Catalyst grading technology for promoting the diesel hydrocracking to naphtha

This paper reports the application of multi-component hydrocracking catalyst grading technology in diesel hydrocracking system to increase naphtha,and studies the influence of catalyst systems with different number of graded beds on the reaction process of diesel hydrocracking.Three hydrocracking catalysts with different physicochemical properties as gradation components,the diesel hydrocracking reaction on catalyst systems of one-component,two-component and three-component graded beds with different loading sequences are carried out and evaluated,respectively.The catalytic mechanism of the multi-component grading system is analyzed.The results show that,with the increase of the number of grading beds,the space velocity of reaction on each catalyst increases,which can effectively control the overreaction process;along the flow direction of feedstock,the loading sequences of catalysts with acidity decreasing and pore properties increasing can satisfy the demand of different catalytic activity for the conversion of reactant with changing composition to naphtha,which has a guiding role in the conversion of feedstock to target products.Therefore,the conversion of diesel,the selectivity and yield of naphtha all increase significantly on the multi-component catalyst system.The research on the grading technology of multi-component catalysts is of great significance to the promotion and application of catalyst systems in various catalytic fields.

Optimization of Hydrocracking Process for Enhanced BTX Production from Coal Tar-Derived Hydrorefined Products

Hydroconversion of coal tar to produce aromatic hydrocarbons(BTX)represents a crucial strategy for the highvalue hierarchical utilization of coal.This study focused on the hydrocracking of hydrorefined products derived from coal tar to enhance the production of benzene,toluene,and xylene(BTX).Various reaction conditions,including reaction temperature,hydrogen pressure,space velocity,and hydrogen-to-oil volume ratio,were systematically explored to optimize BTX yields while also considering the process’s economic feasibility.The results indicate that increasing the reaction temperature from 360℃ to 390℃ significantly favors the production of BTX,with yields increasing from 21.42%to 41.14%.Similarly,an increase in hydrogen pressure from 4 MPa to 6 MPa boosts BTX production,with yields rising from 36.31%to 41.14%.Reducing the space velocity from 2 h^(-1) to 0.5 h^(-1) also favors the BTX production process,with yields increasing from 37.96%to 45.13%.Furthermore,raising the hydrogen-to-oil volume ratio from 750 to 1500 improves BTX yields from 41.61%to 45.44%.Through economic analysis,the optimal conditions for BTX production were identified as a reaction temperature of 390℃,hydrogen pressure of 5-6 MPa,space velocity of 1 h^(-1),and hydrogen-to-oil volume ratio of 1000,achieving a BTX yield of 43.73%.This investigation highlights the importance of a holistic evaluation of hydrocracking conditions to optimize BTX production.Furthermore,the findings offer valuable insights for the design and operation of industrial hydrocracking processes aimed at efficiently converting coal tar-derived hydrorefined feedstock into BTX.

Analysis of the Erosion-Corrosion Mechanism of the Air Cooler in a Hydrocracking Unit:A Numerical and Experimental Study

Corrosion leakages often occur in the air cooler of a hydrocracking unit,with the failure sites mainly located in the entrance area of the tubes.An analysis of the macroscopic morphology and corrosion products confirmed that the damage was caused by erosion-corrosion(E-C).Numerical and experimental methods were applied to investigate the E-C mechanism in the air cooler.Computational fluid dynamics(CFD)was used to calculate the hydrodynamic parameters of the air cooler.The results showed that there was a biased flow in the air cooler,which led to a significant increase in velocity,turbulent kinetic energy and wall shear within 0.2 m of the tube entrance.A visualization experiment was then performed to determine the principles of migration and transformation of multiphase flow in the air cooler tubes.Various flow patterns(pure droplet flow,mist flow,and annular flow)and their evolutionary processes were clearly depicted experimentally.The initiation mechanism and processes leading to the development of E-C in the air cooler were also determined.This study provided a comprehensive explanation for the E-C failures that occur in air coolers during operation.

Application of Acid Modified Catalysts with Different SiO_(2) Contents in the Hydrocracking of Light Cycle Oil for Light Aromatics Production

A series of functionalized USY/SiO_(2) zeolite composite supports were synthesized using the coating coprecipitation method,with tetraethyl orthosilicate(TEOS)as the silicon source and different ratios of USY to TEOS.Active metals nickel(Ni)and molybdenum(Mo)were loaded onto the supports using the impregnation method.Finally,a series of hydrogenation catalysts were synthesized.The characterization results showed that,compared with the USY catalyst,the addition of a certain quantity of SiO_(2) resulted in the disappearance of the strong acid sites on the catalyst,the number of weak acid and medium strong acid sites decreased,and a certain number of secondary mesoporous structures were formed.The addition of SiO_(2) reduced the secondary cracking of benzene,toluene,xylene,and ethylbenzene(BTXE)effectively,while excessive amounts of SiO_(2) reduced the hydrogenation activity of the catalyst,leading to a decline in the final yield of BTXE.At a maximum SiO_(2) content of 45%,the hydrogenation depth of light cycle oil(LCO)reached an optimum value.The hydrogenation performance of LCO was investigated in a fixed bed reactor at 380℃,4 MPa,and H2/oil volume ratio of 800:1,where the gasoline and diesel fractions reached 80.00%and 16.74%,respectively.NiMo-YS45 had the highest BTXE selectivity,and the final yield of BTXE reached 21.27%.

Development and Performance Evaluation of Catalyst for Productive Ethylene Cracking Feedstock in Selective Hydrocracking of Straight Run Diesel Oil

The upgrading of diesel oil to produce ethylene rich cracking feedstock is an important and promising technical route to reduce the ratio of diesel to gasoline. In the present work, a hydrocracking catalyst suitable for selective hydrocracking of straight run diesel oil to produce high-quality ethylene cracking feedstock at low cost was developed, by optimizing the composition of catalyst support materials, using amorphous silicon aluminum and aluminum oxide with high mesopore content as the main support, and modified Y zeolite with excellent aromatic ring opening selectivity as the acidic component. The catalyst has in-depth characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2-low temperature adsorption-desorption, NH3-temperature-programmed desorption, and IR techniques. And its catalytic cracking straight run diesel oil performance was evaluated. The results show that the prepared catalyst has high polycyclic aromatic hydrocarbon ring opening cracking selectivity. However, alkanes retained in diesel distillates can achieve the goal of producing more ethylene cracking feedstocks with low BMCI value under low and moderate pressure conditions. This work may shed significant technical insight for oil refining transformation.

Impacts of support properties on the vacuum residue slurry-phase hydrocracking performance of Mo catalysts

To deeply understand the effects of support properties on the performance of Mo-based slurry-phase hydrocracking catalysts,four Mo-based catalysts supported on amorphous silica alumina(ASA),γ-Al_(2)O_(3),ultra-stable Y(USY)zeolite and SiO_(2) were prepared by the incipient wetness impregnation method,respectively,and their catalytic performances were compared in the vacuum residue(VR)hydrocracking process.It is found that the Mo/ASA catalyst exhibits the highest VR conversion among the different catalysts,indicating that both the appropriate amount of acid sites,especially B acid sites and larger mesoporous volume of ASA can enhance the VR hydrocracking into light distillates.Furthermore,Mo catalysts supported on the different supports show quite different product distributions in VR hydrocracking.The Mo/ASA catalyst provides higher yields of naphtha and middle distillates and lower yields of gas and coke compared with other catalysts,it is attributed to the highest MoS_(2) slab dispersion,the highest sulfuration degree of Mo species,and the most Mo atoms located at the edge sites for the Mo/ASA catalyst,as observed by HRTEM and XPS analyses.These features of Mo/ASA are beneficial for the hydrogenation of intermediate products and polycyclic aromatic hydrocarbons to restrict the gas and coke formation.

Effect of Catalyst Properties on Hydrocracking of Pyrolytic Lignin to Liquid Fuel in Supercritical Ethanol

The metal-acid bifunctional catalysts have been used for bio-oil upgrading and pyrolytic lignin hydrocracking. In this work, the effects of the metal-acid bifunctional catalyst prop- erties, including acidity, pore size and supported metal on hydrocracking of pyrolytic lignin in supercritical ethanol and hydrogen were investigated at 260 ℃. A series of catalysts were prepared and characterized by BET, XRD, and NHa-TPD techniques. The results showed that enhancing the acidity of the catalyst without metal can promote pyrolytic lignin poly- merization to form more solid and condensation to produce more water. The pore size of microporous catalyst was smaller than mesoporous catalyst. Together with strong acid- ity, it caused pyrolytic lignin further hydrocrack to numerous gas. Introducing Ru into acidic catalysts promoted pyrolytic lignin hydrocracking and inhibited the polymerization and condensation, which caused the yield of pyrolytic lignin liquefaction product to increase significantly. Therefore, bifunctional catalyst with high hydrocracking activity metal Ru supported on materials with acidic sites and mesopores was imperative to get satisfactory results for the conversion of pyrolytic lignin to liquid products under supercritical conditions and hydrogen atmosphere.

Selective hydrocracking of light cycle oil into high-octane gasoline over bi-functional catalysts

Light cycle oil(LCO) with high content of poly-aromatics was difficult to upgrade and convert,which had hindered upgrading fuel quality to meet with the standard of automotive diesel for the purpose of sustainable development.The hydrocracking behaviors of typical aromatics in LCO of naphthalene and tetralin were investigated over NiMo and CoMo catalysts.Several characterization methods including N2-adsoprtion and desorption,ammonia temperature-programmed desorption(NH3-TPD),Pyridine infrared spectroscopy(Py-IR),CO infrared spectroscopy(CO-IR),Raman and X-ray photoelectron spectroscopy(XPS) were applied to determine the properties of different catalysts.The results showed that CoMo catalyst with high concentration of S-edges could hydrosaturate more naphthalene to tetralin but exhibit lower yield of high-value light aromatics(carbon numbers less than 10) than NiMo catalyst.NiMo catalyst with high concentration of Mo-edges also presented a higher selectivity of converting naphthalene into cyclanes than CoMo catalyst.Subsequently,the naphthalene and LCO hydrocracking performances were also investigated over different catalysts systems.The activity evaluation and kinetic analysis results showed that the naphthalene hydrocracking conversion and the yield of light aromatics for CoMo-AY/NiMo-AY grading catalysts were higher than NiMo-AY/CoMo-AY grading catalysts at same condition.A stepwise reaction principle was proposed to explain the high efficiency of CoMo-AY/NiMoAY grading catalysts.Finally,the LCO hydrocracking evaluation results confirmed that CoMo-AY/NiMoAY catalysts grading system with low carbon deposition and high stability could remain high percentage of active phases,which was more efficient to convert LCO to high-octane gasoline.

Hydrocracking diversity in n-dodecane isomerization on Pt/ZSM-22 and Pt/ZSM-23 catalysts and their catalytic performance for hydrodewaxing of lube base oil

Nobel metallic Pt/ZSM-22 and Pt/ZSM-23 catalysts were prepared for hydroisomerization of normal dodecane and hydrodewaxing of heavy waxy lube base oil.The hydroisomerization performance of n-dodecane indicated that the Pt/ZSM-23 catalyst preferred to crack the C-C bond near the middle of n-dodecane chain,while the Pt/ZSM-22 catalyst was favorable for breaking the carbon chain near the end of n-dodecane.As a result,more than 2%of light products(gas plus naphtha)and3%more of heavy lube base oil with low-pour point and high viscosity index were produced on Pt/ZSM-22 than those on Pt/ZSM-23 while using the heavy waxy vacuum distillate oil as feedstock.

Development and Application of Hydrocracking Catalysts RHC-1/RHC-5 for Maximizing High Quality Chemical Raw Materials Yield

To adapt to the change in the demand of the oil refining market,two hydrocracking catalysts,RHC-1 and RHC-5,were developed to improve the quality of tail oil.The catalysts were designed based on the theory of selective ring-opening.By selecting more acidic molecular sieves,the problem of poor selectivity of conventional materials can be solved to properly match up to the hydrogenation performance of catalysts.Compared with the performance of previous catalysts,the quality of the tail oil achieved by the said catalysts is better,and the BMCI is reduced by 1—2 units.In the long cycle operation of the petroleum industry,the good quality of the tail oil has been verified and the adaptability of the process conditions is good.When the RHC-1 catalyst is used to process heavy feed under medium pressure,a BMCI value of about12 can be obtained along with a nearly 60%yield of tail oil.The total yield of chemical raw material(steaming cracking feed+catalytic reforming feed)can exceed 80%,and the hydrogen consumption has dropped by nearly 50%as compared to the conventional hydrocracking conversion rate.When processing a mixed CGO and VGO feed with the full conversion mode under a hydrogen pressure of 13.0 MPa,the RHC-5 catalyst can yield about 68.4%of heavy naphtha with a potential aromatic content of up to 50.6,while the total yield of chemical raw materials can reach more than 98%.The results of industrial application of these catalysts show that more than 30%of high quality tail oil can be obtained via processing of inferior quality feed,and its BMCI value can reach 10.7.The total yield of chemical raw materials can reach more than65%.The industrial operation process has implemented two operating cycles totaling 8 years.

Effect of preparation methods on the hydrocracking performance of NiMo/Al_(2)O_(3) catalysts

In this work,NiMo catalysts with various contents of MoO_(3)were prepared through incipient wetness impregnation by a twostep method(NMxA)and onepot method(NMxB).The catalysts were then characterized by XRD,XPS,NH3TPD,H_(2)TPR,HRTEM,and N_(2)adsorptiondesorption technologies.The performance of the NiMo/Al_(2)O_(3) catalysts was investigated by hydrocracking lowtemperature coal tar.When the MoO3 content was 15 wt%,the interaction between Ni species and Al_(2)O_(3) on the NM15B catalyst was stronger than that on the NM15A catalyst,resulting in the poor performance of the former.When the MoO^(3) content was 20 wt%,MoO_(3) agglomerated on the surface of the NM20A catalyst,leading to decreased number of active sites and specific surface area and reduced catalytic performance.The increase in the number of MoS_(2) stack layers strengthened the interaction between Ni and Mo species of the NM20B catalyst and consequently improved its catalytic performance.When the MoO_(3) content reached 25 wt%,the active metals agglomerated on the surface of the NiMo catalysts,thereby directly decreasing the number of active sites.In conclusion,the twostep method is suitable for preparing catalysts with large pore diameter and low MoO_(3) content loading,and the onepot method is more appropriate for preparing catalysts with large specific surface area and high MoO_(3) content.Moreover,the NMxA catalysts had larger average pore diameter than the NMxB catalysts and exhibited improved desulfurization performance.

光学体表成像设备Catalyst的故障维修案例及日常保养方法

本文介绍了光学体表成像设备Catalyst HD的工作原理,以及处理常见的硬件和软件故障的方法,并提供了日常维护保养方法。其中,对于硬件故障,利用Catalyst HD系统的MutilZsn软件来判断Catalyst投影器和摄像头故障,对于软件故障方面,探讨了Catalyst HD系统在医用直线加速器上常见的Authorization Pending联锁问题的触发原因。本文为科室更好地开展光学体表引导放疗技术,高效地运用好设备提供参考意见。

Surface dealuminated Beta zeolites supported WO3 catalyst and its catalytic performance in tetralin hydrocracking

In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeolites with acid treatment.Hydrocracking catalysts were prepared by loading WO_(3)onto these dealuminated Beta zeolites.It was shown that the surface SiO_(2)/Al_(2)O_(3)of selectively dealuminated Beta zeolites was higher than that of conventionally dealuminated samples for the same bulk SiO_(2)/Al_(2)O_(3),and the hydrogenation activity of the catalyst of the selectively dealuminated Beta zeolites was lower than that of conventionally dealuminated Beta zeolites.The experimental results for tetralin hydrocracking to BTX showed that the catalysts based on the selectively dealuminated Beta zeolites had higher BTX selectivity and lower coke formation rate than that the catalysts based on the conventionally dealuminated Beta zeolites.

Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Catalytic effect in lithium metal batteries: From heterogeneous catalyst to homogenous catalyst

Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.

Development of Light Cycle Oil(LCO) Hydrocracking Technology over a Commercial W-Ni Based Catalyst

Because of its high density and low cetane number, the light cycle oil(LCO) containing heavy aromatics(60%—80%) can hardly be transformed through the conventional hydro-upgrading technology. In this report, a novel LCO hydrocracking technology(FD2G) was proposed for the utilization of LCO to manufacture high value-added products. Through the ingenious combination of hydroprocessing catalyst and the hydrocracking process, the high octane gasoline and the ultra-low sulfur diesel(ULSD) blendstocks were produced simultaneously. The influence of catalyst type, reaction temperature, pressure, respectively, on the research octane number(RON) of produced gasoline was studied in a fixed bed hydrogenation reactor. It indicated that high reaction temperature and medium pressure would favor the production of highoctane gasoline through the conversion of bi-aromatic and tri-aromatic hydrocarbons. The typical results of FD2 G technology on commercial units showed that it could produce clean diesel with a sulfur content of less than 10 μg/g and clean gasoline with a research octane number(RON) of up to 92. It would be contributed to the achievement of the maximum profit of a refinery, the FD2 G technology could provide a higher economic efficiency than the other diesel quality upgrading technology under the current gasoline and diesel price system.

Tetralin Hydrocracking Reaction Network to Single-Ring Aromatics on Bifunctional Catalysts

Conversion of LCO(light cycle oil)to BTX(benzene,toluene,and xylene)is an economically valuable method for refineries.However,this approach still faces difficulties as the main reactions are not clearly understood.Here we study the detailed hydrocracking pathway of typical reactants,1-methylnaphthalene and tetralin,through molecular simulations and experiments to improve our understanding of the conversion process of LCO to BTX.Molecular simulations demonstrate that the rate-determining step is the isomerization pathway of six-membered ring to five-membered ring in tetralin as its activation energy(ΔEa)is the highest among all the reactions and the order ofΔEa of reactions is isomerization>ring-opening≈side-chain cleavage.The results of experiments show that with the increase in reaction depth,i.e.,through a high temperature(350-370℃)and low LHSV(4.5-6.0 h^(−1)),isomerization,ring-opening,and side-chain cleavage reactions occurred,thus improving the selectivity and yield of alkyl aromatics.

p-d Orbital Hybridization Engineered Single-Atom Catalyst for Electrocatalytic Ammonia Synthesis

The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.

Optimizing high-coordination shell of Co-based single-atom catalysts for efficient ORR and zinc-air batteries

Atom-level modulation of the coordination environment for single-atom catalysts(SACs)is considered as an effective strategy for elevating the catalytic performance.For the MNxsite,breaking the symmetrical geometry and charge distribution by introducing relatively weak electronegative atoms into the first/second shell is an efficient way,but it remains challenging for elucidating the underlying mechanism of interaction.Herein,a practical strategy was reported to rationally design single cobalt atoms coordinated with both phosphorus and nitrogen atoms in a hierarchically porous carbon derived from metal-organic frameworks.X-ray absorption spectrum reveals that atomically dispersed Co sites are coordinated with four N atoms in the first shell and varying numbers of P atoms in the second shell(denoted as Co-N/P-C).The prepared catalyst exhibits excellent oxygen reduction reaction(ORR)activity as well as zinc-air battery performance.The introduction of P atoms in the Co-SACs weakens the interaction between Co and N,significantly promoting the adsorption process of ^(*)OOH,resulting in the acceleration of reaction kinetics and reduction of thermodynamic barrier,responsible for the increased intrinsic activity.Our discovery provides insights into an ultimate design of single-atom catalysts with adjustable electrocatalytic activities for efficient electrochemical energy conversion.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.