Search results for: Catalytic Naphtha Reforming

Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to COx free hydrogen and carbon nanomaterials. The catalytic runs were carried out from 550-800oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, XRD, SEM, TEM and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity at 800oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs and branched CNFs depending on the catalyst composition and reaction temperature were obtained.

Keywords: Carbon nanotubes, Cobalt, Hydrogen Production, Methane decomposition.

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Authors: Phavanee Narataruksa, Karn Pana-Suppamassadu, Sabaithip TungkamaniRungrote Kokoo, Prayut Jiamrittiwong

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The major focus of this work was to characterize hydrodynamics in a packed-bed with and without static mixer by using Computational Fluid Dynamic (CFD). The commercial software: COMSOL MULTIPHYSICSTM Version 3.3 was used to simulate flow fields of mixed-gas reactants i.e. CO and H2. The packed-bed was a single tube with the inside diameter of 0.8 cm and the length of 1.2 cm. The static mixer was inserted inside the tube. The number of twisting elements was 1 with 0.8 cm in diameter and 1.2 cm in length. The packed-bed with and without static mixer were both packed with approximately 700 spherical structures representing catalyst pellets. Incompressible Navier-Stokes equations were used to model the gas flow inside the beds at steady state condition, in which the inlet Reynolds Number (Re) was 2.31. The results revealed that, with the insertion of static mixer, the gas was forced to flow radially inward and outward between the central portion of the tube and the tube wall. This could help improving the overall performance of the packed-bed, which could be utilized for heterogeneous catalytic reaction such as reforming and Fischer- Tropsch reactions.

Keywords: Packed Bed, Static Mixer, Computational Fluid Dynamic (CFD).

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Authors: M. Michalska-Domańska, P. Jóźwik, Z. Bojar

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Intermetallic Ni3Al – based alloys belong to a group of advanced materials characterized by good chemical and physical properties (such as structural stability, corrosion resistance) which offer advenced technological applications. The paper presents the study of catalytic properties of Ni3Al foils (thickness approximately 50 &m) in the methanol and hexane decomposition. The egzamined material posses microcrystalline structure without any additional catalysts on the surface. The better catalytic activity of Ni3Al foils with respect to quartz plates in both methanol and hexane decomposition was confirmed. On thin Ni3Al foils the methanol conversion reaches approximately 100% above 480 oC while the hexane conversion reaches approximately 100% (98,5%) at 500 oC. Deposit formed during the methanol decomposition is built up of carbon nanofibers decorated with metal-like nanoparticles.

Keywords: hexane decomposition, methanol decomposition, Ni3Al thin foils, Ni nanoparticles

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Authors: Vishnu S. Prasad, Preeti Aghalayam

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The major harmful automobile exhausts are nitric oxide (NO) and unburned hydrocarbon (HC). Reduction of NO using unburned fuel HC as a reductant is the technique used in hydrocarbon-selective catalytic reduction (HC-SCR). In this work, we study the microkinetic modelling of NO reduction using propene as a reductant on Pt catalysts. The selectivity of NO reduction to N₂O is detected in some ranges of operating conditions, whereas the effect of inlet O₂% causes a number of changes in the feasible regimes of operation.

Keywords: Microkinetic modelling, NOx, Pt on alumina catalysts, selective catalytic reduction.

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Authors: Thitipong Auttanat, Siriporn Jongpatiwut, Thirasak Rirksomboon

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The catalytic dehydroxylation of glycerol to propylene glycol was investigated over Cu-ZnO/Al2O3 prepared by incipient wetness impregnation (IWI) method with different purity feedstocks - refined glycerol and technical grade glycerol. The main purpose is to investigate the effects of feed impurities that cause the catalyst deactivation. The prepared catalyst were tested for its catalytic activity and selectivity in a continuous flow fixed bed reactor at 523 K, 500 psig, H2/feed molar ratio of 4 and WHSV of 3 h-1. The results showed that conversion of refined glycerol and technical grade glycerol at time on stream 6 hour are 99% and 71% and selectivity to propylene glycol are 87% and 56% respectively. The ICP-EOS and TPO results indicated that the cause of catalyst deactivation was the amount of impurities in the feedstock. The higher amount of impurities (especially Na and K) the lower catalytic activity.

Keywords: Cu-ZnO/Al2O3, dehydroxylation, glycerol, propylene glycol,

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Authors: Zhi Zhang, Tao Tang, Guangda Lu, Cheng Qin, Huogen Huang, Shaotao Zheng

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High purity hydrogen and the valuable by-product of carbon nanotubes (CNTs) can be produced by the methane catalytic decomposition. The methane conversion and the performance of CNTs were determined by the choices of catalysts and the condition of decomposition reaction. In this paper, Ni/MgO and Ni/O-D (oxidized diamond) catalysts were prepared by wetness impregnation method. The effects of reaction temperature and space velocity of methane on the methane conversion were investigated in a fixed-bed. The surface area, structure and micrography were characterized with BET, XPS, SEM, EDS technology. The results showed that the conversion of methane was above 8% within 150 min (T=500) for 33Ni/O-D catalyst and higher than 25% within 120 min (T=650) for 41Ni/MgO catalyst. The initial conversion increased with the increasing temperature of the decomposition reaction, but their catalytic activities decreased rapidly while at too higher temperature. To decrease the space velocity of methane was propitious to promote the methane conversion, but not favor of the hydrogen yields. The appearance of carbon resulted from the methane decomposition lied on the support type and the condition of catalytic reaction. It presented as fiber shape on the surface of Ni/O-D at the relatively lower temperature such as 500 and 550, but as grain shape stacked on and overlayed on the surface of the metal nickel while at 650. The carbon fiber can form on the Ni/MgO surface at 650 and the diameter of the carbon fiber increased with the decreasing space velocity.

Keywords: methane, catalytic decomposition, hydrogen, carbon nanofiber

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Authors: Lalita Saeaeh, Sirirat Jitkarnka

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Pyrolysis of waste tire is one of alternative technique to produce petrochemicals, such as light olefins, mixed C4, and monoaromatics. Noble metals supported on acid zeolite catalysts were reported as potential catalysts to produce the high valuable products from waste tire pyrolysis. Especially, Pd supported on HBeta gave a high yield of olefins, mixed C4, and mono-aromatics. Due to the high prices of noble metals, the objective of this work was to investigate whether or not a non-noble Ni metal can be used as a substitute of a noble metal, Pd, supported on HBeta as a catalyst for waste tire pyrolysis. Ni metal was selected in this work because Ni has high activity in cracking, isomerization, hydrogenation and the ring opening of hydrocarbons Moreover, Ni is an element in the same group as Pd noble metal, which is VIIIB group, aiming to produce high valuable products similarly obtained from Pd. The amount of Ni was varied as 5, 10, and 20% by weight, for comparison with a fixed 1 wt% Pd, using incipient wetness impregnation. The results showed that as a petrochemical-producing catalyst, 10%Ni/HBeta performed better than 1%Pd/HBeta because it did not only produce the highest yield of olefins and cooking gases, but the yields were also higher than 1%Pd/HBeta. 5%Ni/HBeta can be used as a substitute of 1%Pd/HBeta for similar crude production because its crude contains the similar amounts of naphtha and saturated HCs, although it gave no concentration of light mono-aromatics (C6-C11) in the oil. Additionally, 10%Ni/HBeta that gave high olefins and cooking gases was found to give a fairly high concentration of the light mono-aromatics in the oil.

Keywords: Catalytic pyrolysis; Waste tire; Pd; Ni; HBeta

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Authors: Mohammed Nasir Kajama, Ngozi Claribelle Nwogu, Edward Gobina

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Pt/γ-Al2O3 membrane catalysts were prepared via an evaporative-crystallization deposition method. The obtained Pt/γ- Al2O3 catalyst activity was tested after characterization (SEM-EDAX observation, BET measurement, permeability assessment) in the catalytic oxidation of selected volatile organic compound (VOC) i.e. propane, fed in mixture of oxygen. The VOC conversion (nearly 90%) obtained by varying the operating temperature showed that flow-through membrane reactor might do better in the abatement of VOCs.

Keywords: VOC combustion, flow-through membrane reactor, platinum supported alumina catalysts.

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M. S. Shaharun

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Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO₂ to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO₂ to methanol in microactivity fixed-bed reactor at 250^oC, 2.25 MPa, and H₂/CO₂ ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H₂ and CO₂ and accelerate the CO₂ conversion, resulting in higher methanol production under mild reaction conditions.

Keywords: Hydrogenation of carbon dioxide, methanol synthesis, Cu/ZnO-based catalyst, mesoporous silica (SBA-15), and metal ratio.

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Authors: Anushree, Chhaya Sharma, Satish Kumar

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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: 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: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: Activated char, bio-oil, catalytic pyrolysis, HZSM5, sewage sludge.

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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

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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

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

Abstract:

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

Abstract:

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

Abstract:

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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