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: Biomass such as corn and cassava wastes if left to decay will release significant quantities of greenhouse gases (GHG) including carbon dioxide and methane. The biomass wastes can be converted into biochar via thermochemical process such as slow pyrolysis. This approach can reduce the biomass wastes as well as preserve its carbon content. Biochar has the potential to be used as a carbon sequester and soil amendment. The aim of this study is to investigate the characteristics of the corn cob, cassava stem, and cassava rhizome in order to identify their potential as pyrolysis feedstocks for biochar production. This was achieved by using the proximate and elemental analyses as well as calorific value and lignocellulosic determination. The second objective is to investigate the effect of pyrolysis temperature on the biochar produced. A fixed bed slow pyrolysis reactor was used to pyrolyze the corn cob, cassava stem, and cassava rhizome. The pyrolysis temperatures were varied between 400 °C and 600 °C, while the heating rate and the holding time were fixed at 5 °C/min and 1 hour, respectively. Corn cob, cassava stem, and cassava rhizome were found to be suitable feedstocks for pyrolysis process because they contained a high percentage of volatile matter more than 80 mf wt.%. All the three feedstocks contained low nitrogen and sulphur content less than 1 mf wt.%. Therefore, during the pyrolysis process, the feedstocks give off very low rate of GHG such as nitrogen oxides and sulphur oxides. Independent of the types of biomass, the percentage of biochar yield is inversely proportional to the pyrolysis temperature. The highest biochar yield for each studied temperature is from slow pyrolysis of cassava rhizome as the feedstock contained the highest percentage of ash compared to the other two feedstocks. The percentage of fixed carbon in all the biochars increased as the pyrolysis temperature increased. The increment of pyrolysis temperature from 400 °C to 600 °C increased the fixed carbon of corn cob biochar, cassava stem biochar and cassava rhizome biochar by 26.35%, 10.98%, and 6.20% respectively. Irrespective of the pyrolysis temperature, all the biochars produced were found to contain more than 60 mf wt.% fixed carbon content, much higher than its feedstocks.
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: Heavy metals have a damaging impact for the environment, animals and humans due to their extreme toxicity and removing them from wastewaters is a very important and interesting task in the field of water pollution control. Biosorption is a relatively new method for treatment of wastewaters and recovery of heavy metals. In this study, a continuous fixed bed study was carried out by using Bacillus thuringiensis as a biosorbent for the removal of Cu and Mn ions from Sarcheshmeh Acid Mine Drainage (AMD). The effect of operating parameters such as flow rate and bed height on the sorption characteristics of B. thuringiensis was investigated at pH 6.0 for each metal ion. The experimental results showed that the breakthrough time decreased with increasing flow rate and decreasing bed height. The data also indicated that the equilibrium uptake of both metals increased with decreasing flow rate and increasing bed height. BDST, Thomas, and Yoon–Nelson models were applied to experimental data to predict the breakthrough curves. All models were found suitable for describing the whole dynamic behavior of the column with respect to flow rate and bed height. In order to regenerate the adsorbent, an elution step was carried out with 1 M HCl and five adsorption-desorption cycles were carried out in continuous manner.
Abstract: The discharge of dye in industrial effluents is of great concern because their presence and accumulation have a toxic or carcinogenic effect on living species. The removal of such compounds at such low levels is a difficult problem. The adsorption process is an effective and attractive proposition for the treatment of dye contaminated wastewater. Activated carbon adsorption in fixed beds is a very common technology in the treatment of water and especially in processes of decolouration. However, it is expensive and the powdered one is difficult to be separated from aquatic system when it becomes exhausted or the effluent reaches the maximum allowable discharge level. The regeneration of exhausted activated carbon by chemical and thermal procedure is also expensive and results in loss of the sorbent. The focus of this research was to evaluate the adsorption potential of the raw clay in removing rhodamine B from aqueous solutions using a laboratory fixed-bed column. The continuous sorption process was conducted in this study in order to simulate industrial conditions. The effect of process parameters, such as inlet flow rate, adsorbent bed height, and initial adsorbate concentration on the shape of breakthrough curves was investigated. A glass column with an internal diameter of 1.5 cm and height of 30 cm was used as a fixed-bed column. The pH of feed solution was set at 8.5. Experiments were carried out at different bed heights (5 - 20 cm), influent flow rates (1.6- 8 mL/min) and influent rhodamine B concentrations (20 - 80 mg/L). The obtained results showed that the adsorption capacity increases with the bed depth and the initial concentration and it decreases at higher flow rate. The column regeneration was possible for four adsorption–desorption cycles. The clay column study states the value of the excellent adsorption capacity for the removal of rhodamine B from aqueous solution. Uptake of rhodamine B through a fixed-bed column was dependent on the bed depth, influent rhodamine B concentration, and flow rate.
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: The present study investigates the effectiveness of
newly designed clayey pellets (fired clay pellets diameter sizes of 5
and 8 mm, and unfired clay pellets with the diameter size of 15 mm)
as the beds in the column adsorption process. The adsorption
experiments in the batch mode were performed before the column
experiment with the purpose to determine the order of adsorbent
package in the column which was to be designed in the investigation.
The column experiment was performed by using a known mass of the
clayey beds and the volume of the waste printing developer, which
was purified. The column was filled in the following order: fired clay
pellets of the diameter size of 5 mm, fired clay pellets of the diameter
size of 8 mm, and unfired clay pellets of the diameter size of 15 mm.
The selected order of the adsorbents showed a high removal
efficiency for zinc (97.8%) and copper (81.5%) ions. These
efficiencies were better than those in the case of the already existing
mode adsorption. The obtained experimental data present a good
basis for the selection of an appropriate column fill, but further
testing is necessary in order to obtain more accurate results.
Abstract: Biomass briquette gasification is regarded as a
promising route for efficient briquette use in energy generation, fuels
and other useful chemicals. However, previous research has been
focused on briquette gasification in fixed bed gasifiers such as
updraft and downdraft gasifiers. Fluidised bed gasifier has the
potential to be effectively sized to medium or large scale. This study
investigated the use of fuel briquettes produced from blends of rice
husks and corn cobs biomass, in a bubbling fluidised bed gasifier.
The study adopted a combination of numerical equations and Aspen
Plus simulation software, to predict the product gas (syngas)
composition base on briquette density and biomass composition
(blend ratio of rice husks to corn cobs). The Aspen Plus model was
based on an experimentally validated model from the literature. The
results based on a briquette size 32 mm diameter and relaxed density
range of 500 to 650kg/m3, indicated that fluidisation air required in
the gasifier increased with increase in briquette density, and the
fluidisation air showed to be the controlling factor compared with the
actual air required for gasification of the biomass briquettes. The
mass flowrate of CO2 in the predicted syngas composition increased
with an increase in air flow, in the gasifier, while CO decreased and
H2 was almost constant. The ratio of H2 to CO for various blends of
rice husks and corn cobs did not significantly change at the designed
process air, but a significant difference of 1.0 was observed between
10/90 and 90/10 % blend of rice husks and corn cobs.
Abstract: Incineration of municipal solid waste (MSW) is one of
the key scopes in the global clean energy strategy. A computational
fluid dynamics (CFD) model was established in order to reveal these
features of the combustion process in a fixed porous bed of MSW.
Transporting equations and process rate equations of the waste bed
were modeled and set up to describe the incineration process,
according to the local thermal conditions and waste property
characters. Gas phase turbulence was modeled using k-ε turbulent
model and the particle phase was modeled using the kinetic theory of
granular flow. The heterogeneous reaction rates were determined
using Arrhenius eddy dissipation and the Arrhenius-diffusion
reaction rates. The effects of primary air flow rate and temperature in
the burning process of simulated MSW are investigated
experimentally and numerically. The simulation results in bed are
accordant with experimental data well. The model provides detailed
information on burning processes in the fixed bed, which is otherwise
very difficult to obtain by conventional experimental techniques.
Abstract: 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.
Abstract: A mathematical model study was carried out to investigate gasification of biomass fuels using high temperature air and steam as a gasifying agent using high-temperature air up to 1000°C. In this study, a 2D computational fluid dynamics model was developed to study the gasification process in an updraft gasifier, considering drying, pyrolysis, combustion, and gasification reactions. The gas and solid phases were resolved using a Euler−Euler multiphase approach, with exchange terms for the momentum, mass, and energy. The standard k−ε turbulence model was used in the gas phase, and the particle phase was modeled using the kinetic theory of granular flow. The results show that the present model giving a promise way in its capability and sensitivity for the parameter affects that influence the gasification process.
Abstract: The development of alternative energy is interesting in the present especially, hydrogen production because it is an important energy resource in the future. This paper studied the hydrogen production from catalytic dehydrogenation of ethanol through via low temperature (
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: This paper involves a study of the heavy metal pollution of the soils around one of cement plants in Libya called Suk-Alkhameas and surrounding urban areas caused by cement kiln dust (CKD) emitted. Samples of soil was collected from sites at four directions around the cement factory at distances 250m, 1000m, and 3000m from the factory and at (0-10)cm deep in the soil. These samples are analyzed for Fe (iii), Zn(ii), and Pb (ii) as major pollutants. These values are compared with soils at 25 Km distances from the factory as a reference or control samples. The results show that the concentration of Fe ions in the surface soil was within the acceptable range of 1000ppm. However, for Zn and Pb ions the concentrations at the east and north sides of the factory were found six fold higher than the benchmark level. This high value was attributed to the wind which blows usually from south to north and from west to east. This work includes an investigation of the adsorption isotherms and adsorption efficiency of CKD as adsorbent of heavy metal ions (Fe (iii), Zn(ii), and Pb(ii)) from the polluted soils of Suk-Alkameas city. The investigation was conducted in batch and fixed bed column flow technique. The adsorption efficiency of the studied heavy metals ions removals onto CKD depends on the pH of the solution. The optimum pH values are found to be in the ranges of 8-10 and decreases at lower pH values. The removal efficiency of these heavy metals ions ranged from 93% for Pb, 94% for Zn, and 98% for Fe ions for 10 g.l-1 adsorbent concentration. The maximum removal efficiency of these ions was achieved at 50-60 minutes contact times at which equilibrium is reached. Fixed bed column experimental measurements are also made to evaluate CKD as an adsorbent for the heavy metals. Results obtained are with good agreement with Langmuir and Drachsal assumption of multilayer formation on the adsorbent surface.
Abstract: This paper reported an experimental research of
steady-state heat transfer behaviour of a gas flowing through a fixed
bed under the different operating conditions. Studies had been carried
out in a fixed-bed packed methanol synthesis catalyst percolated by air
at appropriate flow rate. Both radial and axial direction temperature
distribution had been investigated under the different operating
conditions. The effects of operating conditions including the reactor
inlet air temperature, the heating pipe temperature and the air flow rate
on temperature distribution was investigated and the experimental
results showed that a higher inlet air temperature was conducive to
uniform temperature distribution in the fixed bed. A large temperature
drop existed at the radial direction, and the temperature drop increased
with the heating pipe temperature increasing under the experimental
conditions; the temperature profile of the vicinity of the heating pipe
was strongly affected by the heating pipe temperature. A higher air
flow rate can improve the heat transfer in the fixed bed. Based on the
thermal distribution, heat transfer models of the fixed bed could be
established, and the characteristics of the temperature distribution in
the fixed bed could be finely described, that had an important practical
significance.
Abstract: The paper aims at investigating influence of medium
capacity on linear adsorbed solute dispersion into chemically
heterogeneous fixed beds. A discrete chemical heterogeneity
distribution is considered in the one-dimensional advectivedispersive
equation. The partial differential equation is solved using
finite volumes method based on the Adam-Bashforth algorithm.
Increased dispersion is estimated by comparing breakthrough curves
second order moments and keeping identical hydrodynamic
properties. As a result, dispersion increase due to chemical
heterogeneity depends on the column size and surprisingly on the
solid capacity. The more intense capacity is, the more important
solute dispersion is. Medium length which is known to favour this
effect vanishing according to the linear adsorption in fixed bed seems
to create nonmonotonous variation of dispersion because of the
heterogeneity. This nonmonotonous behaviour is also favoured by
high capacities.
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.