this micro-scale system is described, and the startup time and minimization of hydrogen usage are discussed.

Keywords: Micro-combustion, Self-ignition, Hydrogen addition, Heat transfer, Catalytic combustion, Transient simulation.

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Authors: Umpawan Satitthai, Apanee Luengnaruemitchai, Erdogan Gulari

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In this study, oxidative steam reforming of methanol (OSRM) over a Au/CeO2–Fe2O3 catalyst prepared by a depositionprecipitation (DP) method was studied to produce hydrogen in order to feed a Proton Exchange Membrane Fuel Cell (PEMFC). The support (CeO2, Fe2O3, and CeO2–Fe2O3) were prepared by precipitation and co-precipitation methods. The impact of the support composition on the catalytic performance was studied by varying the Ce/(Ce+Fe) atomic ratio, it was found that the 1%Au/CF(0.25) calcined at 300 °C exhibited the highest catalytic activity in the whole temperature studied. In addition, the effect of Au content was investigated and 3%Au/CF(0.25) exhibited the highest activity under the optimum condition in the temperature range of 200 °C to 400 °C. The catalysts were characterized by various techniques: XRD, TPR, XRF, and UV-vis.

Keywords: CeO2, Fe2O3, Gold catalyst, Hydrogen production, Methanol, Oxidative steam reforming.

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Authors: D. Salari, A. Niaei, P. Chitsaz Yazdi, M. Derakhshani, S. R. Nabavi

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This work aims to test the application of computational fluid dynamics (CFD) modeling to fixed bed catalytic cracking reactors. Studies of CFD with a fixed bed design commonly use a regular packing with N=2 to define bed geometry. CFD allows us to obtain a more accurate view of the fluid flow and heat transfer mechanisms present in fixed bed equipment. Naphtha was used as feedstock and the reactor length was 80cm. It is divided in three sections that catalyst bed packed in the middle section of the reactor. The reaction scheme was involved one primary reaction and 24 secondary reactions. Because of high CPU times in these simulations, parallel processing have been used. In this study the coke formation process in fixed bed and empty tube reactor was simulated and coke in these reactors are compared. In addition, the effect of steam ratio and feed flow rate on coke formation was investigated.

Keywords: Coke Formation, CFD Simulation, Fixed Bed, Catalyitic Cracking.

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Authors: Jian Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

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Cobalt catalysts were supported on extruded silica carrier and different-type (SiO₂, γ-Al₂O₃) commercial supports with different shapes and sizes to produce heavy hydrocarbons for Fischer-Tropsch synthesis. The catalysts were characterized by N₂ physisorption and H₂-TPR. The catalytic performance of the catalysts was tested in a fixed bed reactor. The results of Fischer-Tropsch synthesis performance showed that the cobalt catalyst supported on spherical silica supports displayed a higher activity and a higher selectivity to C₅⁺ products, due to the fact that the active components were only distributed in the surface layer of spherical carrier, and the influence of gas diffusion restriction on catalytic performance was weakened. Therefore, it can be concluded that the eggshell cobalt catalyst was superior to precious metals modified catalysts in the synthesis of heavy hydrocarbons.

Keywords: Fischer-Tropsch synthesis, cobalt catalyst, support shape, heavy hydrocarbons.

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Authors: V. Pérez-Herranz, C. González-Buch, E. M. Ortega, S. Mestre

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In this work new macroporous Ni electrodes modified with Au nanoparticles for hydrogen production have been developed. The supporting macroporous Ni electrodes have been obtained by means of the electrodeposition at high current densities. Then, the Au nanoparticles were synthesized and added to the electrode surface. The electrocatalytic behaviour of the developed electrocatalysts was studied by means of pseudo-steady-state polarization curves, electrochemical impedance spectroscopy (EIS) and hydrogen discharge curves. The size of the Au synthetized nanoparticles shows a monomodal distribution, with a very sharp band between 10 and 50 nm. The characteristic parameters d10, d50 and d90 were 14, 20 and 31 nm respectively. From Tafel polarization data has been concluded that the Au nanoparticles improve the catalytic activity of the developed electrodes towards the HER respect to the macroporous Ni electrodes. EIS permits to obtain the electrochemically active area by means of the roughness factor value. All the developed electrodes show roughness factor values in the same order of magnitude. From the activation energy results it can be concluded that the Au nanoparticles improve the intrinsic catalytic activity of the macroporous Ni electrodes.

Keywords: Au nanoparticles, hydrogen evolution reaction, porous Ni electrodes.

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Authors: Chinwendu R. Nnabalu, Gioia Falcone, Imma Bortone

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Petroleum refining is a chemical process in which the raw material (crude oil) is converted to finished commercial products for end users. The fluid catalytic cracking (FCC) unit is a key asset in refineries, requiring optimised processes in the context of engineering design. Following the first stage of separation of crude oil in a distillation tower, an additional 40 per cent quantity is attainable in the gasoline pool with further conversion of the downgraded product of crude oil (residue from the distillation tower) using a catalyst in the FCC process. Effective removal of sulphur oxides, nitrogen oxides, carbon and heavy metals from FCC gasoline requires greater separation efficiency and involves an enormous environmental significance. The FCC unit is primarily a reactor and regeneration system which employs cyclone systems for separation.  Catalyst losses in FCC cyclones lead to high particulate matter emission on the regenerator side and fines carryover into the product on the reactor side. This paper aims at demonstrating the importance of FCC unit design criteria in terms of technical performance and compliance with environmental legislation. A systematic review of state-of-the-art FCC technology was carried out, identifying its key technical challenges and sources of emissions.  Case studies of petroleum refineries in Nigeria were assessed against selected global case studies. The review highlights the need for further modelling investigations to help improve FCC design to more effectively meet product specification requirements while complying with stricter environmental legislation.

Keywords: Design, emissions, fluid catalytic cracking, petroleum refineries.

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Authors: Zhiqiang Xu, Hongfang Ma, Haitao Zhang, Weixin Qian, Weiyong Ying

Abstract:

SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH₃-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.

Keywords: Crystallization, MTO, Si/Al ratio, SSZ-13.

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Authors: Mona Lisa M. Oliveira, Nara A. Policarpo, Ana Luiza B. P. Barros, Carla A. Silva

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Selective catalytic reduction systems for nitrogen oxides reduction by ammonia has been the chosen technology by most of diesel vehicle (i.e. bus and truck) manufacturers in Brazil, as also in Europe. Furthermore, at some conditions, over-stoichiometric ammonia availability is also needed that increases the NH₃ slips even more. Ammonia (NH₃) by this vehicle exhaust aftertreatment system provides a maximum efficiency of NOx removal if a significant amount of NH₃ is stored on its catalyst surface. In the other words, the practice shows that slightly less than 100% of the NOx conversion is usually targeted, so that the aqueous urea solution hydrolyzes to NH₃ via other species formation, under relatively low temperatures. This paper presents a model based on neural networks integrated with a road vehicle simulator that allows to estimate NH₃-slip emission factors for different driving conditions and patterns. The proposed model generates high NH₃slips which are not also limited in Brazil, but more efforts needed to be made to elucidate the contribution of vehicle-emitted NH₃ to the urban atmosphere.

Keywords: Ammonia slip, neural-network, vehicles emissions, SCR-NOx.

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Authors: N. Marzban, J. K. Heydarzadeh M. Pourmohammadbagher, M. H. Hatami, A. Samia

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A nano-alumina-zirconia composite catalyst was synthesized by a simple aqueous sol-gel method using AlCl₃.6H₂O and ZrCl₄ as precursors. Thermal decomposition of the precursor and subsequent formation of γ-Al₂O₃ and t-Zr were investigated by thermal analysis. XRD analysis showed that γ-Al₂O₃ and t-ZrO₂ phases were formed at 700 °C. FT-IR analysis also indicated that the phase transition to γ-Al₂O₃ occurred in corroboration with X-ray studies. TEM analysis of the calcined powder revealed that spherical particles were in the range of 8-12 nm. The nano-alumina-zirconia composite particles were mesoporous and uniformly distributed in their crystalline phase. In order to measure the catalytic activity, esterification reaction was carried out. Biodiesel, as a renewable fuel, was formed in a continuous packed column reactor. Free fatty acid (FFA) was esterified with ethanol in a heterogeneous catalytic reactor. It was found that the synthesized γ-Al₂O₃/ZrO₂ composite had the potential to be used as a heterogeneous base catalyst for biodiesel production processes.

Keywords: Nano-alumina-zirconia, composite catalyst, thin film, biodiesel.

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Authors: S. Mahmoudi, A. Belhaj Mohamed, M. Saidi, F. Rezgui

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Depositional environment and source potential of the different organic-rich levels of Devonian age (up to 990m thick) from the onshore EC-1 well (Southern Tunisia) were investigated based on the analysis of more than 130 cutting samples by different geochemical techniques (Rock-Eval pyrolysis, GC-MS). The obtained results including Rock Eval Pyrolysis data and biomarker distribution (terpanes, steranes and aromatics) have been used to describe the depositional environment and to assess the thermal maturity of the Devonian organic matter. These results show that the Emsian deposits exhibit poor to fair TOC contents. The associated organic matter is composed of mixed kerogen (type II/III), as indicated by the predominance of C29 steranes over C27 and C28 homologous, that was deposited in a slightly reduced environment favoring organic matter preservation. Thermal maturity assessed from Tmax, TNR and MPI-1 values shows a mature stage of organic matter. The Middle Devonian (Eifelian) shales are rich in type II organic matter that was deposited in an open marine depositional environment. The TOC values are high and vary between 2 and 7% indicating good to excellent source rock. The relatively high HI values (reaching 547 mg HC/g TOC) and the low values of t19/t23 tricyclic terpane ratio (< 0.2) confirm the marine origin of the organic matter (type II). During the Upper Devonian, the organic matter was deposited under variable redox conditions, oxic to suboxic which is clearly indicated by the low C35/C34 hopanes ratio, immature to marginally mature with the vitrinite reflectance ranging from 0.5 to 0.7 Ro and Tmax value of 426°C-436 °C and the TOC values range between 0.8% to 4%.

Keywords: Depositional environment, Devonian, Source rock.

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Authors: S. Totong, K. Faungnawakij, N. Laosiripojana

Abstract:

The development of alternative energy is interesting in the present especially, hydrogen production because it is an important energy resource in the future. This paper studied the hydrogen production from catalytic dehydrogenation of ethanol through via low temperature (<500°C) reaction. Copper (Cu) and silver (Ag) supported on fumed silica (SiO2) were selected in the present work; in addition, bimetallic material; Ag-Cu supported on SiO2 was also investigated. The catalysts were prepared by the incipient wetness impregnation method and characterized via X-ray diffraction (XRD), temperature-programmed reduction (TPR)and nitrogen adsorption measurements. The catalytic dehydrogenation of ethanol was carried out in a fixed bed continuous flow reactor at atmospheric pressure. The effect of reaction temperature between 300-375°C was studied in order to maximize the hydrogen yield. It was found that Ag-Cu/SiO2 exhibited the highest hydrogen yield compared to Ag/SiO2 and Cu/SiO2 at low reaction temperature (300°C) with full ethanol conversion. The highest hydrogen yield observed was 40% and will be further used as a reactant in fuel cells to generate electricity or feedstock of chemical production. 

Keywords: Catalyst, dehydrogenation, ethanol, hydrogen production.

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Authors: Saeid Khajehmandali, Fattah Mollakarimi, Zohreh Seyf

Abstract:

There was a high rate of corrosion in Pyrolysis Gasoline Hydrogenation (PGH) unit of Arak Petrochemical Company (ARPC), and it caused some operational problem in this plant. A commercial chemical had been used as anti-corrosion in the depentanizer column overhead in order to control the corrosion rate. Injection of commercial corrosion inhibitor caused some operational problems such as fouling in some heat exchangers. It was proposed to replace this commercial material with another more effective trouble free, and well-known additive by R&D and operation specialists. At first, the system was simulated by commercial simulation software in electrolytic system to specify low pH points inside the plant. After a very comprehensive study of the situation and technical investigations ,ammonia / monoethanol amine solution was proposed as neutralizer or corrosion inhibitor to be injected in a suitable point of the plant. For this purpose, the depentanizer column and its accessories system was simulated again in case of this solution injection. According to the simulation results, injection of new anticorrosion substance has no any side effect on C5 cut product and operating conditions of the column. The corrosion rate will be cotrolled, if the pH remains at the range of 6.5 to 8 . Aactual plant test run was also carried out by injection of ammonia / monoethanol amine solution at the rate of 0.6 Kg/hr and the results of iron content of water samples and corrosion test coupons confirmed the simulation results. Now, ammonia / monoethanol amine solution is injected to a suitable pint inside the plant and corrosion rate has decreased significantly.

Keywords: Corrosion, Pyrolysis Gasoline, Simulation, Corrosion test copoun.

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Authors: A. Udayakumar, M. Rizvan Basha, M. Stalin, V.V Bhanu Prasad

Abstract:

Three dimensional non-Interlaced carbon fibre reinforced silicon carbide (3-D-Cf/SiC) composites with pyrocarbon interphase were fabricated using isothermal chemical vapor infiltration (ICVI) combined with polymer impregnation pyrolysis (PIP) process. Polysilazane (PSZ) is used as a preceramic polymer to obtain silicon carbide matrix. Thermo gravimetric analysis (TGA), Infrared spectroscopic analysis (IR) and X-ray diffraction (XRD) analysis were carried out on PSZ pyrolysed at different temperatures to understand the pyrolysis and obtaining the optimum pyrolysing condition to yield β-SiC phase. The density of the composites was 1.94 g cm-3 after the 3-D carbon preform was SiC infiltrated for 280 h with one intermediate polysilazane pre-ceramic PIP process. Mechanical properties of the composite materials were investigated under tensile, flexural, shear and impact loading. The values of tensile strength were 200 MPa at room temperature (RT) and 195 MPa at 500°C in air. The average RT flexural strength was 243 MPa. The lower flexural strength of these composites is because of the porosity. The fracture toughness obtained from single edge notched beam (SENB) technique was 39 MPa.m1/2. The work of fracture obtained from the load-displacement curve of SENB test was 22.8 kJ.m-2. The composites exhibited excellent impact resistance and the dynamic fracture toughness of 44.8 kJ.m-2 is achieved as determined from instrumented Charpy impact test. The shear strength of the composite was 93 MPa, which is significantly higher compared 2-D Cf/SiC composites. Microstructure evaluation of fracture surfaces revealed the signatures of fracture processes and showed good support for the higher toughness obtained.

Keywords: 3-D-Cf/SiC, charpy impact test, composites, dynamic fracture toughness, polysilazane, pyrocarbon, Interphase.

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Authors: Ezgi Dündar-Tekkaya, Nilgün Karatepe

Abstract:

Carbon nanotubes (CNTs) with their high mechanical, electrical, thermal and chemical properties are regarded as promising materials for many different potential applications. Having unique properties they can be used in a wide range of fields such as electronic devices, electrodes, drug delivery systems, hydrogen storage, textile etc. Catalytic chemical vapor deposition (CCVD) is a common method for CNT production especially for mass production. Catalysts impregnated on a suitable substrate are important for production with chemical vapor deposition (CVD) method. Iron catalyst and MgO substrate is one of most common catalyst-substrate combination used for CNT. In this study, CNTs were produced by CCVD of acetylene (C2H2) on magnesium oxide (MgO) powder substrate impregnated by iron nitrate (Fe(NO3)3•9H2O) solution. The CNT synthesis conditions were as follows: at synthesis temperatures of 500 and 800°C multiwall and single wall CNTs were produced respectively. Iron (Fe) catalysts were prepared by with Fe:MgO ratio of 1:100, 5:100 and 10:100. The duration of syntheses were 30 and 60 minutes for all temperatures and catalyst percentages. The synthesized materials were characterized by thermal gravimetric analysis (TGA), transmission electron microscopy (TEM) and Raman spectroscopy.

Keywords: Carbon nanotube, catalyst, catalytic chemical vapordeposition, iron

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