scholarly journals Dynamic metal-polymer interaction for the design of chemoselective and long-lived hydrogenation catalysts

2020 ◽  
Vol 6 (28) ◽  
pp. eabb7369 ◽  
Author(s):  
Songhyun Lee ◽  
Seung-Jae Shin ◽  
Hoyong Baek ◽  
Yeonwoo Choi ◽  
Kyunglim Hyun ◽  
...  
Keyword(s):  
Catalyst Deactivation ◽  
Coke Formation ◽  
Inorganic Materials ◽  
Polyphenylene Sulfide ◽  
Partial Hydrogenation ◽  
Pd Catalysts ◽  
Hydrogenation Catalysts ◽  
Soft Engineering ◽  
Metal Polymer ◽  
Polymer Interaction

Metal catalysts are generally supported on hard inorganic materials because of their high thermochemical stabilities. Here, we support Pd catalysts on a thermochemically stable but “soft” engineering plastic, polyphenylene sulfide (PPS), for acetylene partial hydrogenation. Near the glass transition temperature (~353 K), the mobile PPS chains cover the entire surface of Pd particles via strong metal-polymer interactions. The Pd-PPS interface enables H2 activation only in the presence of acetylene that has a strong binding affinity to Pd and thus can disturb the Pd-PPS interface. Once acetylene is hydrogenated to weakly binding ethylene, re-adsorption of PPS on the Pd surface repels ethylene before it is further hydrogenated to ethane. The Pd-PPS interaction enables selective partial hydrogenation of acetylene to ethylene even in an ethylene-rich stream and suppresses catalyst deactivation due to coke formation. The results manifest the unique possibility of harnessing dynamic metal-polymer interaction for designing chemoselective and long-lived catalysts.

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.

scholarly journals Catalytic Hot Gas Cleanup of Biomass Gasification Producer Gas via Steam Reforming Using Nickel-Supported Clay Minerals

Energies ◽  
2021 ◽  
Vol 14 (7) ◽  
pp. 1875
Author(s):  
Prashanth Reddy Buchireddy ◽  
Devin Peck ◽  
Mark Zappi ◽  
Ray Mark Bricka
Keyword(s):  
Catalytic Activity ◽  
Surface Area ◽  
Steam Reforming ◽  
Catalyst Deactivation ◽  
Nickel Content ◽  
Coke Formation ◽  
Biomass Gasification ◽  
Supported Nickel Catalyst ◽  
Fuel Gas ◽  
Removal Efficiencies

Amongst the issues associated with the commercialization of biomass gasification, the presence of tars has been one of the most difficult aspects to address. Tars are an impurity generated from the gasifier and upon their condensation cause problems in downstream equipment including plugging, blockages, corrosion, and major catalyst deactivation. These problems lead to losses of efficiency as well as potential maintenance issues resulting from damaged processing units. Therefore, the removal of tars is necessary in order for the effective operation of a biomass gasification facility for the production of high-value fuel gas. The catalytic activity of montmorillonite and montmorillonite-supported nickel as tar removal catalysts will be investigated in this study. Ni-montmorillonite catalyst was prepared, characterized, and tested in a laboratory-scale reactor for its efficiency in reforming tars using naphthalene as a tar model compound. Efficacy of montmorillonite-supported nickel catalyst was tested as a function of nickel content, reaction temperature, steam-to-carbon ratio, and naphthalene loading. The results demonstrate that montmorillonite is catalytically active in removing naphthalene. Ni-montmorillonite had high activity towards naphthalene removal via steam reforming, with removal efficiencies greater than 99%. The activation energy was calculated for Ni-montmorillonite assuming first-order kinetics and was found to be 84.5 kJ/mole in accordance with the literature. Long-term activity tests were also conducted and showed that the catalyst was active with naphthalene removal efficiencies greater than 95% maintained over a 97-h test period. A little loss of activity was observed with a removal decrease from 97% to 95%. To investigate the decrease in catalytic activity, characterization of fresh and used catalyst samples was performed using thermogravimetric analysis, transmission electron microscopy, X-ray diffraction, and surface area analysis. The loss in activity was attributed to a decrease in catalyst surface area caused by nickel sintering and coke formation.

scholarly journals Efficiency of using heteropoly compounds of the type (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O as catalysts for the production of ethylene

2019 ◽  
Vol 60 (11) ◽  
pp. 85-92
Author(s):  
Nikita A. Panurin ◽  
◽  
Natalya Yu. Isaeva ◽  
Ekaterina B. Markova ◽  
Tatiana F. Sheshko ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Catalyst Deactivation ◽  
Coke Formation ◽  
Fluorescence Analysis ◽  
Heteropoly Compound ◽  
Cascade Reactions ◽  
Environmental Benefits ◽  
Heteropoly Compounds ◽  
X Ray ◽  
Cell Parameters

Carrying out heterogeneous acid catalysis with the use of heteropoly compounds has received considerable attention due to the great economic and environmental benefits. In spite of this, its industrial application is limited as there are difficulties in catalyst regeneration (settling) caused by its relatively low thermal stability. The aim of present work was to search and select catalysts related to the class of heteropoly compounds for propane cracking, to test the selectivity of the prosses as well as to discuss possible approaches for solving the problem of catalyst deactivation, that can contribute to achieve stable characteristics of solid heteropoly catalysts. Among these approaches are: the development of new catalysts with high thermal stability, the modification of catalysts to promote coke combustion, the inhibition of coke formation on heteropoly compound catalysts during the process, carrying out the reactions in supercritical media and also the cascade reactions using a multifunctional heteropoly catalyst. The obtained catalyst was also studied by physicochemical methods to get deep knowledge about which features of these compounds influence on the catalytic activity. A highly active and selective catalyst for ammonium octomolybdenocobaltate(II) ammonium (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O was synthesized for cracking associated petroleum gases. The qualitative, quantitative, and structural composition as well as the specific surface area of the obtained catalyst was established by the methods of X-ray diffraction, X-ray phase and fluorescence analysis. It was revealed that ammonium octomolybdenocobaltate(II) crystallizes in a triclinic syngony with cell parameters: а = 8.6292(9) Å b = 9.4795(10) Å c = 12.2071(13) Å α = 104.326(2)° β = 109.910(2)° γ = 100.820(2)°.

scholarly journals Analysis and Model-Based Description of the Total Process of Periodic Deactivation and Regeneration of a VOx Catalyst for Selective Dehydrogenation of Propane

Catalysts ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1374
Author(s):  
Andreas Brune ◽  
Andreas Seidel-Morgenstern ◽  
Christof Hamel
Keyword(s):  
Catalyst Deactivation ◽  
Process Development ◽  
Coke Formation ◽  
Fixed Bed ◽  
Reaction Network ◽  
Fixed Bed Reactor ◽  
Side Reactions ◽  
Model Based ◽  
Total Process

This study intends to provide insights into various aspects related to the reaction kinetics of the VOx catalyzed propane dehydrogenation including main and side reactions and, in particular, catalyst deactivation and regeneration, which can be hardly found in combination in current literature. To kinetically describe the complex reaction network, a reduced model was fitted to lab scale experiments performed in a fixed bed reactor. Additionally, thermogravimetric analysis (TGA) was applied to investigate the coking behavior of the catalyst under defined conditions considering propane and propene as precursors for coke formation. Propene was identified to be the main coke precursor, which agrees with results of experiments using a segmented fixed bed reactor (FBR). A mechanistic multilayer-monolayer coke growth model was developed to mathematically describe the catalyst coking. Samples from long-term deactivation experiments in an FBR were used for regeneration experiments with oxygen to gasify the coke deposits in a TGA. A power law approach was able to describe the regeneration behavior well. Finally, the results of periodic experiments consisting of several deactivation and regeneration cycles verified the long-term stability of the catalyst and confirmed the validity of the derived and parametrized kinetic models for deactivation and regeneration, which will allow model-based process development and optimization.

The Influence Of The Support On The Deactivation Behaviour of Pt-Sn Reforming Catalysts

2005 ◽  
Vol 3 (1) ◽  
Author(s):  
Ignacio Contreras ◽  
Gustavo Pérez ◽  
Tomás Viveros
Keyword(s):  
Active Sites ◽  
Catalyst Deactivation ◽  
Mixed Oxides ◽  
Kinetic Constant ◽  
Coke Formation ◽  
Formation Kinetic ◽  
Catalytic Behavior ◽  
Reforming Catalysts ◽  
Metal Support Interaction ◽  
S Model

The effect of Al2O3-ZrO2, Al2O3-TiO2 and Al2O3-La2O3 mixed oxides on the deactivation of bifunctional Pt-Sn/ Al2O3 reforming catalysts has been investigated. The n-heptane reforming at 500°C was used as a test reaction. Changes in the catalytic behavior due to differences of the acidity and the support-metal interaction were observed. Levenspiel´s and Beltramini´s deactivation models were developed assuming a series fouling for the carbonaceous deposits. Through the Beltramini’s model it was possible to distinguish the amount of acidity that participates in the deactivation processes. Both models successfully correlated with the experimental profiles of n-heptane activity decay. The following deactivation decreasing order, Al2O3-TiO2-1>Al2O3-ZrO2-25>Al2O3-TiO2-2> Al2O3>Al2O3-La2O3-10 was found with both deactivation models. A quasi-linear correlation between the deactivation order and the coke formation kinetic constant (Levenspiel’s parameters) was observed. The catalyst acidity and the n-heptane conversion were correlated with Beltramini’s model. It was found that a high acidity (12 X 10-17 acid sites/g cat.) or metal dispersion (83%) increases the catalyst deactivation and it is necessary to have a balance of active sites in order to have a catalyst working as a bifunctional catalyst. On the other hand, the auto-regeneration Beltramini’s parameter suggests that the lowest deactivation of the Pt-Sn/ Al2O3-La2O3-10 catalyst is attributed to the cleaning capacity of the active sites. It was observed that the highest deactivation (80-92%) of the platinum-tin catalysts supported in alumina-titania mixed oxides were a result of the strong metal-support interaction (SMSI) effect. The Pt-Sn/Al2O3-La2O3-10 showed the best catalytic behavior with high initial and residual conversions (70 and 48%, respectively) and low deactivation (17 %) at a 50-minute reaction time. Furthermore, in the Pt-Sn/Al2O3 catalyst, the benzene yield was 1%, while the Pt-Sn/Al2O3-La2O3-10 showed a total inhibition of benzene production yield at residual conversions.

Hydrodeoxygenation of Phenol over Pd Catalysts. Effect of Support on Reaction Mechanism and Catalyst Deactivation

ACS Catalysis ◽  
2017 ◽  
Vol 7 (3) ◽  
pp. 2058-2073 ◽  
Author(s):  
Priscilla M. de Souza ◽  
Raimundo C. Rabelo-Neto ◽  
Luiz E. P. Borges ◽  
Gary Jacobs ◽  
Burtron H. Davis ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Catalyst Deactivation ◽  
Pd Catalysts ◽  
Effect Of Support

Optimization of Vapor Phase Pyridine Synthesis Hindered by Rapid Catalyst Deactivation

2008 ◽  
Vol 6 (1) ◽  
Author(s):  
Suresh Kumar Reddy Kuppi Reddy ◽  
Inkollu Sreedhar ◽  
Kondapuram Vijaya Raghavan ◽  
Shivanand Janardan Kulkarni ◽  
Machiraju Ramakrishna
Keyword(s):  
Catalyst Deactivation ◽  
A Priori ◽  
Coke Formation ◽  
Product Distribution ◽  
Combined Effects ◽  
Reactor Operation ◽  
Proper Selection ◽  
Pyridine Bases ◽  
Deactivation Process ◽  
Selection Of

The synthesis of pyridine bases from acetaldehyde, formaldehyde and ammonia through aminocyclization continues to provide the best prospect for meeting growing demand. A proper selection of catalyst and standardization of process parameters are vital to achieve a market friendly product distribution and reactor operation. In this work, the major responsible factors for enhancing the activity and selectivity of HZS-5 catalysts have been identified and their individual and combined effects on aldehyde conversion, coke formation and selectivity to pyridine formation have been assessed. A priori assessment of catalyst time on stream behavior has been achieved by modeling the catalyst deactivation process.

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