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: Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.
Abstract: In an energy-intensive world, minimizing energy consumption is paramount to cost saving and reducing the carbon footprint. Improving mixture procedures utilizing warm mix additive Fischer-Tropsch (FT) wax in ethylene vinyl acetate (EVA) and modified bitumen highlights a greener and sustainable approach to modified bitumen. In this study, the impact of FT wax on optimized EVA/waste crumb rubber modified bitumen is assayed with a maximum loading of 2.5%. The rationale of the FT wax loading is to maintain the original maximum loading of EVA in the optimized mixture. The phase change abilities of FT wax enable EVA co-crystallization with the support of the elastomeric backbone of crumb rubber. Less than 1% loading of FT wax worked in the EVA/crumb rubber modified bitumen energy-sustainability nexus. Response surface methodology approach to the mixture design is implemented amongst the different loadings of FT wax, EVA for a consistent amount of crumb rubber and bitumen. Rheological parameters (complex shear modulus, phase angle and rutting parameter) were the factors used as performance indicators of the different optimized mixtures. The low temperature chemistry of the optimized mixtures is analyzed using elementary beam theory and the elastic-viscoelastic correspondence principle. Master curves and black space diagrams are developed and used to predict age-induced cracking of the different long term aged mixtures. Modified binder rheology reveals that the strain response is not linear and that there is substantial re-arrangement of polymer chains as stress is increased, this is based on the age state of the mixture and the FT wax and EVA loadings. Dominance of individual effects is evident over effects of synergy in co-interaction of EVA and FT wax. All-inclusive FT wax and EVA formulations were best optimized in mixture 4 with mixture 7 reflecting increase in ease of workability. Findings show that interaction chemistry of bitumen, crumb rubber EVA, and FT wax is first and second order in all cases involving individual contributions and co-interaction amongst the components of the mixture.
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: High temperature Fischer-Tropsch synthesis process
use fixed fluidized bed as a reactor. In order to understand the flow
behavior in the fluidized bed better, the research of how the radial
velocity affects the entire flow field is necessary. Laser Doppler
Velocimetry (LDV) was used to study the radial velocity distribution
along the diameter direction of the cross-section of the particle in a
fixed fluidized bed. The velocity in the cross-section is fluctuating
within a small range. The direction of the speed is a random
phenomenon. In addition to r/R is 1, the axial velocity are more than 6
times of the radial velocity, the radial velocity has little impact on the
axial velocity in a fixed fluidized bed.
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.
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.
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: Fischer-Tropsch synthesis is one of the most
important catalytic reactions that convert the synthetic gas to light
and heavy hydrocarbons. One of the main issues is selecting the type
of reactor. The slurry bubble reactor is suitable choice for Fischer-
Tropsch synthesis because of its good qualification to transfer heat
and mass, high durability of catalyst, low cost maintenance and
repair. The more common catalysts for Fischer-Tropsch synthesis are
Iron-based and Cobalt-based catalysts, the advantage of these
catalysts on each other depends on which type of hydrocarbons we
desire to produce. In this study, Fischer-Tropsch synthesis is modeled
with Iron and Cobalt catalysts in a slurry bubble reactor considering
mass and momentum balance and the hydrodynamic relations effect
on the reactor behavior. Profiles of reactant conversion and reactant
concentration in gas and liquid phases were determined as the
functions of residence time in the reactor. The effects of temperature,
pressure, liquid velocity, reactor diameter, catalyst diameter, gasliquid
and liquid-solid mass transfer coefficients and kinetic
coefficients on the reactant conversion have been studied. With 5%
increase of liquid velocity (with Iron catalyst), H2 conversions
increase about 6% and CO conversion increase about 4%, With 8%
increase of liquid velocity (with Cobalt catalyst), H2 conversions
increase about 26% and CO conversion increase about 4%. With
20% increase of gas-liquid mass transfer coefficient (with Iron
catalyst), H2 conversions increase about 12% and CO conversion
increase about 10% and with Cobalt catalyst H2 conversions increase
about 10% and CO conversion increase about 6%. Results show that
the process is sensitive to gas-liquid mass transfer coefficient and
optimum condition operation occurs in maximum possible liquid
velocity. This velocity must be more than minimum fluidization
velocity and less than terminal velocity in such a way that avoid
catalysts particles from leaving the fluidized bed.
Abstract: The adsorption properties of CO and H2 on iron-based
catalyst with addition of Zr and Ni were investigated using
temperature programmed desorption process. It was found that on the
carburized iron-based catalysts, molecular state and dissociative state
CO existed together. The addition of Zr was preferential for the
molecular state adsorption of CO on iron-based catalyst and the
presence of Ni was beneficial to the dissociative adsorption of CO. On
H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron
sites and surface oxide sites. On CO reduced catalysts, hydrogen
probably existed as the most stable CH and OH species. The addition
of Zr was not benefit to the dissociative adsorption of hydrogen on
iron-based catalyst and the presence of Ni was preferential for the
dissociative adsorption of hydrogen.
Abstract: In this study, a reformer model simulation to use
refinery (Farashband refinery, Iran) waste natural gas. In the
petroleum and allied sectors where natural gas is being encountered
(in form of associated gas) without prior preparation for its positive
use, its combustion (which takes place in flares, an equipment through
which they are being disposed) has become a great problem because
of its associated environmental problems in form of gaseous emission.
The proposed model is used to product syngas from waste natural gas.
A detailed steady model described by a set of ordinary differential and
algebraic equations was developed to predict the behavior of the
overall process. The proposed steady reactor model was validated
against process data of a reformer synthesis plant recorded and a good
agreement was achieved. H2/CO ratio has important effect on Fischer-
Tropsch synthesis reactor product and we try to achieve this parameter
with best designing reformer reactor. We study different kind of
reformer reactors and then select auto thermal reforming process of
natural gas in a fixed bed reformer that adjustment H2/CO ratio with
CO2 and H2O injection. Finally a strategy was proposed for prevention
of extra natural gas to atmosphere.
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.