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.
Abstract: Polyoxymethylene dimethyl ethers (PODEn) 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 PODEn 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·gcat-1·h-1 in a fixed bed reactor. Methanol conversion and PODE3-6 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 PODE3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE3-6, respectively. The concentration of PODE3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE3-6 from methanol and formaldehyde solution is feasible.
Abstract: 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.
Abstract: 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.
Abstract: Fixed bed adsorption has become a frequently used
industrial application in wastewater treatment processes. Various low
cost adsorbents have been studied for their applicability in treatment
of different types of effluents. In this work, the intention of the study
was to explore the efficacy and feasibility for azo dye, Acid Orange 7
(AO7) adsorption onto fixed bed column of NaOH Treated eggshell
(TES). The effect of various parameters like flow rate, initial dye
concentration, and bed height were exploited in this study. The
studies confirmed that the breakthrough curves were dependent on
flow rate, initial dye concentration solution of AO7 and bed depth.
The Thomas, Yoon–Nelson, and Adams and Bohart models were
analysed to evaluate the column adsorption performance. The
adsorption capacity, rate constant and correlation coefficient
associated to each model for column adsorption was calculated and
mentioned. The column experimental data were fitted well with
Thomas model with coefficients of correlation R2 ≥0.93 at different
conditions but the Yoon–Nelson, BDST and Bohart–Adams model
(R2=0.911), predicted poor performance of fixed-bed column. The
(TES) was shown to be suitable adsorbent for adsorption of AO7
using fixed-bed adsorption column.
Abstract: Torrefaction of biomass pellets is considered as a
useful pretreatment technology in order to convert them into a high
quality solid biofuel that is more suitable for pyrolysis, gasification,
combustion, and co-firing applications. In the course of torrefaction,
the temperature varies across the pellet, and therefore chemical
reactions proceed unevenly within the pellet. However, the
uniformity of the thermal distribution along the pellet is generally
assumed. The torrefaction process of a single cylindrical pellet is
modeled here, accounting for heat transfer coupled with chemical
kinetics. The drying sub-model was also introduced. The nonstationary
process of wood pellet decomposition is described by the
system of non-linear partial differential equations over the
temperature and mass. The model captures well the main features of
the experimental data.
Abstract: Thermochemical conversion of non-edible biomass offers an efficient and economically process to provide valuable fuels and prepare chemicals derived from biomass in the context of developing countries. Pyrolysis has advantages over other thermochemical conversion techniques because it can convert biomass directly into solid, liquid and gaseous products by thermal decomposition of biomass in the absence of oxygen. The present paper aims to focus on the slow thermochemical conversion processes for non-edible Jatropha curcus seed cake. The present discussion focuses on the effect of nitrogen gas flow rate on products composition (wt %). In addition, comparative analysis has been performed for different mesh size for product composition. Result shows that, slow pyrolysis experiments of Jatropha curcus seed cake in fixed bed reactor yield the bio-oil 18.42 wt % at a pyrolysis temperature of 500°C, particle size of -6+8 mesh number and nitrogen gas flow rate of 150 ml/min.
Abstract: Selective oxidation of H2S to elemental sulfur in a
fixed bed reactor over newly synthesized alumina nanocatalysts was
physio-chemically investigated and results compared with a
commercial Claus catalyst. Amongst these new materials, Al2O3-
supported sodium oxide prepared with wet chemical technique and
Al2O3 nanocatalyst prepared with spray pyrolysis method were the
most active catalysts for selective oxidation of H2S to elemental
sulfur. Other prepared nanocatalysts were quickly deactivated,
mainly due to the interaction with H2S and conversion into sulfides.
Abstract: This work investigated the steady state and dynamic
simulation of a fixed bed industrial naphtha reforming reactors. The
performance of the reactor was investigated using a heterogeneous
model. For process simulation, the differential equations are solved
using the 4th order Runge-Kutta method .The models were validated
against measured process data of an existing naphtha reforming plant.
The results of simulation in terms of components yields and
temperature of the outlet were in good agreement with empirical data.
The simple model displays a useful tool for dynamic simulation,
optimization and control of naphtha reforming.
Abstract: In this paper 2D Simulation of catalytic Fixed Bed Reactor in Fischer-Tropsch Synthesis of GTL technology has been performed utilizing computational fluid dynamics (CFD). Synthesis gas (a mixture of carbon monoxide and hydrogen) has been used as feedstock. The reactor was modeled and the model equations were solved employing finite volume method. The model was validated against the experimental data reported in literature. The comparison showed a good agreement between simulation results and the experimental data. In addition, the model was applied to predict the concentration contours of the reactants and products along the length of reactor.
Abstract: In this study, we sought to investigate the mercury
removal efficiency of manganese oxides from natural gas. The
fundamental studies on mercury removal with manganese oxides
sorbents were carried out in a laboratory scale fixed bed reactor at 30
°C with a mixture of methane (20%) and nitrogen gas laden with 4.8
ppb of elemental mercury. Manganese oxides with varying surface
area and crystalline phase were prepared by conventional precipitation
method in this study. The effects of surface area, crystallinity and
other metal oxides on mercury removal efficiency were investigated.
Effect of Ag impregnation on mercury removal efficiency was also
investigated. Ag supported on metal oxide such titania and zirconia as
reference materials were also used in this study for comparison. The
characteristics of mercury removal reaction with manganese oxide
was investigated using a temperature programmed desorption (TPD)
technique.
Manganese oxides showed very high Hg removal activity (about
73-93% Hg removal) for first time use. Surface area of the manganese
oxide samples decreased after heat-treatment and resulted in complete
loss of Hg removal ability for repeated use after Hg desorption in the
case of amorphous MnO2, and 75% loss of the initial Hg removal
activity for the crystalline MnO2. Mercury desorption efficiency of
crystalline MnO2 was very low (37%) for first time use and high (98%)
after second time use. Residual potassium content in MnO2 may have
some effect on the thermal stability of the adsorbed Hg species.
Desorption of Hg from manganese oxides occurs at much higher
temperatures (with a peak at 400 °C) than Ag/TiO2 or Ag/ZrO2.
Mercury may be captured on manganese oxides in the form of mercury
manganese oxide.
Abstract: In this work, axisymetric CFD simulation of fixed bed
GTL reactor has been conducted, using computational fluid dynamics
(CFD). In fixed bed CFD modeling, when N (tube-to-particle
diameter ratio) has a large value, it is common to consider the packed
bed as a porous media. Synthesis gas (a mixture of predominantly
carbon monoxide and hydrogen) was fed to the reactor. The reactor
length was 20 cm, divided to three sections. The porous zone was in
the middle section of the reactor. The model equations were solved
employing finite volume method. The effects of particle diameter,
bed voidage, fluid velocity and bed length on pressure drop have
been investigated. Simulation results showed these parameters could
have remarkable impacts on the reactor pressure drop.
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.
Abstract: 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.
Abstract: 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.
Abstract: Modeling of a heterogeneous industrial fixed bed
reactor for selective dehydrogenation of heavy paraffin with Pt-Sn-
Al2O3 catalyst has been the subject of current study. By applying
mass balance, momentum balance for appropriate element of reactor
and using pressure drop, rate and deactivation equations, a detailed
model of the reactor has been obtained. Mass balance equations have
been written for five different components. In order to estimate
reactor production by the passage of time, the reactor model which is
a set of partial differential equations, ordinary differential equations
and algebraic equations has been solved numerically.
Paraffins, olefins, dienes, aromatics and hydrogen mole percent as
a function of time and reactor radius have been found by numerical
solution of the model. Results of model have been compared with
industrial reactor data at different operation times. The comparison
successfully confirms validity of proposed model.
Abstract: The remediation of water resources pollution in
developing countries requires the application of alternative
sustainable cheaper and efficient end-of-pipe wastewater treatment
technologies. The feasibility of use of South African cheap and
abundant pine tree (Pinus patula) sawdust for development of lowcost
AC of comparable quality to expensive commercial ACs in the
abatement of water pollution was investigated. AC was developed at
optimized two-stage N2-superheated steam activation conditions in a
fixed bed reactor, and characterized for proximate and ultimate
properties, N2-BET surface area, pore size distribution, SEM, pHPZC
and FTIR. The sawdust pyrolysis activation energy was evaluated by
TGA. Results indicated that the chars prepared at 800oC and 2hrs
were suitable for development of better quality AC at 800oC and 47%
burn-off having BET surface area (1086m2/g), micropore volume
(0.26cm3/g), and mesopore volume (0.43cm3/g) comparable to
expensive commercial ACs, and suitable for water contaminants
removal. The developed AC showed basic surface functionality at
pHPZC at 10.3, and a phenol adsorption capacity that was higher than
that of commercial Norit (RO 0.8) AC. Thus, it is feasible to develop
better quality low-cost AC from (Pinus patula) sawdust using twostage
N2-steam activation in fixed-bed reactor.
Abstract: The rate of production of main products of the Fischer-Tropsch reactions over Fe/HZSM5 bifunctional catalyst in a fixed bed reactor is investigated at a broad range of temperature, pressure, space velocity, H2/CO feed molar ratio and CO2, CH4 and water flow rates. Model discrimination and parameter estimation were performed according to the integral method of kinetic analysis. Due to lack of mechanism development for Fisher – Tropsch Synthesis on bifunctional catalysts, 26 different models were tested and the best model is selected. Comprehensive one and two dimensional heterogeneous reactor models are developed to simulate the performance of fixed-bed Fischer – Tropsch reactors. To reduce computational time for optimization purposes, an Artificial Feed Forward Neural Network (AFFNN) has been used to describe intra particle mass and heat transfer diffusion in the catalyst pellet. It is seen that products' reaction rates have direct relation with H2 partial pressure and reverse relation with CO partial pressure. The results show that the hybrid model has good agreement with rigorous mechanistic model, favoring that the hybrid model is about 25-30 times faster.
Abstract: Fixed-bed slow pyrolysis experiments of rice husk
have been conducted to determine the effect of pyrolysis
temperature, heating rate, particle size and reactor length on the
pyrolysis product yields. Pyrolysis experiments were performed at
pyrolysis temperature between 400 and 600°C with a constant
heating rate of 60°C/min and particle sizes of 0.60-1.18 mm. The
optimum process conditions for maximum liquid yield from the rice
husk pyrolysis in a fixed bed reactor were also identified. The highest
liquid yield was obtained at a pyrolysis temperature of 500°C,
particle size of
1.18-1.80 mm, with a heating rate of 60°C/min in a 300 mm length
reactor. The obtained yield of, liquid, gas and solid were found be in
the range of 22.57-31.78 %, 27.75-42.26 % and 34.17-42.52 % (all
weight basics) respectively at different pyrolysis conditions. The
results indicate that the effects of pyrolysis temperature and particle
size on the pyrolysis yield are more significant than that of heating
rate and reactor length. The functional groups and chemical
compositions present in the liquid obtained at optimum conditions
were identified by Fourier Transform-Infrared (FT-IR) spectroscopy
and Gas Chromatography/ Mass Spectroscopy (GC/MS) analysis
respectively.
Abstract: Deoxygenation of beef fat for the production of hydrogenated biodiesel is investigated in a high pressure continuous flow fixed bed reactor over palladium-supported mesoporous titania catalyst synthesized via a combined single-step sol-gel process with surfactant-assisted templating method (SATM). The catalyst possessed a mesoporous charactheristic with high surface area and narrow pore size distribution. The main products of all Pd/TiO2 catalysts are n-heptadecane (n-C17) and n-pentadecane (n-C15) resulting from decarbonylation reaction. Pd/TiO2 catalyst synthesized via a combined single-step sol-gel process with SATM (SSSG) gave higher activity and selectivity to the desired products when compared to IWI/SG-TiO2 and IWI/P25-TiO2, respectively. SSSG catalyst gave the average conversion up to 80-90 % and 80 % for the selectivity in diesel range hydrocarbons. This result may cause by the higher surface area and the ability in dispersion of palladium ion in mesoporous of TiO2 during sol-gel process.