Search results for: Dehydrogenation and hydrogenation

Authors: Ahtesham Javaid, Costin S. Bildea

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.

Keywords: Dehydrogenation and hydrogenation, Reaction coupling, Design and control, Process integration.

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Authors: Weicai Yang, Xianfeng Dong, Dapeng Zeng, Bo Lin, Jun Tang

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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.

Keywords: V-5Cr-5Ti alloy, HDH, microstructures, mechanical properties.

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Authors: Ke Zhang, Fang Li, Haitao Zhang, Hongfang Ma, Weiyong Ying, Dingye Fang

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.

Keywords: Acetic acid, hydrogenation, Pt-Sn catalysts, ethanol.

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Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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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.

Keywords: Acetic acid, hydrogenation, PtSn, operating condition.

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Authors: Deepa Govindarajan, Debdut Roy

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).

Keywords: Dehydrogenation, alumina, platinum-tin catalyst, dechlorination.

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Authors: S. Totong, K. Faungnawakij, N. Laosiripojana

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 (<500°C) reaction. Copper (Cu) and silver (Ag) supported on fumed silica (SiO2) were selected in the present work; in addition, bimetallic material; Ag-Cu supported on SiO2 was also investigated. The catalysts were prepared by the incipient wetness impregnation method and characterized via X-ray diffraction (XRD), temperature-programmed reduction (TPR)and nitrogen adsorption measurements. The catalytic dehydrogenation of ethanol was carried out in a fixed bed continuous flow reactor at atmospheric pressure. The effect of reaction temperature between 300-375°C was studied in order to maximize the hydrogen yield. It was found that Ag-Cu/SiO2 exhibited the highest hydrogen yield compared to Ag/SiO2 and Cu/SiO2 at low reaction temperature (300°C) with full ethanol conversion. The highest hydrogen yield observed was 40% and will be further used as a reactant in fuel cells to generate electricity or feedstock of chemical production. 

Keywords: Catalyst, dehydrogenation, ethanol, hydrogen production.

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

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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 250^oC, 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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Authors: Leila Vafajoo, Farhad Khorasheh, Mehrnoosh Hamzezadeh Nakhjavani, Moslem Fattahi

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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.

Keywords: Dehydrogenation, Pt-Sn/Al2O3 Catalyst, Modeling, Nelder-Mead, Optimization

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Authors: G. Zahedi, H. Yaghoobi

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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.

Keywords: Dehydrogenation, fixed bed reactor, modeling, linear alkyl benzene.

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Authors: N. Hataivichian, K. Suriye, S. Kunjara Na Ayudhya, P. Praserthdam, S. Phatanasri

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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.

Keywords: Alumina, dehydrogenation, platinum, transition metal.

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Authors: Chin S. Y., Radzi, S. N. R., Maharon, I. H., Shafawi, M. A.

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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.

Keywords: kinetic model, dehydrogenation, simulation, modeling, propane

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Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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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.  

Keywords: Acetic acid hydrogenation, ethanol, PtSn, cylindrical particles.

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Authors: R. Jitrwung, K. Krekkeitsakul, C. Kumpidet, J. Tepkeaw, K. Jaikengdee, A. Wannajampa, W. Pathaveekongka

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Flue gas discharging from coal fired or gas combustion power plant is containing partially carbon dioxide (CO2). CO2 is a greenhouse gas which has been concerned to the global warming. Carbon Capture Storage and Utilization (CCSU) is a topic which is a tool to deal with this CO2 realization. In this paper, the Flue gas is drawn down from the chimney and filtered then it is compressed to build up the pressure until 8 barg. This compressed flue gas is sent to three stages Pressure Swing Adsorption (PSA) which is filled with activated carbon. The experiment showed the optimum adsorption pressure at 7 barg at which CO2 can be adsorbed step by step in 1st, 2nd, and 3rd stages obtaining CO2 concentration 29.8, 66.4, and 96.7% respectively. The mixed gas concentration from the last step composed of 96.7% CO2, 2.7% N2 and 0.6% O2. This mixed CO2 product gas obtained from 3 stages PSA contained high concentration of CO2 which is ready to be used for methanol synthesis. The mixed CO2 was experimented in 5-liter methanol synthesis reactor skid by 3 step processes: steam reforming, reverse water gas shift then hydrogenation. The result showed that the ratio of mixed CO2 and CH4 70/30, 50/50, 30/70 and 10/90 yielded methanol 2.4, 4.3, 5.6 and 5.3 L/day and saved 40, 30, 15, and 7% CO2 respectively. The optimum condition (positive in both methanol and CO2 consumption) was mixed CO2/CH4 ratio 47/53% by volume which yielded 4.2 L/day methanol and saved 32% CO2 compared with traditional methanol production from methane steam reforming (5 L/day) but no CO2 consumption.

Keywords: Carbon capture storage and utilization, pressure swing adsorption, reforming, methanol.

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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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.

Keywords: CNT, CO hydro-deoxygenation, DFT, liquid fuels, XPS, XTL.

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Authors: Lalita Saeaeh, Sirirat Jitkarnka

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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.

Keywords: Catalytic pyrolysis; Waste tire; Pd; Ni; HBeta

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Authors: Reyna Singh, David Lokhat, Milan Carsky

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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. 

Keywords: Catalyst, coal, liquefaction, temperature-staged.

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Authors: Saeid Khajehmandali, Fattah Mollakarimi, Zohreh Seyf

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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.

Keywords: Corrosion, Pyrolysis Gasoline, Simulation, Corrosion test copoun.

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