scholarly journals Directed transforming of coke to active intermediates in methanol-to-olefins catalyst to boost light olefins selectivity

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jibin Zhou ◽  
Mingbin Gao ◽  
Jinling Zhang ◽  
Wenjuan Liu ◽  
Tao Zhang ◽  
...  
Keyword(s):  
Density Functional ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Density Functional Theory Calculations ◽  
Steam Gasification ◽  
Coke Deposition ◽  
Light Olefins ◽  
Structured Illumination ◽  
Structured Illumination Microscopy ◽  
Light Olefins Selectivity

AbstractMethanol-to-olefins (MTO), the most important catalytic process producing ethylene and propylene from non-oil feedstocks (coal, natural gas, biomass, CO2, etc.), is hindered by rapid catalyst deactivation due to coke deposition. Common practice to recover catalyst activity, i.e. removing coke via air combustion or steam gasification, unavoidably eliminates the active hydrocarbon pool species (HCPs) favoring light olefins formation. Density functional theory calculations and structured illumination microscopy reveal that naphthalenic cations, active HCPs enhancing ethylene production, are highly stable within SAPO-34 zeolites at high temperature. Here, we demonstrate a strategy of directly transforming coke to naphthalenic species in SAPO-34 zeolites via steam cracking. Fluidized bed reactor-regenerator pilot experiments show that an unexpectedly high light olefins selectivity of 85% is achieved in MTO reaction with 88% valuable CO and H2 and negligible CO2 as byproducts from regeneration under industrial-alike continuous operations. This strategy significantly boosts the economics and sustainability of MTO process.

scholarly journals Mechanism of selective benzene hydroxylation catalyzed by iron-containing zeolites

2018 ◽  
Vol 115 (48) ◽  
pp. 12124-12129 ◽  
Author(s):  
Benjamin E. R. Snyder ◽  
Max L. Bols ◽  
Hannah M. Rhoda ◽  
Pieter Vanelderen ◽  
Lars H. Böttger ◽  
...  
Keyword(s):  
High Activity ◽  
Active Site ◽  
Active Sites ◽  
High Performance ◽  
Density Functional ◽  
Catalyst Deactivation ◽  
Density Functional Theory Calculations ◽  
Oxidation Catalysis ◽  
Spectroscopic Techniques ◽  
Benzene Hydroxylation

A direct, catalytic conversion of benzene to phenol would have wide-reaching economic impacts. Fe zeolites exhibit a remarkable combination of high activity and selectivity in this conversion, leading to their past implementation at the pilot plant level. There were, however, issues related to catalyst deactivation for this process. Mechanistic insight could resolve these issues, and also provide a blueprint for achieving high performance in selective oxidation catalysis. Recently, we demonstrated that the active site of selective hydrocarbon oxidation in Fe zeolites, named α-O, is an unusually reactive Fe(IV)=O species. Here, we apply advanced spectroscopic techniques to determine that the reaction of this Fe(IV)=O intermediate with benzene in fact regenerates the reduced Fe(II) active site, enabling catalytic turnover. At the same time, a small fraction of Fe(III)-phenolate poisoned active sites form, defining a mechanism for catalyst deactivation. Density-functional theory calculations provide further insight into the experimentally defined mechanism. The extreme reactivity of α-O significantly tunes down (eliminates) the rate-limiting barrier for aromatic hydroxylation, leading to a diffusion-limited reaction coordinate. This favors hydroxylation of the rapidly diffusing benzene substrate over the slowly diffusing (but more reactive) oxygenated product, thereby enhancing selectivity. This defines a mechanism to simultaneously attain high activity (conversion) and selectivity, enabling the efficient oxidative upgrading of inert hydrocarbon substrates.

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 Effect of Water Molecule on Photo-Assisted Nitrous Oxide Decomposition over Oxotitanium Porphyrin: A Theoretical Study

Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 157
Author(s):  
Phornphimon Maitarad ◽  
Vinich Promarak ◽  
Liyi Shi ◽  
Supawadee Namuangruk
Keyword(s):  
Nitrous Oxide ◽  
Density Functional ◽  
Catalyst Deactivation ◽  
Activation Barrier ◽  
N2o Decomposition ◽  
Density Functional Theory Calculations ◽  
Catalytic Performance ◽  
Nitrous Oxide Decomposition ◽  
Catalytic Reactors ◽  
Rate Determining Step

Water vapor has generally been recognized as an inhibitor of catalysts in nitrous oxide (N2O) decomposition because it limits the lifetime of catalytic reactors. Oxygen produced in reactions also deactivates the catalytic performance of bulk surface catalysts. Herein, we propose a potential catalyst that is tolerant of water and oxygen in the process of N2O decomposition. By applying density functional theory calculations, we investigated the reaction mechanism of N2O decomposition into N2 and O2 catalyzed by oxotitanium(IV) porphyrin (TiO-por) with interfacially bonded water. The activation energies of reaction Path A and B are compared under thermal and photo-assisted conditions. The obtained calculation results show that the photo-assisted reaction in Path B is highly exothermic and proceeds smoothly with the low activation barrier of 27.57 kcal/mol at the rate determining step. The produced O2 is easily desorbed from the surface of the catalyst, requiring only 4.96 kcal/mol, indicating the suppression of catalyst deactivation. Therefore, TiO-por is theoretically proved to have the potential to be a desirable catalyst for N2O decomposition with photo-irradiation because of its low activation barrier, water resistance, and ease of regeneration.

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.

Modelling Catalyst Deactivation by External Coke Deposition during Fluid Catalytic Cracking

2010 ◽  
Vol 8 (1) ◽  
Author(s):  
Gladys Jiménez-García ◽  
Roberto Quintana-Solórzano ◽  
Ricardo Aguilar-López ◽  
Rafael Maya-Yescas
Keyword(s):  
Catalytic Cracking ◽  
Catalyst Deactivation ◽  
Catalyst Activity ◽  
Effective Diffusivity ◽  
Fluid Catalytic Cracking ◽  
Coke Deposition ◽  
Negative Exponential Function ◽  
Operating Variables ◽  
Laboratory Reactor ◽  
Negative Exponential

Although the Fluid Catalytic Cracking (FCC) is an economic important process, simulation of its kinetics is rather empirical—mainly it is a consequence of the complex interactions among operating variables and the complex kinetics that take place. A crucial issue is the inevitable catalyst reversible deactivation, consequence of both, coke (by-product) deposition on the catalyst surface (external) and inside the catalytic zeolite (internal). In order to tackle this problem, two main proposals to evaluate deactivation rate by coking have been extensively applied, both use a probability distribution function called "the negative exponential function"—one of them uses the time that catalyst has been in the reacting stream (named Time-on-Stream), and the other is related to the coke amount on/inside the catalyst (denoted as Coke-on-Catalyst). These two deactivation models can be unified by tracking catalyst activity as function of the decrease on effective diffusivity due to pore occlusion (external) by coke—this situation leads to an increase of Thiele modules and consequently a decrease of the effectiveness factor of each reaction. This tracking of catalyst activity incorporates, implicitly, rates of reaction and transport phenomena taking place in the catalyst pores and is therefore phenomenological rather than statistical. In this work, the activity profiles predicted previously are reproduced at MAT laboratory reactor. The same approach is used to model an industrial riser and the results are in agreement with previous reports.

Field Effect Modulation of Electrocatalytic Hydrogen Evolution at Back-Gated Two-Dimensional MoS2 Electrodes

2019 ◽  
Author(s):  
Yan Wang ◽  
Sagar Udyavara ◽  
Matthew Neurock ◽  
C. Daniel Frisbie
Keyword(s):  
Electric Field ◽  
Hydrogen Evolution ◽  
Active Sites ◽  
Density Functional ◽  
Electrode Materials ◽  
Density Functional Theory Calculations ◽  
Electronic Charge ◽  
Back Side ◽  
Gate Electrode ◽  
Conventional Manner

<div> <div> <div> <p> </p><div> <div> <div> <p>Electrocatalytic activity for hydrogen evolution at monolayer MoS2 electrodes can be enhanced by the application of an electric field normal to the electrode plane. The electric field is produced by a gate electrode lying underneath the MoS2 and separated from it by a dielectric. Application of a voltage to the back-side gate electrode while sweeping the MoS2 electrochemical potential in a conventional manner in 0.5 M H2SO4 results in up to a 140-mV reduction in overpotential for hydrogen evolution at current densities of 50 mA/cm2. Tafel analysis indicates that the exchange current density is correspondingly improved by a factor of 4 to 0.1 mA/cm2 as gate voltage is increased. Density functional theory calculations support a mechanism in which the higher hydrogen evolution activity is caused by gate-induced electronic charge on Mo metal centers adjacent the S vacancies (the active sites), leading to enhanced Mo-H bond strengths. Overall, our findings indicate that the back-gated working electrode architecture is a convenient and versatile platform for investigating the connection between tunable electronic charge at active sites and overpotential for electrocatalytic processes on ultrathin electrode materials.</p></div></div></div><br><p></p></div></div></div>

A New Phase of the Na+ Ion Conductor Na3PS4

2019 ◽  
Author(s):  
Theodosios Famprikis ◽  
James Dawson ◽  
François Fauth ◽  
Emmanuelle Suard ◽  
Benoit Fleutot ◽  
...  
Keyword(s):  
Solid Electrolytes ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Orthorhombic Crystal ◽  
Orthorhombic Crystal Structure ◽  
Ion Conductor ◽  
Solid State Batteries ◽  
Density Analysis ◽  
Two Phases ◽  
Dynamics Simulations

<div> <p>Solid electrolytes are crucial for next‑generation solid‑state batteries and Na<sub>3</sub>PS<sub>4</sub> is one of the most promising Na<sup>+</sup> conductors for such applications. At present, two phases of Na<sub>3</sub>PS<sub>4</sub> have been identified and it had been thought to melt above 500 °C. In contrast, we show that it remains solid above this temperature and transforms into a third polymorph, γ, exhibiting superionic behavior. We propose an orthorhombic crystal structure for γ‑Na<sub>3</sub>PS<sub>4</sub> based on scattering density analysis of diffraction data and density functional theory calculations. We show that the Na<sup>+</sup> superionic behavior is associated with rotational motion of the thiophosphate polyanions pointing to a rotor phase, based on <i>ab initio</i> molecular dynamics simulations and supported by high‑temperature synchrotron and neutron diffraction, thermal analysis and impedance spectroscopy. These findings are of importance for the development of new polyanion‑based solid electrolytes.</p> </div>

On the Linear Geometry of Lanthanide Hydroxide (Ln—OH, Ln=La-Lu)

2019 ◽  
Author(s):  
Hassan Harb ◽  
Lee Thompson ◽  
Hrant Hratchian
Keyword(s):  
Triple Bond ◽  
Density Functional ◽  
Valence Electron ◽  
Density Functional Theory Calculations ◽  
Electron Configuration ◽  
Functional Theory ◽  
Key Species ◽  
Pi Orbitals ◽  
Lanthanide Hydroxide ◽  
Linear Geometry

Lanthanide hydroxides are key species in a variety of catalytic processes and in the preparation of corresponding oxides. This work explores the fundamental structure and bonding of the simplest lanthanide hydroxide, LnOH (Ln=La-Lu), using density functional theory calculations. Interestingly, the calculations predict that all structures of this series will be linear. Furthermore, these results indicate a valence electron configuration featuring an occupied sigma orbital and two occupied pi orbitals for all LnOH compounds, suggesting that the lanthanide-hydroxide bond is best characterized as a covalent triple bond.

On the Linear Geometry of Lanthanide Hydroxide (Ln—OH, Ln=La-Lu)

2019 ◽  
Author(s):  
Hassan Harb ◽  
Lee Thompson ◽  
Hrant Hratchian
Keyword(s):  
Triple Bond ◽  
Density Functional ◽  
Valence Electron ◽  
Density Functional Theory Calculations ◽  
Electron Configuration ◽  
Functional Theory ◽  
Key Species ◽  
Pi Orbitals ◽  
Lanthanide Hydroxide ◽  
Linear Geometry

Lanthanide hydroxides are key species in a variety of catalytic processes and in the preparation of corresponding oxides. This work explores the fundamental structure and bonding of the simplest lanthanide hydroxide, LnOH (Ln=La-Lu), using density functional theory calculations. Interestingly, the calculations predict that all structures of this series will be linear. Furthermore, these results indicate a valence electron configuration featuring an occupied sigma orbital and two occupied pi orbitals for all LnOH compounds, suggesting that the lanthanide-hydroxide bond is best characterized as a covalent triple bond.

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