Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 87

Search results for: Pd catalyst

87 Refining Waste Spent Hydroprocessing Catalyst and Their Metal Recovery

Authors: Meena Marafi, Mohan S. Rana

Abstract:

Catalysts play an important role in producing valuable fuel products in petroleum refining; but, due to feedstock’s impurities catalyst gets deactivated with carbon and metal deposition. The disposal of spent catalyst falls under the category of hazardous industrial waste that requires strict agreement with environmental regulations. The spent hydroprocessing catalyst contains Mo, V and Ni at high concentrations that have been found to be economically significant for recovery. Metal recovery process includes deoiling, decoking, grinding, dissolving and treatment with complexing leaching agent such as ethylene diamine tetra acetic acid (EDTA). The process conditions have been optimized as a function of time, temperature and EDTA concentration in presence of ultrasonic agitation. The results indicated that optimum condition established through this approach could recover 97%, 94% and 95% of the extracted Mo, V and Ni, respectively, while 95% EDTA was recovered after acid treatment.

Keywords: Spent catalyst, deactivation, hydrotreating, spent catalyst.

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86 Effects of Catalyst Tubes Characteristics on a Steam Reforming Process in Ammonia

Authors: M.Boumaza

Abstract:

The tubes in an Ammonia primary reformer furnace operate close to the limits of materials technology in terms of the stress induced as a result of very high temperatures, combined with large differential pressures across the tube wall. Operation at tube wall temperatures significantly above design can result in a rapid increase in the number of tube failures, since tube life is very sensitive to the absolute operating temperature of the tube. Clearly it is important to measure tube wall temperatures accurately in order to prevent premature tube failure by overheating.. In the present study, the catalyst tubes in an Ammonia primary reformer has been modeled taking into consideration heat, mass and momentum transfer as well as reformer characteristics.. The investigations concern the effects of tube characteristics and superficial tube wall temperatures on of the percentage of heat flux, unconverted methane and production of Hydrogen for various values of steam to carbon ratios. The results show the impact of catalyst tubes length and diameters on the performance of operating parameters in ammonia primary reformers.

Keywords: Catalyst, tubes, reformer, performance

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85 Trans-Esterification for Production of Biodiesel from Waste Frying Oil (WFO)

Authors: N. Akhavan Moghaddam, K. Tahvildari, S.Taghvaie

Abstract:

Biodisel is a type of biofuel having similar properties of diesel fuel but lacks substances (undesirable emissions) such as sulfur, nitrogen and aromatic polycyclic. Upon filtration of waste oil, the biodiesel fuel was produced via carrying out transestrification reaction of triglycerides followed by conducting viscosity, density, flash point, cloud point, pour point and copper strip corrosion tests on the samples and comparing with EN14214 and ASTM 6751 standards and all results were found in the permitted limit. The highest yield of biodiesel production reaction was found 46.6435 g when Sodium Hydroxide catalyst in amount of 0.375g was employed, 44.2347 g when Sodium methoxide catalyst in amount of 0.5g was employed and 56.5124 g when acid sulfuric catalyst in amount of 1g was employed and 47.3290 g when two stage reaction was done.

Keywords: Biodiesel, Transesterification, Basic catalyst, Acidic catalyst.

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84 Effect of Substituent on Titanocene/MMAO Catalyst for Ethylene/1-Hexene Copolymerization

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

Abstract:

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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83 Microbial Leaching Process to Recover Valuable Metals from Spent Petroleum Catalyst Using Iron Oxidizing Bacteria

Authors: Debabrata Pradhan, Dong J. Kim, Jong G. Ahn, Seoung W. Lee

Abstract:

Spent petroleum catalyst from Korean petrochemical industry contains trace amount of metals such as Ni, V and Mo. Therefore an attempt was made to recover those trace metal using bioleaching process. Different leaching parameters such as Fe(II) concentration, pulp density, pH, temperature and particle size of spent catalyst particle were studied to evaluate their effects on the leaching efficiency. All the three metal ions like Ni, V and Mo followed dual kinetics, i.e., initial faster followed by slower rate. The percentage of leaching efficiency of Ni and V were higher than Mo. The leaching process followed a diffusion controlled model and the product layer was observed to be impervious due to formation of ammonium jarosite (NH4)Fe3(SO4)2(OH)6. In addition, the lower leaching efficiency of Mo was observed due to a hydrophobic coating of elemental sulfur over Mo matrix in the spent catalyst.

Keywords: Bioleaching, diffusion control, shrinking core, spentpetroleum catalyst.

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82 Methanation Catalyst for Low CO Concentration

Authors: Hong-fang Ma, Cong-yi He, Hai-tao Zhang, Wei-yong Ying, Ding-ye Fang

Abstract:

A Ni-based catalyst supported by γ-Al2O3 was prepared by impregnation method, and the catalyst was used in a low CO and CO2 concentration methanation system. The effect of temperature, pressure and space velocity on the methanation reaction was investigated in an experimental fixed-bed reactor. The methanation reaction was operated at the conditions of 190-240°C, 3000-24000ml•g-1•h-1 and 1.5-3.5MPa. The results show that temperature and space velocity play important role on the reaction. With the increase of reaction temperature the CO and CO2 conversion increase and the selectivity of CH4 increase. And with the increase of the space velocity the conversion of CO and CO2 and the selectivity of CH4 decrease sharply.

Keywords: Coke oven gas, methanation, catalyst, fixed-bed.

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81 Biodiesel Production from Palm Oil using Heterogeneous Base Catalyst

Authors: Sirichai Chantara-arpornchai, Apanee Luengnaruemitchai, Samai Jai-In

Abstract:

In this study, the transesterification of palm oil with methanol for biodiesel production was studied by using CaO–ZnO as a heterogeneous base catalyst prepared by incipient-wetness impregnation (IWI) and co-precipitation (CP) methods. The reaction parameters considered were molar ratio of methanol to oil, amount of catalyst, reaction temperature, and reaction time. The optimum conditions–15:1 molar ratio of methanol to oil, a catalyst amount of 6 wt%, reaction temperature of 60 °C, and reaction time of 8 h–were observed. The effects of Ca loading, calcination temperature, and catalyst preparation on the catalytic performance were studied. The fresh and spent catalysts were characterized by several techniques, including XRD, TPR, and XRF.

Keywords: CaO, ZnO, biodiesel, heterogeneous catalyst, trans-esterification.

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80 Production of Carbon Nanotubes by Iron Catalyst

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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79 Characterization of Fish Bone Catalyst for Biodiesel Production

Authors: Sarina Sulaiman, N. Khairudin, P. Jamal, M. Z. Alam, Zaki Zainudin, S. Azmi

Abstract:

In this study, fish bone waste was used as a new catalyst for biodiesel production. Instead of discarding the fish bone waste, it will be utilized as a source for catalyst that can provide significant benefit to the environment. Also, it can be substitute as a calcium oxide source instead of using eggshell, crab shell and snail shell. The XRD and SEM analysis proved that calcined fish bone contains calcium oxide, calcium phosphate and hydroxyapatite. The catalyst was characterized using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD).

Keywords: Calcinations, fish bone, transesterification, waste catalyst.

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78 Bioleaching of Spent Catalyst using Moderate Thermophiles with Different Pulp Densities and Varying Size Fractions without Fe Supplemented Growth Medium

Authors: Haragobinda Srichandan, Chandra Sekhar Gahan, Dong-Jin Kim, Seoung-Won Lee

Abstract:

Bioleaching of spent catalyst using moderate thermophilic chemolithotrophic acidophiles in growth medium without Fe source was investigated with two different pulp densities and three different size fractions. All the experiments were conducted on shake flasks at a temperature of 65 °C. The leaching yield of Ni and Al was found to be promising with very high leaching yield of 92-96% followed by Al as 41-76%, which means both Ni and Al leaching were favored by the moderate thermophilic bioleaching compared to the mesophilic bioleaching. The acid consumption was comparatively higher for the 10% pulp density experiments. Comparatively minimal difference in the leaching yield with different size fractions and different pulp densities show no requirement of grinding and using low pulp density less than 10%. This process would rather be economical as well as eco-friendly process for future optimization of the recovery of metal values from spent catalyst.

Keywords: Bioleaching, spent catalyst, leaching yield, thermophile.

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77 Conversion in Chemical Reactors using Hollow Cylindrical Catalyst Pellet

Authors: Mohammad Asif

Abstract:

Heterogeneous catalysis is vital for a number of chemical, refinery and pollution control processes. The use of catalyst pellets of hollow cylindrical shape provide several distinct advantages over other common shapes, and can therefore help to enhance conversion levels in reactors. A better utilization of the catalytic material is probably most notable of these features due to the absence of the pellet core, which helps to significantly lower the effect of the internal transport resistance. This is reflected in the enhancement of the effectiveness factor. For the case of the first order irreversible kinetics, a substantial increase in the effectiveness factor can be obtained by varying shape parameters. Important shape parameters of a finite hollow cylinder are the ratio of the inside to the outside radii (κ) and the height to the diameter ratio (γ). A high value of κ the generally helps to enhance the effectiveness factor. On the other hand, lower values of the effectiveness factors are obtained when the dimension of the height and the diameter are comparable. Thus, the departure of parameter γ from the unity favors higher effectiveness factor. Since a higher effectiveness factor is a measure of a greater utilization of the catalytic material, higher conversion levels can be achieved using the hollow cylindrical pellets possessing optimized shape parameters.

Keywords: Finite hollow cylinder, Catalyst pellet, Effectiveness factor, Thiele Modulus, Conversion

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76 Palladium-Catalyzed Hydrodechlorination for Water Remediation: Catalyst Deactivation and Regeneration

Authors: Dalia Angeles-Wedler, Katrin Mackenzie, Frank-Dieter Kopinke

Abstract:

Palladium-catalyzed hydrodechlorination is a promising alternative for the treatment of environmentally relevant water bodies, such as groundwater, contaminated with chlorinated organic compounds (COCs). In the aqueous phase hydrodechlorination of COCs, Pd-based catalysts were found to have a very high catalytic activity. However, the full utilization of the catalyst-s potential is impeded by the sensitivity of the catalyst to poisoning and deactivation induced by reduced sulfur compounds (e.g. sulfides). Several regenerants have been tested before to recover the performance of sulfide-fouled Pd catalyst. But these only delivered partial success with respect to re-establishment of the catalyst activity. In this study, the deactivation behaviour of Pd/Al2O3 in the presence of sulfide was investigated. Subsequent to total deactivation the catalyst was regenerated in the aqueous phase using potassium permanganate. Under neutral pH condition, oxidative regeneration with permanganate delivered a slow recovery of catalyst activity. However, changing the pH of the bulk solution to acidic resulted in the complete recovery of catalyst activity within a regeneration time of about half an hour. These findings suggest the superiority of permanganate as regenerant in re-activating Pd/Al2O3 by oxidizing Pd-bound sulfide.

Keywords: Deactivation, hydrodechlorination, Pd catalyst, regeneration.

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75 Hydrogenation of CO2 to Methanol over Copper-Zinc Oxide-Based Catalyst

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

Abstract:

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 250oC, 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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74 Production of Biodiesel from Roasted Chicken Fat and Methanol: Free Catalyst

Authors: Jorge Ramírez-Ortiz, Merced Martínez Rosales, Horacio Flores Zúñiga

Abstract:

Transesterification reactions free of catalyst between roasted chicken fat with methanol were carried out in a batch reactor in order to produce biodiesel to temperatures from 120°C to 140°C. Parameters related to the transesterification reactions, including temperature, time and the molar ratio of chicken fat to methanol also investigated. The maximum yield of the reaction was of 98% under conditions of 140°C, 4 h of reaction time and a molar ratio of chicken fat to methanol of 1:31. The biodiesel thus obtained exhibited a viscosity of 6.3 mm2/s and a density of 895.9 kg/m3. The results showed this process can be right choice to produce biodiesel since this process does not use any catalyst. Therefore, the steps of neutralization and washing are avoided, indispensables in the case of the alkaline catalysis.

Keywords: Biodiesel, non-catalyst, roasted chicken fat, transesterification.

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73 Fungal Leaching of Hazardous Heavy Metals from a Spent Hydrotreating Catalyst

Authors: R. Mafi Gholami, S. M. Borghei, S. M. Mousavi

Abstract:

In this study, the ability of Aspergillus niger and Penicillium simplicissimum to extract heavy metals from a spent refinery catalyst was investigated. For the first step, a spent processing catalyst from one of the oil refineries in Iran was physically and chemically characterized. Aspergillus niger and Penicillium simplicissimum were used to mobilize Al/Co/Mo/Ni from hazardous spent catalysts. The fungi were adapted to the mixture of metals at 100-800 mg L-1 with increments in concentration of 100 mg L-1. Bioleaching experiments were carried out in batch cultures. To investigate the production of organic acids in sucrose medium, analyses of the culture medium by HPLC were performed at specific time intervals after inoculation. The results obtained from Inductive coupled plasma-optical emission spectrometry (ICP-OES) showed that after the one-step bioleaching process using Aspergillus niger, maximum removal efficiencies of 27%, 66%, 62% and 38% were achieved for Al, Co, Mo and Ni, respectively. However, the highest removal efficiencies using Penicillium simplicissimum were of 32%, 67%, 65% and 38% for Al, Co, Mo and Ni, respectively

Keywords: Aspergillus niger, Bioleaching, Heavy metals, Penicillium simplicissimum, Spent catalyst

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72 Effect of Recycle Gas on Activity and Selectivity of Co-Ru/Al2O3 Catalyst in Fischer- Tropsch Synthesis

Authors: A.A.Rohani, B.Hatami, L.Jokar, F.khorasheh, A.A.Safekordi

Abstract:

In industrial scale of Gas to Liquid (GTL) process in Fischer-Tropsch (FT) synthesis, a part of reactor outlet gases such as CO2 and CH4 as side reaction products, is usually recycled. In this study, the influence of CO2 and CH4 on the performance and selectivity of Co-Ru/Al2O3 catalyst is investigated by injection of these gases (0-20 vol. % of feed) to the feed stream. The effect of temperature and feed flow rate, are also inspected. The results show that low amounts of CO2 in the feed stream, doesn`t change the catalyst activity significantly but increasing the amount of CO2 (more than 10 vol. %) cause the CO conversion to decrease and the selectivity of heavy components to increase. Methane acts as an inert gas and doesn`t affect the catalyst performance. Increasing feed flow rate has negative effect on both CO conversion and heavy component selectivity. By raising the temperature, CO conversion will increase but there are more volatile components in the product. The effect of CO2 on the catalyst deactivation is also investigated carefully and a mechanism is suggested to explain the negative influence of CO2 on catalyst deactivation.

Keywords: Alumina, Carbon dioxide, Cobalt catalyst, Conversion, Fischer Tropsch, Selectivity

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71 Modeling of Catalyst Deactivation in Catalytic Wet Air Oxidation of Phenol in Fixed Bed Three-Phase Reactor

Authors: Akram Golestani, Mohammad Kazemeini, Farhad Khorasheh, Moslem Fattahi

Abstract:

Modeling and simulation of fixed bed three-phase catalytic reactors are considered for wet air catalytic oxidation of phenol to perform a comparative numerical analysis between tricklebed and packed-bubble column reactors. The modeling involves material balances both for the catalyst particle as well as for different fluid phases. Catalyst deactivation is also considered in a transient reactor model to investigate the effects of various parameters including reactor temperature on catalyst deactivation. The simulation results indicated that packed-bubble columns were slightly superior in performance than trickle beds. It was also found that reaction temperature was the most effective parameter in catalyst deactivation.

Keywords: Catalyst deactivation, Catalytic wet air oxidation, Trickle-bed, Wastewater.

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70 Porous Carbon Nanoparticles Co-Doped with Nitrogen and Iron as an Efficient Catalyst for Oxygen Reduction Reaction

Authors: Bita Bayatsarmadi, Shi-Zhang Qiao

Abstract:

Oxygen Reduction Reaction (ORR) performance of iron and nitrogen co-doped porous carbon nanoparticles (Fe-NPC) with various physical and (electro) chemical properties have been investigated. Fe-NPC nanoparticles are synthesized via a facile soft-templating procedure by using Iron (III) chloride hexa-hydrate as iron precursor and aminophenol-formaldehyde resin as both carbon and nitrogen precursor. Fe-NPC nanoparticles shows high surface area (443.83 m2g-1), high pore volume (0.52 m3g-1), narrow mesopore size distribution (ca. 3.8 nm), high conductivity (IG/ID=1.04), high kinetic limiting current (11.71 mAcm-2) and more positive onset potential (-0.106 V) compared to metal-free NPC nanoparticles (-0.295V) which make it high efficient ORR metal-free catalysts in alkaline solution. This study may pave the way of feasibly designing iron and nitrogen containing carbon materials (Fe-N-C) for highly efficient oxygen reduction electro-catalysis.

Keywords: Electro-catalyst, mesopore structure, oxygen reduction reaction, soft-template.

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69 Preparation and Characterization of MoO3/Al2O3 Catalyst for Oxidative Desulfurization of Diesel using H2O2: Effect of Drying Method and Mo Loading

Authors: Azam Akbari, Mohammadreza Omidkhah, Jafar Toufighi Darian

Abstract:

The mesoporous MoO3/γ-Al2O3 catalyst was prepared by incipient wetness impregnation method aiming to investigate the effect of drying method and molybdenum content on the catalyst property and performance towards the oxidation of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyle dibenzothiophene (4,6-DMDBT) with H2O2 for deep oxidative desulfurization of diesel fuel. The catalyst was characterized by XRD, BET, BJH and SEM method. The catalyst with 10wt.% and 15wt.% Mo content represent same optimum performance for DBT and 4,6-DMDBT removal, but a catalyst with 10wt.% Mo has higher efficiency than 15wt.% Mo for BT conversion. The SEM images show that use of rotary evaporator in drying step reaches a more homogenous impregnation. The oxidation reactivity of different sulfur compounds was studied which followed the order of DBT>4,6-DMDBT>>BT.

Keywords: desulfurization, oxidation, MoO3/Al2O3 catalyst

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68 Comparison of Bioleaching of Metals from Spent Petroleum Catalyst Using Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

Authors: Haragobinda Srichandan, Ashish Pathak, Dong Jin Kim, Seoung-Won Lee

Abstract:

The present investigation deals with bioleaching of spent petroleum catalyst using At. ferrooxidans and At. thiooxidans. The spent catalyst used in the present study was pretreated with acetone to remove the oily hydrocarbons. FESEM and XPS analysis indicated the presence of metals in sulfide and oxide forms in spent catalyst. Both At. ferrooxidans and At. thiooxidans were found to be highly effective in producing the acid. Bioleaching with At. ferrooxidans and At. thiooxidans led to higher recovery of metals compare to control. During bioleaching similar recoveries of metals were obtained using At. ferrooxidans and At. thiooxidans. This might be due to the presence of metals as soluble oxides and sulphides in the spent catalyst. At the end of bioleaching, about 87-90% Ni, 34% Al, 65-73% Mo and 92-97% V were leached using above bacteria. It is elucidated that bioleaching with At. thiooxidans is comparatively more advantageous due to lower cost of sulphur.  

Keywords: Spent catalyst, At. ferrooxidans, Bioleaching, Metal recovery.

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67 Intrinsic Kinetics of Methanol Dehydration over Al2O3 Catalyst

Authors: Liang Zhang, Hai-Tao Zhang, W ei-Yong Ying, Ding-Ye Fang

Abstract:

Dehydration of methanol to dimethyl ether (DME) over a commercial Al2O3 catalyst was studied in an isothermal integral fixed bed reactor. The experiments were performed on the temperature interval 513-613 K, liquid hourly space velocity (LHSV) of 0.9-2.1h-1, pressures between 0.1 and 1.0 MPa. The effect of different operation conditions on the dehydration of methanol was investigated in a laboratory scale experiment. A new intrinsic kinetics equation based on the mechanism of Langmuir-Hinshelwood dissociation adsorption was developed for the dehydration reaction by fitting the expressions to the experimental data. An activation energy of 67.21 kJ/mol was obtained for the catalyst with the best performance. Statistic test showed that this new intrinsic kinetics equation was acceptable.

Keywords: catalyst, dimethyl ether, intrinsic kinetics, methanol

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66 Effect of the Support Shape on Fischer-Tropsch Cobalt Catalyst Performance

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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65 Investigation of the Synthesis of Alcohols Byproducts in Fischer-Tropsch Synthesis on Modified Fe-Cu Catalyst: Reactivity and Mechanism

Authors: Wanyu Mao, Qiwen Sun, Weiyong Ying, Dingye Fang

Abstract:

The influence of copper promoters and reaction conditions on the formation of alcohols byproducts of a common Fischer-Tropsch synthesis used iron-based catalysts were investigated. A good compromise of 28%Cu/FeKLaSiO2 can lead to the optimization of an improved Fischer-Tropsch catalyst. The product distribution shifts towards hydrocarbons with increasing the reaction temperature, while pressure promotes the formation of alcohols. It was found that the production of either alcohols or hydrocarbons followed A-S-F distributions, and their α parameters were essentially different which indicated a competition in the growing chain between the two species. TPD after acetaldehyde adsorption gave strong evidence of the insertion of a C1 oxygen-containing species into an alkyl chain.

Keywords: Fischer-Tropsch synthesis, Fe-Cu catalyst, alcohols byproducts, reaction pathways

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64 Global Kinetics of Direct Dimethyl Ether Synthesis Process from Syngas in Slurry Reactor over a Novel Cu-Zn-Al-Zr Slurry Catalyst

Authors: Zhen Chen, Haitao Zhang, Weiyong Ying, Dingye Fang

Abstract:

The direct synthesis process of dimethyl ether (DME) from syngas in slurry reactors is considered to be promising because of its advantages in caloric transfer. In this paper, the influences of operating conditions (temperature, pressure and weight hourly space velocity) on the conversion of CO, selectivity of DME and methanol were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst, which is far more suitable to liquid phase dimethyl ether synthesis process than bifunctional catalyst commercially. A Langmuir- Hinshelwood mechanism type global kinetics model for liquid phase DME direct synthesis based on methanol synthesis models and a methanol dehydration model has been investigated by fitting our experimental data. The model parameters were estimated with MATLAB program based on general Genetic Algorithms and Levenberg-Marquardt method, which is suitably fitting experimental data and its reliability was verified by statistical test and residual error analysis.

Keywords: alcohol/ether fuel, Cu-Zn-Al-Zr slurry catalyst, global kinetics, slurry reactor

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63 Rigorous Modeling of Fixed-Bed Reactors Containing Finite Hollow Cylindrical Catalyst with Michaelis-Menten Type of Kinetics

Authors: Mohammad Asif

Abstract:

A large number of chemical, bio-chemical and pollution-control processes use heterogeneous fixed-bed reactors. The use of finite hollow cylindrical catalyst pellets can enhance conversion levels in such reactors. The absence of the pellet core can significantly lower the diffusional resistance associated with the solid phase. This leads to a better utilization of the catalytic material, which is reflected in the higher values for the effectiveness factor, leading ultimately to an enhanced conversion level in the reactor. It is however important to develop a rigorous heterogeneous model for the reactor incorporating the two-dimensional feature of the solid phase owing to the presence of the finite hollow cylindrical catalyst pellet. Presently, heterogeneous models reported in the literature invariably employ one-dimension solid phase models meant for spherical catalyst pellets. The objective of the paper is to present a rigorous model of the fixed-bed reactors containing finite hollow cylindrical catalyst pellets. The reaction kinetics considered here is the widely used Michaelis–Menten kinetics for the liquid-phase bio-chemical reactions. The reaction parameters used here are for the enzymatic degradation of urea. Results indicate that increasing the height to diameter ratio helps to improve the conversion level. On the other hand, decreasing the thickness is apparently not as effective. This could however be explained in terms of the higher void fraction of the bed that causes a smaller amount of the solid phase to be packed in the fixed-bed bio-chemical reactor.

Keywords: Fixed-bed reactor, Finite hollow cylinder, Catalyst pellet, Conversion, Michaelis-Menten kinetics.

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62 Conversion of Jatropha curcas Oil to Ester Biolubricant Using Solid Catalyst Derived from Saltwater Clam Shell Waste (SCSW)

Authors: Said Nurdin, Fatimah A. Misebah, Rosli M. Yunus, Mohd S. Mahmud, Ahmad Z. Sulaiman

Abstract:

The discarded clam shell waste, fossil and edible oil as biolubricant feedstocks create environmental impacts and food chain dilemma, thus this work aims to circumvent these issues by using activated saltwater clam shell waste (SCSW) as solid catalyst for conversion of Jatropha curcas oil as non-edible sources to ester biolubricant. The characterization of solid catalyst was done by Differential Thermal Analysis-Thermo Gravimetric Analysis (DTATGA), X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) and Fourier Transformed Infrared Spectroscopy (FTIR) analysis. The calcined catalyst was used in the transesterification of Jatropha oil to methyl ester as the first step, and the second stage was involved the reaction of Jatropha methyl ester (JME) with trimethylolpropane (TMP) based on the various process parameters. The formated biolubricant was analyzed using the capillary column (DB-5HT) equipped Gas Chromatography (GC). The conversion results of Jatropha oil to ester biolubricant can be found nearly 96.66%, and the maximum distribution composition mainly contains 72.3% of triester (TE).

Keywords: Conversion, ester biolubricant, Jatropha curcas oil, solid catalyst.

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61 Development of a Nano-Alumina-Zirconia Composite Catalyst as an Active Thin Film in Biodiesel Production

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

Abstract:

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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60 Mathematical Modeling for Continuous Reactive Extrusion of Poly Lactic Acid formation by Ring Opening Polymerization Considering Metal/Organic Catalyst and Alternative Energies

Authors: Satya P. Dubey, Hrushikesh A. Abhyankar, Veronica Marchante, James L. Brighton, Björn Bergmann

Abstract:

PLA emerged as a promising polymer because of its property as a compostable, biodegradable thermoplastic made from renewable sources. PLA can be polymerized from monomers (Lactide or Lactic acid) obtained by fermentation processes from renewable sources such as corn starch or sugarcane. For PLA synthesis, ring opening polymerization (ROP) of Lactide monomer is one of the preferred methods. In the literature, the technique mainly developed for ROP of PLA is based on metal/bimetallic catalyst (Sn, Zn and Al) or other organic catalysts in suitable solvent. However, the PLA synthesized using such catalysts may contain trace elements of the catalyst which may cause toxicity. This work estimated the usefulness and drawbacks of using different catalysts as well as effect of alternative energies and future aspects for PLA production.

Keywords: Alternative energy, bio-degradable, metal catalyst, poly lactic acid (PLA), ring opening polymerization (ROP).

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59 Effect of Catalyst Preparation on the Performance of CaO-ZnO Catalysts for Transesterification

Authors: Pathravut Klinklom, Apanee Luengnaruemitchai, Samai Jai-In

Abstract:

In this research, CaO-ZnO catalysts (with various Ca:Zn atomic ratios of 1:5, 1:3, 1:1, and 3:1) prepared by incipientwetness impregnation (IWI) and co-precipitation (CP) methods were used as a catalyst in the transesterification of palm oil with methanol for biodiesel production. The catalysts were characterized by several techniques, including BET method, CO2-TPD, and Hemmett Indicator. The effects of precursor concentration, and calcination temperature on the catalytic performance were studied under reaction conditions of a 15:1 methanol to oil molar ratio, 6 wt% catalyst, reaction temperature of 60°C, and reaction time of 8 h. At Ca:Zn atomic ratio of 1:3 gave the highest FAME value owing to a basic properties and surface area of the prepared catalyst.

Keywords: CaO, ZnO, Biodiesel, Impregnation, Coprecipitation.

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58 Modeling Converters during the Warm-up Period for Hydrocarbon Oxidation

Authors: Sanchita Chauhan, V.K. Srivastava

Abstract:

Catalytic converters are used for minimizing the release of pollutants to the atmosphere. It is during the warm-up period that hydrocarbons are seen to be released in appreciable quantities from these converters. In this paper the conversion of a fast oxidizing hydrocarbon propylene is analysed using two numerical methods. The quasi steady state method assumes the accumulation terms to be negligible in the gas phase mass and energy balance equations, however this term is present in the solid phase energy balance. The unsteady state model accounts for the accumulation term to be present in the gas phase mass and energy balance and in the solid phase energy balance. The results derived from the two models for gas concentration, gas temperature and solid temperature are compared.

Keywords: Propylene, catalyst, quasi steady state, unsteady state.

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