Abstract: Pt-Sn catalysts have been prepared using magnesium aluminate as a support with two different Mg/Al ratio. The supports/catalysts have been characterized by N2-adsorption, XRD, and temperature programmed desorption of NH3 and thermogravimetry analysis (TGA). The catalysts have been evaluated at 595 0C for the propane dehydrogenation reaction at 0.5 barg pressure using a feed containing pure propane with steam to hydrocarbon ratio of 1 mol/mol and weight hourly space velocity (WHSV) 0.9 h-1. Chlorine quantification studies have been developed using Carbon-Hydrogen-Nitrogen-Sulphur (CHNS) analyzer. The dechlorinated catalyst with higher alumina content showed better performance (38-43% propane conversion, 91-94% propylene selectivity) in propane conversion and propylene selectivity than Pt-Sn-MG-AL-DC-1 (30-18% propane conversion, 83-90% propylene selectivity).
Abstract: Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H2) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H2, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.
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.
Abstract: Alumina supported PtSn catalysts with cylindrical particles were prepared and characterized by using low temperature N2 adsorption/desorption and X-ray diffraction. Low temperature N2 adsorption/desorption demonstrate that the tableting changed the texture properties of catalysts. XRD pattern indicate that the crystal structure of supports had no change after reaction. The performances over particles of PtSn/Al2O3 catalysts were investigated with regards to reaction temperature, pressure, and H2/AcOH mole ratio. After tableting, the conversion of acetic acid and selectivity of ethanol and acetyl acetate decreased. High reaction temperature and pressure can improve conversion of acetic acid. H2/AcOH mole ratio of 9.36 showed the best performance on acetic acid hydrogenation. High pressure had benefits for the selectivity of ethanol and other two parameters had no obvious effect on selectivity.
Abstract: Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N2 adsorption/desorption, H2-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al2O3 can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al2O3 were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.
Abstract: The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal remains an abundant resource. The aim of this work was to produce a high value hydrocarbon liquid product using a Direct Coal Liquefaction (DCL) process at, relatively mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated in a dual reactor lab-scale pilot plant facility. The objectives included maximising thermal dissolution of the coal in the presence of tetralin as the hydrogen donor solvent in the first stage with 2:1 and 3:1 solvent: coal ratios. Subsequently, in the second stage, hydrogen saturation, in particular, hydrodesulphurization (HDS) performance was assessed. Two commercial hydrotreating catalysts were investigated viz. NickelMolybdenum (Ni-Mo) and Cobalt-Molybdenum (Co-Mo). GC-MS results identified 77 compounds and various functional groups present in the first and second stage liquid product. In the first stage 3:1 ratios and liquid product yields catalysed by magnetite were favoured. The second stage product distribution showed an increase in the BTX (Benzene, Toluene, Xylene) quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, Ni-Mo had an improved performance over Co-Mo. Co-Mo is selective to a higher concentration of cyclohexane. For 16 days on stream each, Ni-Mo had a higher activity than Co-Mo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.
Abstract: The effect of transition metal doping on Pt/Al2O3
catalyst used in propane dehydrogenation reaction at 500°C was
studied. The preparation methods investigated were sequential
impregnation (Pt followed by the 2nd metal or the 2nd metal followed
by Pt) and co-impregnation. The metal contents of these catalysts
were fixed as the weight ratio of Pt per the 2nd metal of around 0.075.
These catalysts were characterized by N2-physisorption, TPR, COchemisorption
and NH3-TPD. It was found that the impregnated 2nd
metal had an effect upon reducibility of Pt due to its interaction with
transition metal-containing structure. This was in agreement with the
CO-chemisorption result that the presence of Pt metal, which is a
result from Pt species reduction, was decreased. The total acidity of
bimetallic catalysts is decreased but the strong acidity is slightly
increased. It was found that the stability of bimetallic catalysts
prepared by co-impregnation and sequential impregnation where the
2nd metal was impregnated before Pt were better than that of
monometallic catalyst (undoped Pt one) due to the forming of Pt sites
located on the transition metal-oxide modified surface. Among all
preparation methods, the sequential impregnation method- having Pt
impregnated before the 2nd metal gave the worst stability because this
catalyst lacked the modified Pt sites and some fraction of Pt sites was
covered by the 2nd metal.
Abstract: The design and plantwide control of an integrated
plant where the endothermic 1,4-butanediol dehydrogenation and the
exothermic furfural hydrogenation is simultaneously performed in a
single reactor is studied. The reactions can be carried out in an
adiabatic reactor using small hydrogen excess and with reduced
parameter sensitivity. The plant is robust and flexible enough to
allow different production rates of γ-butyrolactone and 2-methyl
furan, keeping high product purities. Rigorous steady state and
dynamic simulations performed in AspenPlus and AspenDynamics to
support the conclusions.
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: Pyrolysis of waste tire is one of alternative technique
to produce petrochemicals, such as light olefins, mixed C4, and monoaromatics.
Noble metals supported on acid zeolite catalysts were
reported as potential catalysts to produce the high valuable products
from waste tire pyrolysis. Especially, Pd supported on HBeta gave a
high yield of olefins, mixed C4, and mono-aromatics. Due to the high
prices of noble metals, the objective of this work was to investigate
whether or not a non-noble Ni metal can be used as a substitute of a
noble metal, Pd, supported on HBeta as a catalyst for waste tire pyrolysis.
Ni metal was selected in this work because Ni has high activity
in cracking, isomerization, hydrogenation and the ring opening of
hydrocarbons Moreover, Ni is an element in the same group as Pd
noble metal, which is VIIIB group, aiming to produce high valuable
products similarly obtained from Pd. The amount of Ni was varied as
5, 10, and 20% by weight, for comparison with a fixed 1 wt% Pd,
using incipient wetness impregnation. The results showed that as a
petrochemical-producing catalyst, 10%Ni/HBeta performed better
than 1%Pd/HBeta because it did not only produce the highest yield of
olefins and cooking gases, but the yields were also higher than
1%Pd/HBeta. 5%Ni/HBeta can be used as a substitute of
1%Pd/HBeta for similar crude production because its crude contains
the similar amounts of naphtha and saturated HCs, although it gave
no concentration of light mono-aromatics (C6-C11) in the oil. Additionally,
10%Ni/HBeta that gave high olefins and cooking gases was
found to give a fairly high concentration of the light mono-aromatics
in the oil.
Abstract: Low oxygen content vanadium powder was
prepared by hydrogenation dehydrogenization (HDH). The
effect of purification treatment on hydrogen absorption kinetics
of dendritic vanadium was tested, and the effects of milling
technique on powder yield and grain size were studied. The
crystal phase, oxygen and nitrgen content, and grain size of
prepared powder were characterized and analyzed by X-ray
diffraction (XRD), oxygen and nitrogen analyzer and grain size
analyzer. The results show that the alkaline cleaning can
improve the hydrogen absorption of vanadium. The yield of
vanadium hydride powder can reach as high as 90% by 4h
ball-milling, The resultant product also have an oxygen content
less than 600μg/g, and the grain size is smaller than 37μm.
Meanwhile, the XRD results show that the phase of hydride
vanadium powder is mainly VH0.81. After a hydrogen
desorption treatment in vacuum at 700Ôäâ, the phase of the
powder converts into V and a little of V2H.
Abstract: There was a high rate of corrosion in Pyrolysis
Gasoline Hydrogenation (PGH) unit of Arak Petrochemical Company
(ARPC), and it caused some operational problem in this plant. A
commercial chemical had been used as anti-corrosion in the
depentanizer column overhead in order to control the corrosion rate.
Injection of commercial corrosion inhibitor caused some
operational problems such as fouling in some heat exchangers. It was
proposed to replace this commercial material with another more
effective trouble free, and well-known additive by R&D and
operation specialists.
At first, the system was simulated by commercial simulation
software in electrolytic system to specify low pH points inside the
plant. After a very comprehensive study of the situation and technical
investigations ,ammonia / monoethanol amine solution was proposed
as neutralizer or corrosion inhibitor to be injected in a suitable point
of the plant. For this purpose, the depentanizer column and its
accessories system was simulated again in case of this solution
injection.
According to the simulation results, injection of new anticorrosion
substance has no any side effect on C5 cut product and
operating conditions of the column. The corrosion rate will be
cotrolled, if the pH remains at the range of 6.5 to 8 . Aactual plant
test run was also carried out by injection of ammonia / monoethanol
amine solution at the rate of 0.6 Kg/hr and the results of iron content
of water samples and corrosion test coupons confirmed the
simulation results.
Now, ammonia / monoethanol amine solution is injected to a
suitable pint inside the plant and corrosion rate has decreased
significantly.
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: In the present study, a procedure was developed to
determine the optimum reaction rate constants in generalized
Arrhenius form and optimized through the Nelder-Mead method. For
this purpose, a comprehensive mathematical model of a fixed bed
reactor for dehydrogenation of heavy paraffins over Pt–Sn/Al2O3
catalyst was developed. Utilizing appropriate kinetic rate expressions
for the main dehydrogenation reaction as well as side reactions and
catalyst deactivation, a detailed model for the radial flow reactor was
obtained. The reactor model composed of a set of partial differential
equations (PDE), ordinary differential equations (ODE) as well as
algebraic equations all of which were solved numerically to
determine variations in components- concentrations in term of mole
percents as a function of time and reactor radius. It was demonstrated
that most significant variations observed at the entrance of the bed
and the initial olefin production obtained was rather high. The
aforementioned method utilized a direct-search optimization
algorithm along with the numerical solution of the governing
differential equations. The usefulness and validity of the method was
demonstrated by comparing the predicted values of the kinetic
constants using the proposed method with a series of experimental
values reported in the literature for different systems.
Abstract: A kinetic model for propane dehydrogenation in an
industrial moving bed reactor is developed based on the reported
reaction scheme. The kinetic parameters and activity constant are
fine tuned with several sets of balanced plant data. Plant data at
different operating conditions is applied to validate the model and
the results show a good agreement between the model
predictions and plant observations in terms of the amount of main
product, propylene produced. The simulation analysis of key
variables such as inlet temperature of each reactor (Tinrx) and
hydrogen to total hydrocarbon ratio (H2/THC) affecting process
performance is performed to identify the operating condition to
maximize the production of propylene. Within the range of operating
conditions applied in the present studies, the operating condition to
maximize the propylene production at the same weighted average
inlet temperature (WAIT) is ΔTinrx1= -2, ΔTinrx2= +1, ΔTinrx3= +1 ,
ΔTinrx4= +2 and ΔH2/THC= -0.02. Under this condition, the surplus
propylene produced is 7.07 tons/day as compared with base case.
Abstract: Three alumina-supported Pt-Sn catalysts have been
prepared by means of co-impregnation and characterized by XRD and
N2 adsorption. The influence of catalyst composition and reaction
conditions on the conversion and selectivity were investigated in the
hydrogenation of acetic acid in an isothermal integral fixed bed
reactor. The experiments were performed on the temperature interval
468-548 K, liquid hourly space velocity (LHSV) of 0.3-0.7h-1,
pressures between 1.0 and 5.0Mpa. A good compromise of
0.75%Pt-1.5%Sn can act as an optimized acetic acid hydrogenation
catalyst, and the conversion and selectivity can be tuned through the
variation of reaction conditions.