Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However...Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.展开更多
Ce-encapsulated Beta zeolite was synthesized by a one-pot hydrothermal method with citric acid complexing Ce in the absence of Na species.Additional citric acid can effectively prevent the deposition of Ce species dur...Ce-encapsulated Beta zeolite was synthesized by a one-pot hydrothermal method with citric acid complexing Ce in the absence of Na species.Additional citric acid can effectively prevent the deposition of Ce species during the hydrothermal synthesis of zeolites,leading to uniform distribution of Ce cluster in the framework of Beta zeolites.Moreover,the sodium-free synthesis system resulted that the Brønsted acid sites were mainly located on the straight channels and external surface of Beta zeolites,improving the utilization of Brønsted acid sites.In addition,Ce encapsulated Beta zeolites showed enhanced activity and robust stability in the alkylation of benzene with 1-dodecene based on the synergistic effect between Ce species and Brønsted acid sites,which pave the way for its practical application in the production of alkylbenzene.展开更多
Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive...Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.展开更多
Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to uti...Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.展开更多
Light olefins are important organic building blocks in the chemicals industry.The main low-carbon olefin production methods,such as catalytic cracking and steam cracking,have considerable room for improvement in their...Light olefins are important organic building blocks in the chemicals industry.The main low-carbon olefin production methods,such as catalytic cracking and steam cracking,have considerable room for improvement in their utilization of hydrocarbons.This review provides a thorough overview of recent studies on catalytic cracking,steam cracking,and the conversion of crude oil processes.To maximize the production of light olefins and reduce carbon emissions,the perceived benefits of various technologies are examined.Taking olefin generation and conversion as a link to expand upstream and downstream processes,a targeted catalytic cracking to olefins(TCO)process is proposed to meet current demands for the transformation of oil refining into chemical production.The main innovations of this process include a multiple feedstock supply,the development of medium-sized catalysts,and a diameter-transformed fluidizedbed reactor with different feeding schemes.In combination with other chemical processes,TCO is expected to play a critical role in enabling petroleum refining and chemical processes to achieve low carbon dioxide emissions.展开更多
CO_(2)hydrogenation has been considered to be a highly promising route for the production of high-value olefins(HVOs)while also mitigating CO_(2)emissions.However,it is challenging to achieve high selectivity and main...CO_(2)hydrogenation has been considered to be a highly promising route for the production of high-value olefins(HVOs)while also mitigating CO_(2)emissions.However,it is challenging to achieve high selectivity and maintain stable performance for HVOs(ethylene,propylene,and linear a-olefins)over a prolonged reaction time due to the difficulty in precise control of carbon coupling and rapid catalyst deactivation.Herein,we present a selective Ba and Na co-modified Fe catalyst enriched with Fe_(5)C_(2)and Fe_(3)C active sites that can boost HVO synthesis with up to 66.1%selectivity at an average CO_(2)conversion of 38%for over 500 h.Compared to traditional NaFe catalyst,the combined effect of Ba and Na additives in the NaBaFe-0.5 catalyst suppressed excess oxidation of FeCxsites by H_(2)O.The absence of Fe3O4phase in the spent NaBaFe-0.5 catalyst reflects the stabilization effect of the co-modifiers on the FeCxsites.This study provides a strategy to design Fe-based catalysts that can be scaled up for the stable synthesis of HVOs from CO_(2)hydrogenation.展开更多
Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the c...Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the corresponding catalyst,developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks.However,owing to the continuing degradation of feedstocks,the original catalyst can no longer maintain its activity.Herein,we describe the rational design of the new catalyst,Epylene,from a new metal-modified hierarchical ZSM-5 zeolite and matrix.Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company.A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst.The properties of the feedstocks and the operating conditions in both runs were similar.The light olefin yield was increased from 33.95%to 36.50%and the coke yield was only 9.58%in the test run,which was lower than that in the base run.展开更多
CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly...CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.展开更多
To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent flu...To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.展开更多
When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilizatio...When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.展开更多
Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}wit...Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}with long carbon chain and biquaternary ammonium cation.Cyclohexene could be epoxidized to cyclohexene oxide in 96.3%conversion and 98.2%selectivity.The catalyst type,solvent type,catalyst loading,initial molar ratio,temperature,cycle performance and substrate extensibility were studied and optimized,the kinetic parameters about overall reaction and unit reaction were also calculated.Dynamic light scattering analysis was carried out to explain the different catalytic performance between catalysts with different carbon chain length.This novel catalyst and the corresponding dynamics and mechanism study could probably help the industrial application on the epoxidation of cyclohexene with H_(2)O_(2).展开更多
A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an...A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an ultradilute solution. Extensive characterization techniques, including XRD, TEM, N_(2) adsorption-desorption, NH_(3)-TPD, and IR measurements, confirmed the successful coating of a microporous ZSM-5 core with a mesoporous MCM-41 shell layer and were further employed to explore the textural properties and acidic properties of the samples. The hexane cracking results revealed a significant enhancement in olefin yields after introducing the MCM-41 shell to ZSM-5. Interestingly, a volcanic trend in olefin yields was observed with the increase in the shell thickness. In particular, the highest olefin yield of 51.5%, exceeding that of the core catalyst by 17.1%, was achieved when the shell thickness was controlled at 40 nm.Moreover, the catalyst lifetime investigation revealed that the core-shell composite catalyst exhibited a minimal reduction in hexane conversion of merely 3.8% over a 120 h reaction period, significantly outperforming the 11.3% reduction exhibited by the core catalyst. This remarkable catalytic performance was attributed to the passivation of external acid sites and the introduction of more developed pore channels by the shell, which effectively mitigated unwanted side reactions. The successful synthesis of these core-shell structured catalysts presents a novel strategy for improving catalytic performance in hexane cracking, in addition to serving as a solid foundation for the design of industrial catalysts for light naphtha cracking.展开更多
The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is prop...The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.展开更多
Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 ...The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.展开更多
The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure(morphology, shape,...The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure(morphology, shape, size, texture, and surface structure) and surface chemistry(elemental components and chemical states). The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation(ODH) and direct dehydrogenation(DDH) of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.展开更多
The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction a...The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes: (i) Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.(ii) The transition states were formed. The energy di?erence between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.展开更多
NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether (DME) conversion to light olefins (DTO). The processes of two-stage light olefin production, DME synthesis and the f...NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether (DME) conversion to light olefins (DTO). The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas (H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%) with low H/C ratio of 1.0 was used as feed gas.展开更多
基金the financial support from the Strategic Priority Research Program of Chinese Academy of Sciences(XDA21010100)。
文摘Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.
基金supported by the National Natural Science Foundation of China(22278090,21978055)Natural Science Foundation of Guangdong Province,China(2022A1515012088)the Science and Technology Planning Project of Guangdong Province,China(2022A0505030073,2022A0505030013).
文摘Ce-encapsulated Beta zeolite was synthesized by a one-pot hydrothermal method with citric acid complexing Ce in the absence of Na species.Additional citric acid can effectively prevent the deposition of Ce species during the hydrothermal synthesis of zeolites,leading to uniform distribution of Ce cluster in the framework of Beta zeolites.Moreover,the sodium-free synthesis system resulted that the Brønsted acid sites were mainly located on the straight channels and external surface of Beta zeolites,improving the utilization of Brønsted acid sites.In addition,Ce encapsulated Beta zeolites showed enhanced activity and robust stability in the alkylation of benzene with 1-dodecene based on the synergistic effect between Ce species and Brønsted acid sites,which pave the way for its practical application in the production of alkylbenzene.
文摘Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.
基金the National Natural Science Foundation of China-Outstanding Youth Foundation (No. 22322814)the National Natural Science Foundation of China (No. 22108144)the Natural Science Foundation of Shandong-Outstanding Youth Foundation (No. ZR2023YQ017)。
文摘Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.
基金financially supported by a research grant from the National Key Research and Development Program of China(2021YFA1501204)China Petroleum and Chemical Corporation(Sinopec Corp.),China(ST22001)。
文摘Light olefins are important organic building blocks in the chemicals industry.The main low-carbon olefin production methods,such as catalytic cracking and steam cracking,have considerable room for improvement in their utilization of hydrocarbons.This review provides a thorough overview of recent studies on catalytic cracking,steam cracking,and the conversion of crude oil processes.To maximize the production of light olefins and reduce carbon emissions,the perceived benefits of various technologies are examined.Taking olefin generation and conversion as a link to expand upstream and downstream processes,a targeted catalytic cracking to olefins(TCO)process is proposed to meet current demands for the transformation of oil refining into chemical production.The main innovations of this process include a multiple feedstock supply,the development of medium-sized catalysts,and a diameter-transformed fluidizedbed reactor with different feeding schemes.In combination with other chemical processes,TCO is expected to play a critical role in enabling petroleum refining and chemical processes to achieve low carbon dioxide emissions.
基金supported by the National Natural Science Foundation of China(21802138,21773234 and 22078315)the‘‘Transformational Technologies for Clean Energy and Demonstration’’,Strategic Priority Research Program of the Chinese Academy of Sciences(XDA 21090203)+3 种基金the Youth Innovation Promotion Association of Chinese Academy of Sciences(2020189)the Natural Science Foundation of Liaoning Province(2022-MS-027)the Youth Science and Technology Star Project Support Program of Dalian City(2021RQ123),DICP(Grant:DICP I202138)the University of Chinese Academy of Sciences(UCAS)for UCAS Scholarship。
文摘CO_(2)hydrogenation has been considered to be a highly promising route for the production of high-value olefins(HVOs)while also mitigating CO_(2)emissions.However,it is challenging to achieve high selectivity and maintain stable performance for HVOs(ethylene,propylene,and linear a-olefins)over a prolonged reaction time due to the difficulty in precise control of carbon coupling and rapid catalyst deactivation.Herein,we present a selective Ba and Na co-modified Fe catalyst enriched with Fe_(5)C_(2)and Fe_(3)C active sites that can boost HVO synthesis with up to 66.1%selectivity at an average CO_(2)conversion of 38%for over 500 h.Compared to traditional NaFe catalyst,the combined effect of Ba and Na additives in the NaBaFe-0.5 catalyst suppressed excess oxidation of FeCxsites by H_(2)O.The absence of Fe3O4phase in the spent NaBaFe-0.5 catalyst reflects the stabilization effect of the co-modifiers on the FeCxsites.This study provides a strategy to design Fe-based catalysts that can be scaled up for the stable synthesis of HVOs from CO_(2)hydrogenation.
基金This research was financially supported by the National Key R&D Program of China(grant number 2022YFB3504000)the Contract Projects of China Petroleum&Chemical Corporation(SINOPEC Corp.)(grant number ST22005).
文摘Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the corresponding catalyst,developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks.However,owing to the continuing degradation of feedstocks,the original catalyst can no longer maintain its activity.Herein,we describe the rational design of the new catalyst,Epylene,from a new metal-modified hierarchical ZSM-5 zeolite and matrix.Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company.A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst.The properties of the feedstocks and the operating conditions in both runs were similar.The light olefin yield was increased from 33.95%to 36.50%and the coke yield was only 9.58%in the test run,which was lower than that in the base run.
基金financial support from European Union(Interreg FWVL V project PSYCHE)from the French National Research Agency(Multiprobe project,ANR-20-CE42-0007)。
文摘CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.
基金supported by the National Key Research and Development Program of China(2017YFB0602504)the General Program of National Natural Science Foundation of China(22178385).
文摘To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.
基金supported by Program of China National Petroleum Corporation(2020B-20122022zS27)the General Program of National Natural Science Foundation of China(22178385).
文摘When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.
基金supported by Natural Science Foundation of Jiangsu Province(BK20210185)National Natural Science Foundation of China(21776122)。
文摘Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}with long carbon chain and biquaternary ammonium cation.Cyclohexene could be epoxidized to cyclohexene oxide in 96.3%conversion and 98.2%selectivity.The catalyst type,solvent type,catalyst loading,initial molar ratio,temperature,cycle performance and substrate extensibility were studied and optimized,the kinetic parameters about overall reaction and unit reaction were also calculated.Dynamic light scattering analysis was carried out to explain the different catalytic performance between catalysts with different carbon chain length.This novel catalyst and the corresponding dynamics and mechanism study could probably help the industrial application on the epoxidation of cyclohexene with H_(2)O_(2).
基金sponsored financially by the National Natural Science Foundation of China (Grant No. 21776076)the Fundamental Research Funds for the Central Universities (Grant No. JKA01211710)。
文摘A series of core-shell zeolites with a ZSM-5 zeolite core and a MCM-41 shell with varying shell thicknesses were successfully fabricated via a cetyltrimethylammonium bromide(CTAB)-directed sol-gel coating method in an ultradilute solution. Extensive characterization techniques, including XRD, TEM, N_(2) adsorption-desorption, NH_(3)-TPD, and IR measurements, confirmed the successful coating of a microporous ZSM-5 core with a mesoporous MCM-41 shell layer and were further employed to explore the textural properties and acidic properties of the samples. The hexane cracking results revealed a significant enhancement in olefin yields after introducing the MCM-41 shell to ZSM-5. Interestingly, a volcanic trend in olefin yields was observed with the increase in the shell thickness. In particular, the highest olefin yield of 51.5%, exceeding that of the core catalyst by 17.1%, was achieved when the shell thickness was controlled at 40 nm.Moreover, the catalyst lifetime investigation revealed that the core-shell composite catalyst exhibited a minimal reduction in hexane conversion of merely 3.8% over a 120 h reaction period, significantly outperforming the 11.3% reduction exhibited by the core catalyst. This remarkable catalytic performance was attributed to the passivation of external acid sites and the introduction of more developed pore channels by the shell, which effectively mitigated unwanted side reactions. The successful synthesis of these core-shell structured catalysts presents a novel strategy for improving catalytic performance in hexane cracking, in addition to serving as a solid foundation for the design of industrial catalysts for light naphtha cracking.
基金the National Key Research and Development Program(2019YFC1805804)the National Natural Science Foundation of China(22008032)+3 种基金the Guangdong Natural Science Foundation(2022A1515011192)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the China Postdoctoral Science Foundation(2021M691059).
文摘The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
基金Synfuels China Co.Ltd.for the financial and equipments support
文摘The ZSM-5 zeolite with an unusual snowflake-shaped morphology was hydrothermally synthesized for the first time,and compared with common ellipsoidal and boat-like shaped samples.These samples were characterized by N2 adsorption-desorption,X-ray fluorescence spectroscopy,scanning electron microscopy,X-ray diffraction,magic angle spinning nuclear magnetic resonance,temperature-programmed desorption of ammonia,and infrared spectroscopy of pyridine adsorption.The results suggest that the BET surface area and SiO2/Al2O3 ratio of these samples are similar,while the snowflake-shaped ZSM-5 zeolite possesses more of the(101) face,and distortion,dislocation,and asymmetry in the framework,resulting in a larger number of acid sites than the conventional samples.Catalysts for the methanol to olefin(MTO) reaction were prepared by loading Ca on the samples.The snowflake-shaped Ca/ZSM-5 zeolite exhibited excellent selectivity for total light olefin(72%) and propene(39%) in MTO.The catalytic performance influenced by the morphology can be mainly attributed to the snowflake-shaped ZSM-5 zeolite possessing distortion,dislocation,and asymmetry in the framework,and lower diffusion limitation than the conventional samples.
基金supported by the National Natural Science Foundation of China(21276041)the Program for New Century Excellent Talents in University of Ministry of Education of China(NCET-12-0079)+1 种基金the Natural Science Foundation of Liaoning Province(2015020200)the Fundamental Research Funds for the Central Universities(DUT15LK41)~~
文摘The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure(morphology, shape, size, texture, and surface structure) and surface chemistry(elemental components and chemical states). The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation(ODH) and direct dehydrogenation(DDH) of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.
文摘The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as flloes: (i) Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl.(ii) The transition states were formed. The energy di?erence between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.
基金ACKNOWLEDGM ENTS This work was supported by the National Natural Science Foundation of China (No.51006110, No.51276183, and No.51036006), the National Natural Research Foundation of China/Japan Science and Technology Agency (No.51161140331), and National Key Basic Research Program 973 Project Founded by MOST of China (No.2013CB228105).
文摘NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether (DME) conversion to light olefins (DTO). The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas (H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%) with low H/C ratio of 1.0 was used as feed gas.