Properties Analysis of Spent Catalyst for Fixed-Bed Residue Hydrotreating Unit: Composition of Deposited Elements Along Catalyst Bed

Element compositions of spent catalyst from a commercial fixed-bed residue hydrotreating unit of Petro-China were analyzed in order to investigate the reasons for the catalyst deactivation. The spent catalysts were sampled from different axial position of the reactor. Depositions of C, H, S, N, Ni and V on the spent catalysts were studied. No necessary relation was observed for the contents of various deposited elements along the bed at the end of a run. The deposition amount of elements was mainly related to local reaction conditions and catalyst loading states in the fixed-bed. The catalysts with high metal depositions have low contents of coke, high contents of sulfur and high H/C, which indicates that residue hydrotreating is an autocatalytic process. Metal sulfides deposited on catalysts have a hydrogenation activity in residue hydrotreating. The coke on residue hydrotreating catalysts mainly comes from some specific condensed ring structures containing nitrogen existed in asphaltene which is difficult to hydrotreat.Key words: Spent catalyst; Residue hydrotreating; Deposited elements; Compositio

Properties Analysis of Spent Catalyst for Fixed-Bed Residue Hydrotreating Unit: Radial Distribution of Deposited Elements in Spent Catalyst Particles

14 spent catalysts, which were sampled from a commercial residue hydrotreating unit at the end of an operation cycle, were analyzed by SEM to describe elements distributions along the radial direction of particles. Different from laboratory equipment, on the whole, V, Ni and S showed U-shaped pattern along the radial direction of spent catalysts. The catalyst bed has been penetrated by deposited metals and deposited massive metals on catalyst, so the pore size of catalyst decreased, diffusion resistance increased and reactants entered internal of the catalysts more difficultly. Most of the organometallic compounds hydrotreated and deposited on outside of the catalyst particles. It is showed that metals deposited on catalyst in forms of metal sulfides because the points of high metal content also have high sulfur contents unexceptionally. The structure of high metal deposition catalyst was destroyed obviously or massive irregular material has deposited on the external surface. It is verified by SEM that there is no any distribution law for deposited elements along the bed height. The change laws of deposited elements along the bed height and radial direction of particles were influenced by various factors in commercial residue hydrotrating.Key words: Residue hydrotreating unit; Spent catalyst; SE

Iron Contamination Mechanism and Reaction Performance Research on FCC Catalyst

FCC (Fluid Catalytic Cracking) catalyst iron poisoning would not only influence units’ product slate; when the poisoning is serious, it could also jeopardize FCC catalysts’ fluidization in reaction-regeneration system and further cause bad influences on units’ stable operation. Under catalytic cracking reaction conditions, large amount of iron nanonodules is formed on the seriously iron contaminated catalyst due to exothermic reaction. These nodules intensify the attrition between catalyst particles and generate plenty of fines which severely influence units’ smooth running. A dense layer could be formed on the catalysts’ surface after iron contamination and the dense layer stops reactants to diffuse to inner structures of catalyst. This causes extremely negative effects on catalyst’s heavy oil conversion ability and could greatly cut down gasoline yield while increasing yields of dry gas, coke, and slurry largely. Research shows that catalyst’s reaction performance would be severely deteriorated when iron content in E-cat (equilibrium catalyst) exceeds 8000 μg/g

Regulating the coordination mode of Ti atoms in the beta zeolite framework to enhance the 1-Hexene Epoxidation

Regulating the Ti active sites in titanosilicates with different coordination modes is of prime scientific and industrial significance to the rational design of efficient catalysts for olefin epoxidation. In this study, the Ti species in Ti-beta zeolite catalysts (open/closed tetra-coordinated Ti sites, hexa-coordinated Ti species, and TiO2) were keenly controlled via the dealumination-metallization approach. By multiple characterizations, kinetics study, and multivariate model analysis, it is found that the open tetra-coordinated framework Ti(OH)(OSi)3 species contribute more to the catalytic performance for 1-hexene epoxidation with H2O2. Moreover, the Ti-beta with rich open tetra-coordinated Ti(OH)(OSi)3 species showed significantly improved reaction performance (TON: 401, conversion: 64%, selectivity: 98%, H2O2 efficiency: 97%) with lower apparent activation energy. This study not only opens up new prospects for the design of efficient titanosilicates by modifying Ti microenvironments but also proposes the strategy to improve the content of open tetra-coordinated Ti sites

Towards the Building Information Modeling-Based Capital Project Lifecycle Management in the Luxury Yacht Industry

It will be a new approach that BIM’s capital project lifecycle management (CPLM) applied to the yacht industry. This paper explored the feasibility of applying the principles and rationales of BIM for capital project lifecycle management in luxury yacht design, engineering, fabrication, construction and operation. The paper examined the premises and backbone technology of BIM. It then evaluated leading naval engineering and shipbuilding software applications and their development trends from the functional lens of BIM. To systematically investigate a BIM-based approach for capital project lifecycle management (CPLM) in the luxury yacht industry, the paper proposed and outlined an implementation framework. A case study and a student competition use case were discussed to delineate the core constituents and processes of the proposed framework. The case of BIM was reviewed. Through the domestic custom luxury yacht design and prototyping student competition, the application of this framework in educational research is demonstrated and the initial quantitative assessment of the framework is carried out. Conclusions: a BIM-based CPLM implementation framework can help the luxury yacht industry capitalize on the global transformation to an information-centric and data-driven new business paradigm in shipbuilding with integrated design, manufacturing and production

Mechanistic Insights into the Pore Confinement Effect on Bimolecular and Monomolecular Cracking Mechanisms of N-octane over HY and HZSM-5 Zeolites: A DFT Study

Bimolecular and monomolecular cracking mechanisms of alkanes simultaneously occur and have a competitive relationship, which strongly influences the product distribution. In this work, the density functional theory (DFT) calculation is first carried out to elucidate two cracking mechanisms in HZSM-5 and HY zeolites. It is found that the overall apparent reaction barrier for the monomolecular cracking reaction at 750 K in the HZSM-5 zeolite is 5.30 kcal/mol, much lower than that (23.12 kcal/mol) for bimolecular cracking reaction, indicating that the monomolecular mechanism is predominant in the HZSM-5 zeolite. In contrast, the bimolecular mechanism is predominant in the HY zeolite because of a lower apparent reaction barrier energy barrier (6.95 kcal/mol) for bimolecular cracking reaction than that (24.34 kcal/mol) for the monomolecular cracking reaction. Moreover, the intrinsic reason for the different mechanisms is further elucidated. The confinement effect can effectively decrease the energy barrier when the size of transition states is comparable to the pore size of zeolite. The insights in this work will be of great significance to the understanding of confinement on catalytic cracking mechanism and to the design of highly efficient cracking catalysts

A DFT Study for Catalytic Deoxygenation of Methyl Butyrate on a Lewis Acid Site of ZSM-5 Zeolite

The catalytic deoxygenation mechanism of fatty acid esters on a Lewis acid site of ZSM-5 zeolite was elucidated via density functional theory (DFT) by using a methyl butyrate (MB) as the model compound for fatty acid esters. The configurations of the initial reactant, transition states, and products together with the activation barrier of each elementary reaction were determined. The activation barrier of different initial cracking reactions decreases in the order of α-C–C > β-C–C > α-C–O > β-C–O. The best reaction path for catalytic deoxygenation of methyl butyrate over Lewis acid site is CH3CH2CH2C(OCH3)=O⋯Lewis → CH3CH2⋯Lewis⋯C(=CH2)OCH3 → CH2=CH2 + CH3COOCH3 + Lewis. The oxygen of methyl butyrate is mainly removed as CO2, methyl acetate, formaldehyde, and butyraldehyde, while ethylene, propylene, and butane are the main hydrocarbon products. In addition, the group generated by cracking of methyl butyrate form a bond with the Lewis acid site, promoting the transformation between a Lewis acid and a Brønsted acid. The corresponding intermediates have a high single point energy, but the poor stability leads to further deoxygenation and cracking reactions. This work provides a theoretical basis for the modification in the number of Brønsted acid and Lewis acid sites in the ZSM-5 zeolite

Nanocarbon‐based electrocatalysts for rechargeable aqueous Li/Zn‐air batteries

Rechargeable aqueous Li/Zn‐air batteries have become the most attractive energy storage devices because of their extremely high theoretical energy density, which enables electric vehicles to drive long range. However, current achievements still suffer from poor cycle life, low practical energy density, low round‐trip efficiency, and high manufacturing costs. One of the key challenges is the sluggish kinetics of oxygen electrochemistry during discharge and charge cycles. Thus, significant breakthroughs in design and synthesis of efficient electrocatalysts for the oxygen redox reaction are highly demanded. Nanocarbons, especially heteroatoms doped nanocarbons, are potential oxygen reduction reaction (ORR) catalysts due to the reasonable balance between catalytic activity, durability, and cost. Importantly, by introduction of transition metal nanoparticles, spinel oxides, layered‐double hydroxides, perovskite oxides, and other metal oxides, the constructed nanocarbon‐based materials could deliver promising bifunctional ORR and oxygen evolution reaction (OER) catalytic properties, which could be employed as air‐cathode materials to improve energy storage performances, even to get commercialized. Here, an overview of the recent progress of nanocarbon‐based electrocatalysts as air‐cathode materials for rechargeable aqueous Li/Zn‐air batteries is provided, aiming to highlight the benefits and issues of nanocarbon‐based electrocatalysts as well as to outline the most promising results and applications so far.MOE (Min. of Education, S’pore

Progress in aqueous rechargeable batteries

Over the past decades, a series of aqueous rechargeable batteries (ARBs) were explored, investigated and demonstrated. Among them, aqueous rechargeable alkali-metal ion (Li+, Na+, K+) batteries, aqueous rechargeable-metal ion (Zn2+, Mg2+, Ca2+, Al3+) batteries and aqueous rechargeable hybrid batteries are standing out due to peculiar properties. In this review, we focus on the fundamental basics of these batteries, and discuss the scientific and/or technological achievements and challenges. By critically reviewing state-of-the-art technologies and the most promising results so far, we aim to analyze the benefits of ARBs and the critical issues to be addressed, and to promote better development of ARBs

Numerical Investigation of the Temperature Field Effect on the Mechanical Responses of Conventional and Cool Pavements

Funding Information: This paper was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—OE 514/15-1 (Project ID 459436571) and SFB/TRR 339 (Project-ID 453596084). The authors are solely responsible for the content. Publisher Copyright: © 2022 by the authors.Conventional asphalt pavement has a deep surface color and large thermal inertia, which leads to the continuous absorption of solar thermal radiation and the sharp rise of surface temperature. This can easily lead to the permanent deformation of pavement, as well as aggravate the urban heat island (UHI) effect. Cool pavement with a reflective coating plays an important role in reducing pavement temperature and alleviating the UHI effect. It is of great significance to study the influence of temperature on the mechanical response of different types of pavement under vehicle loading. Therefore, this study examined the heat exchange theory between pavement and the external environment and utilized the representative climate data of a 24 h period in the summer. Two kinds of three-dimensional finite element models were established for the analysis of temperature distribution and the mechanical responses of conventional pavement and cool pavement. The results show that in this environmental condition, conventional pavement temperatures can exceed 50 °C under high temperatures in summer, which allows for the permanent deformation of pavement and further affects the service life of asphalt pavement. The temperature difference in a conventional pavement surface between 6 h (24.7 °C) and 22 h (30.2 °C) is much less than that between 22 h (30.2 °C) and 13 h (50.1 °C) in the summer. However, the difference in the vertical displacements of the pavement surface between 6 h and 22 h is much larger than that between 22 h and 13 h. One reason is that the difference in temperature distribution between the morning and night leads to changes in pavement structure stiffness, resulting in significant differences in vertical displacement. Cool pavement has a significant cooling effect, which can reduce the surface temperature of a road by more than 15 °C and reduce the vertical displacement of the pavement by approximately 11.3%, which improves the rutting resistance of the pavement. However, the use of cool pavement will not change the horizontal strain at the bottom of the asphalt base and will not improve the fatigue resistance of asphalt pavement. This research will lay the foundation for further clarifying the difference in the mechanical properties between the two types of pavements in the management and maintenance stage.Peer reviewe