scholarly journals Mechanistic Insights into Hydrodeoxygenation of Acetone over Mo/HZSM-5 Bifunctional Catalyst for the Production of Hydrocarbons

Energies ◽  
2021 ◽  
Vol 15 (1) ◽  
pp. 53
Author(s):  
Kai Miao ◽  
Tan Li ◽  
Jing Su ◽  
Cong Wang ◽  
Kaige Wang
Keyword(s):  
Hydrogen Pressure ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Coke Formation ◽  
Bifunctional Catalyst ◽  
Acid Sites ◽  
Coke Deposition ◽  
Enhanced Production ◽  
Bio Oil ◽  
Catalytic Hydropyrolysis

Catalytic hydropyrolysis via the introduction of external hydrogen into catalytic pyrolysis process using hydrodeoxygenation catalysts is one of the major approaches of bio-oil upgrading. In this study, hydrodeoxygenation of acetone over Mo/HZSM-5 and HZSM-5 were investigated with focus on the influence of hydrogen pressure and catalyst deactivation. It is found that doped MoO3 could prolong the catalyst activity due to the suppression of coke formation. The influence of hydrogen pressure on catalytic HDO of acetone was further studied. Hydrogen pressure of 30 bar effectively prolonged catalyst activity while decreased the coke deposition over catalyst. The coke formation over the HZSM-5 and Mo/HZSM-5 under 30 bar hydrogen pressure decreased 66% and 83%, respectively, compared to that under atmospheric hydrogen pressure. Compared to the test with the HZSM-5, 35% higher yield of aliphatics and 60% lower coke were obtained from the Mo/HZSM-5 under 30 bar hydrogen pressure. Characterization of the spent Mo/HZSM-5 catalyst revealed the deactivation was mainly due to the carbon deposition blocking the micropores and Bronsted acid sites. Mo/HZSM-5 was proved to be potentially enhanced production of hydrocarbons.

scholarly journals Process Simulation and Economic Evaluation of Bio-Oil Two-Stage Hydrogenation Production

2019 ◽  
Vol 9 (4) ◽  
pp. 693
Author(s):  
Xiaoyuechuan Ma ◽  
Shusheng Pang ◽  
Ruiqin Zhang ◽  
Qixiang Xu
Keyword(s):  
Process Simulation ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Fuel Oil ◽  
Coke Deposition ◽  
Two Stage ◽  
Bio Oil ◽  
Demonstration Plant ◽  
Two Stages ◽  
Optimal Reaction

Bio-oil hydrogenation upgrading process is a method that can convert crude bio-oil into high-quality bio-fuel oil, which includes two stages of mild and deep hydrogenation. However, coking in the hydrogenation process is the key issue which negatively affects the catalyst activity and consequently the degree of hydrogenation in both stages. In this paper, an Aspen Plus process simulation model was developed for the two-stage bio-oil hydrogenation demonstration plant which was used to evaluate the effect of catalyst coking on the bio-oil upgrading process and the economic performance of the process. The model was also used to investigate the effect of catalyst deactivation caused by coke deposition in the mild stage. Three reaction temperatures in the mild stage (250 °C, 280 °C, and 300 °C) were considered. The simulation results show that 45% yield of final product is obtained at the optimal reaction condition which is 280 °C for the mild stage and 400 °C for the deep stage. Economic analysis shows that the capital cost of industrial production is $15.2 million for a bio-oil upgrading plant at a scale of 107 thousand tons per year. The operating costs are predicted to be $1024.27 per ton of final product.

An analytical microscopic study of metals in fluidized catalytic cracking catalyst

1986 ◽  
Vol 44 ◽  
pp. 854-855
Author(s):  
Clifford S. Rainey
Keyword(s):  
Electron Microscopy ◽  
Spatial Distribution ◽  
Catalytic Cracking ◽  
Catalyst Deactivation ◽  
Coke Formation ◽  
Acid Sites ◽  
Y Zeolite ◽  
Fcc Catalyst ◽  
Fluidized Catalytic Cracking ◽  
High Regeneration

The spatial distribution of V and Ni deposited within fluidized catalytic cracking (FCC) catalyst is studied because these metals contribute to catalyst deactivation. Y zeolite in FCC microspheres are high SiO2 aluminosilicates with molecular-sized channels that contain a mixture of lanthanoids. They must withstand high regeneration temperatures and retain acid sites needed for cracking of hydrocarbons, a process essential for efficient gasoline production. Zeolite in combination with V to form vanadates, or less diffusion in the channels due to coke formation, may deactivate catalyst. Other factors such as metal "skins", microsphere sintering, and attrition may also be involved. SEM of FCC fracture surfaces, AEM of Y zeolite, and electron microscopy of this work are developed to better understand and minimize catalyst deactivation.

Analysis of Precursors of Carbon Deposition in Hydrogen Preparation by Fast Pyrolysis of Bio-Oil via Catalytic Steam Reforming

2012 ◽  
Vol 512-515 ◽  
pp. 338-342 ◽  
Author(s):  
Ping Lan ◽  
Li Hong Lan ◽  
Tao Xie ◽  
An Ping Liao
Keyword(s):  
Steam Reforming ◽  
Molecular Sieve ◽  
Carbon Deposition ◽  
Catalyst Activity ◽  
Coke Formation ◽  
Fast Pyrolysis ◽  
Bio Oil ◽  
Aldehydes And Ketones ◽  
Pyrolysis Of Biomass ◽  
Catalytic Steam Reforming

In the preparation of hydrogen, the bio-oil from pyrolysis of biomass must be further upgraded (catalytic steam reforming)SO as to improve its quality．However the catalyst used in the steam reforming reaction is easy to lose its activity due to being coked' SO that it is important to study the coke formation and its efects on the catalyst activity in the steam reforming process．Fourier Transform Infrared Spectroscopy were used to analyze the precursor of coke on the catalyst Ni/MgO-La2O3-Al2O3 used in steam reforming reaction and the mechanism of coking Was also discussed based on it．The results indicate that precursors of coke deposited inside the pore of the molecular sieve are mainly paraffin, alcohols, aldehydes and ketones, and aromatic compounds.

scholarly journals Inductive Heating Assisted-Catalytic Dehydrogenation of Tetralin as a Hydrogen Source for Downhole Catalytic Upgrading of Heavy Oil

2019 ◽  
Vol 63 (3-4) ◽  
pp. 268-280 ◽  
Author(s):  
Abarasi Hart ◽  
Mohamed Adam ◽  
John P. Robinson ◽  
Sean P. Rigby ◽  
Joseph Wood
Keyword(s):  
Catalyst Deactivation ◽  
Oil Quality ◽  
Coke Formation ◽  
Coke Deposition ◽  
Conventional Heating ◽  
Inductive Heating ◽  
Catalytic Dehydrogenation ◽  
Catalytic Upgrading ◽  
Bed Temperature

AbstractThe Toe-to-Heel Air Injection (THAI) combined with a catalytic add-on (CAPRI, CATalytic upgrading PRocess In-situ) have been a subject of investigation since 2002. The major challenges have been catalyst deactivation due to coke deposition and low temperatures (~ 300 °C) of the mobilised hot oil flowing over the catalyst packing around the horizontal well. Tetralin has been used to suppress coke formation and also improve upgraded oil quality due to its hydrogen-donor capability. Herein, inductive heating (IH) incorporated to the horizontal production well is investigated as one means to resolve the temperature shortfall. The effect of reaction temperature on tetralin dehydrogenation and hydrogen evolution over NiMo/Al2O3 catalyst at 250–350 °C, catalyst-to-steel ball ratio (70% v/v), 18 bar and 0.75 h−1 was investigated. As temperature increased from 250 to 350 °C, tetralin conversion increased from 40 to 88% while liberated hydrogen increased from 0.36 to 0.88 mol based on 0.61 mol of tetralin used. The evolved hydrogen in situ hydrogenated unreacted tetralin to trans and cis-decalins with the selectivity of cis-decalin slightly more at 250 °C while at 300–350 °C trans-decalin showed superior selectivity. With IH the catalyst bed temperature was closer to the desired temperature (300 °C) with a mean of 299.2 °C while conventional heating is 294.3 °C. This thermal advantage and the nonthermal effect from electromagnetic field under IH improved catalytic activity and reaction rate, though coke formation increased.

Integration of Thermal Treatment and Catalytic Transformation for Upgrading Biomass Pyrolysis Oil

2007 ◽  
Vol 5 (1) ◽  
Author(s):  
Beatriz Valle ◽  
Ana Guadalupe Gayubo ◽  
Alaitz Atutxa ◽  
Ainhoa Alonso ◽  
Javier Bilbao
Keyword(s):  
Thermal Treatment ◽  
Thermal Degradation ◽  
Fluidized Bed ◽  
Catalyst Deactivation ◽  
Fluidized Bed Reactor ◽  
Coke Deposition ◽  
Catalytic Transformation ◽  
Pyrolysis Oil ◽  
Bio Oil ◽  
Oil Components

The upgrading of bio-oil by catalytic transformation upon acidic catalysts is aimed at adapting its composition to that of conventional fuel, or at obtaining petrochemical raw materials, such as olefins and aromatics. A further alternative of growing interest for bio-oil upgrading is catalytic reforming for obtaining H2. The viability of any of these alternatives requires minimizing both the plugging problems that arise in the reactor when the bio-oil is fed and the rapid deactivation of the catalyst, which are associated with the thermal degradation of the lignocellulosic components. In this paper, the catalytic transformation of bio-oil (obtained by fast pyrolysis of vegetable biomass) in a fluidized bed reactor upon a Ni-HZSM-5 zeolite catalyst has been studied, and special attention has been paid to the design of the feed preheating zone. Operation in a single-unit (U-shaped steel tube) for the thermal treatment of the bio-oil (in the downward zone of the U-tube) and its catalytic transformation (in a fluidized bed located in the upward zone of the U-tube) has been compared with operation in a two-unit system, where both steps are carried out in separate units connected through a thermostated line (U-shaped tube for thermal treatment, followed by a fluidized bed reactor for catalytic transformation). It has been proven that a separate step of thermal treatment prior to the catalytic transformation notably improves the global process of bio-oil upgrading. Firstly, it contributes to minimizing coke deposition on the acidic catalyst, mainly the deposition of "thermal" coke (which is associated with the thermal degradation of the bio-oil components at high temperatures), leading to an important attenuation of catalyst deactivation. Secondly, the bio-oil components degraded in the thermal treatment can subsequently be subjected to another upgrading treatment (by steam activation or pyrolysis) in order to obtain a high quality char, which involves upgrading the entire bio-oil.

Kinetic Modelling of Propane Dehydrogenation over a Pt–Sn/hierarchical SAPO-34 Zeolite Catalyst, Including Catalyst Deactivation

2017 ◽  
Vol 42 (4) ◽  
pp. 344-360
Author(s):  
Milad Komasi ◽  
Shohreh Fatemi ◽  
Seyed Hesam Mousavi
Keyword(s):  
Catalyst Deactivation ◽  
Kinetic Modelling ◽  
Coke Formation ◽  
Fixed Bed ◽  
Reaction Network ◽  
Normal Pressure ◽  
Fixed Bed Reactor ◽  
Propane Dehydrogenation ◽  
Coke Deposition ◽  
Formation Kinetic

Pt–Sn/hierarchical SAPO-34 was synthesised and kinetically modelled as an efficient and selective catalyst for propylene production through propane dehydrogenation. The kinetics of the reaction network were studied in an integral fixed-bed reactor at three temperatures of 550, 600 and 650 °C and weight hourly space velocities of 4 and 8 h−1 with a feed containing hydrogen and propane with relative molar ratios of 0.2, 0.5 and 0.8, at normal pressure. The experiments were performed in accordance with the full factorial experimental design. The kinetic models were constructed on the basis of different mechanisms and various deactivation models. The kinetics and deactivation parameters were simultaneously predicted and optimised using genetic algorithm optimisation. It was further proven that the Langmuir–Hinshelwood model can well predict propane dehydrogenation kinetics through lumping together all the possible dehydrogenation steps and also by assuming the surface reaction as the rate-determining step. A coke formation kinetic model has also shown appropriate results, confirming the experimental data by equal consideration of both monolayer and multilayer coke deposition kinetic orders and an exponential deactivation model.

scholarly journals Catalyst Stability—Bottleneck of Efficient Catalytic Pyrolysis

Catalysts ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 265
Author(s):  
Jacek Grams ◽  
Agnieszka M. Ruppert
Keyword(s):  
Lignocellulosic Biomass ◽  
Alternative Fuels ◽  
Catalyst Deactivation ◽  
Coke Formation ◽  
Catalyst Stability ◽  
Engine Fuel ◽  
Lignocellulosic Feedstock ◽  
Bio Oil ◽  
The Stability ◽  
Direct Use

The pyrolysis of lignocellulosic biomass is one of the most promising methods of alternative fuels production. However, due to the low selectivity of this process, the quality of the obtained bio-oil is usually not satisfactory and does not allow for its direct use as an engine fuel. Therefore, there is a need to apply catalysts able to upgrade the composition of the mixture of pyrolysis products. Unfortunately, despite the increase in the efficiency of the thermal decomposition of biomass, the catalysts undergo relatively fast deactivation and their stability can be considered a bottleneck of efficient pyrolysis of lignocellulosic feedstock. Therefore, solving the problem of catalyst stability is extremely important. Taking that into account, we presented, in this review, the most important reasons for catalyst deactivation, including coke formation, sintering, hydrothermal instability, and catalyst poisoning. Moreover, we discussed the progress in the development of methods leading to an increase in the stability of the catalysts of lignocellulosic biomass pyrolysis and strengthening their resistance to deactivation.

scholarly journals Surface Characteristics Change of Zinc Modified H-ZSM-5 Zeolites in Methanol to Hydrocarbons Transformation Process

2020 ◽  
Vol 6 (11) ◽  
pp. 23-30
Author(s):  
A. Sidorov ◽  
V. Molchanov ◽  
L. Mushinskii ◽  
R. Brovko
Keyword(s):  
Surface Properties ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Nitrogen Adsorption ◽  
Surface Characteristics ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Transformation Process ◽  
Methanol To Hydrocarbons ◽  
Nitrogen Adsorption Isotherms

The t-plot method is a well-known method for determining the volumes of micro- and/or mesoporous materials and the specific surface area of a sample by comparison with a reference adsorption isotherm of a non-porous material having a similar surface chemical composition. The article describes the applicability of the t-graph method to the analysis of the surface properties of zinc modified samples of zeolite H-ZSM-5 before and after the reactions of methanol transformation into hydrocarbons occur on them. Zeolites are widely used as catalysts in the petrochemical and refining industries. These materials contain active Bronsted acid sites, distributed within the microporous structure of zeolites, which leads to selective catalysis due to the difference in the pore shape of the zeolites used. The size, shape of the zeolite catalyst determines the catalytic performance in terms of both product selectivity and catalyst deactivation. In most zeolite catalyzed hydrocarbon conversion reactions, catalyst activity is lost due to carbon deposition. In this connection, the determination of the surface properties of zeolites is an important task that contributes to the disclosure of the physicochemical essence of the process of deactivation of zeolites. The recalculation of nitrogen adsorption isotherms using the t-plot model made it possible to determine the volume of micro and mesopores. Based on the t-graph data, it can be concluded that during the transformation of methanol into hydrocarbons, carbon accumulates on the surface of the zeolite. In this case, the predominant deposition of carbon on the surface of mesopores, due to the fact that in the process of decontamination, from 61 to 73% of the volume of mesopores is lost. The number of micropores also decreases, but the share of losses is 42–54%, which is 10–15% lower compared to the loss of mesopore volume.

Study of coke deposition phenomena on the SAPO_34 catalyst and its effects on light olefin selectivity during the methanol to olefin reaction

RSC Advances ◽  
2015 ◽  
Vol 5 (100) ◽  
pp. 81965-81980 ◽  
Author(s):  
Reza Bagherian Rostami ◽  
Mohammad Ghavipour ◽  
Zuoxing Di ◽  
Yao Wang ◽  
Reza Mosayyebi Behbahani
Keyword(s):  
Hydrogen Transfer ◽  
Catalyst Deactivation ◽  
Coke Formation ◽  
Great Influence ◽  
Product Distribution ◽  
Coke Deposition ◽  
Light Olefin ◽  
Methanol To Olefin ◽  
Olefin Selectivity ◽  
Transfer Index

Hydrogen transfer index was found to be a key parameter in prediction of coke deposition behavior. A good macro-model of product distribution with coke formation is provided. Temperature had a great influence on distribution of coke species and catalyst deactivation.

scholarly journals Process Intensification of the Propane Dehydrogenation Considering Coke Formation, Catalyst Deactivation and Regeneration—Transient Modelling and Analysis of a Heat-Integrated Membrane Reactor

Catalysts ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1056
Author(s):  
Jan P. Walter ◽  
Andreas Brune ◽  
Andreas Seidel-Morgenstern ◽  
Christof Hamel
Keyword(s):  
Membrane Reactor ◽  
Inner Core ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Coke Formation ◽  
Fixed Bed ◽  
Packed Bed ◽  
Membrane Reactors ◽  
Propane Dehydrogenation ◽  
Heat Integration

A heat-integrated packed-bed membrane reactor is studied based on detailed, transient 2D models for coupling oxidative and thermal propane dehydrogenation in one apparatus. The reactor is structured in two telescoped reaction zones to figure out the potential of mass and heat integration between the exothermic oxidative propane dehydrogenation (ODH) in the shell side, including membrane-assisted oxygen dosing and the endothermic, high selective thermal propane dehydrogenation (TDH) in the inner core. The developing complex concentration, temperature and velocity fields are studied, taking into account simultaneous coke growth corresponding with a loss of catalyst activity. Furthermore, the catalyst regeneration was included in the simulation in order to perform an analysis of a periodic operating system of deactivation and regeneration periods. The coupling of the two reaction chambers in a new type of membrane reactor offers potential at oxygen shortage and significantly improves the achievable propene yield in comparison with fixed bed and well-established membrane reactors in the distributor configuration without inner mass and heat integration. The methods developed allow an overall process optimization with respect to maximum spacetime yield as a function of production and regeneration times.

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