Recent advances in technologies of reactive distillation(RD) offer various design concepts for chemical processes.For separation of cracking C5 fraction, one of the main challenges is improving the conversion of cyclo...Recent advances in technologies of reactive distillation(RD) offer various design concepts for chemical processes.For separation of cracking C5 fraction, one of the main challenges is improving the conversion of cyclopentadiene(CPD) and the recovery of isoprene(IP). In the current work, a novel reactive distillation column with several liquid-holdup regions was designed, since it allows long residence time and provides flexibility for narrowing the efficiency gap between reaction and distillation. By use of Aspen Plus, a corresponding mathematic model was established and verified to be accurate. Following that, comprehensive studies were carried out for the design of liquid-holdup regions position. Details and principles about the separation performance with the liquid-holdup regions were revealed and optimized parameters were determined with 100 theoretical plates,feed position of 35 th plate, and four liquid-holdup regions at 25 th, 60 th, 75 th and 90 th plate. The designed RD column could well meet the technical requirement, and influence of other important factors including residence time, operating pressure and reflux ratio was further investigated.展开更多
Olefin solution polymerization can be used to obtain high-performance polyolefin materials that cannot be obtained via other polymerization processes.Polyolefin elastomers(POE)are a typical example.Due to cost,only a ...Olefin solution polymerization can be used to obtain high-performance polyolefin materials that cannot be obtained via other polymerization processes.Polyolefin elastomers(POE)are a typical example.Due to cost,only a few linear a-olefins(e.g.,1-butene,1-hexene,and 1-octene)are used as comonomers in solution polymerization in industry.However,a-olefin comonomers with other structures may have different effects on polymerization in comparison with common linear ones.Moreover,the properties of the corresponding materials may differ significantly.In this work,copolymers of ethylene with linear and endcyclized a-olefins are synthesized using a metallocene catalyst.The copolymerization of ethylene with linear a-olefins results in a higher turn-over frequency(TOF)and lower incorporation than copolymerization with end-cyclized a-olefins,which may indicate that end-cyclized a-olefins have a higher coordination probability and lower insertion rate.In this reaction,the comonomer is distributed randomly in the polymer chain and efficiently destroys crystallization.End-cyclized a-olefins exhibit a much stronger crystallization destructive capacity(CDC)in the copolymer than linear a-olefins,possibly because linear a-olefins act mainly in the radial direction of the main chain of the polymer,while end-cyclized a-olefins act mainly in the axial direction of the main chain.展开更多
Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partialpressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed ...Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partialpressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed by energydispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The anti-cokingperformance of a mini tube made of a HP40 (25Cr35Ni) alloy was evaluated on a bench scale pyrolysis and coking test unit.The results showed that the surface Fe and Ni content decreased after the oxidation of the two alloys in a low oxygen partialpressure atmosphere. The oxide films were mainly composed of MnCr_(2)O_(4) and Cr_(2)O_(3). The average mass of coke in the minitube with oxide film decreased by 87% relative to that of a tube without an oxide film when the cracking temperature was 900℃. The ethylene, propylene, and butadiene yields in the pyrolysis tests were almost the same for the mini tubes withand without an oxide film. The oxide film on the alloy surface effectively inhibited catalytic filamentous coke formation.An industrial test showed that the run length of the cracking furnace with the in-situ coating technology was significantlyextended.展开更多
According to the present theories of plastic toughening, it is impossible to enhance the toughness, stiffness and/or heat resistance of plastics simultaneously by using rubber. A series of novel nano-rubber particles ...According to the present theories of plastic toughening, it is impossible to enhance the toughness, stiffness and/or heat resistance of plastics simultaneously by using rubber. A series of novel nano-rubber particles (UFPR) were introduced, which were prepared through irradiating common rubber lattices and spray drying them. Epoxies toughened with UFPR showed a much better toughening effect than those with CTBN, and the heat resistance of epoxy was unexpectedly elevated. For polypropylene toughening, UFPR can improve the toughness, stiffness and heat resistance of PP simultaneously. These special toughening effects overcome the deficiencies in rubber toughening technology and are worth further investigating.展开更多
In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including...In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.展开更多
A five-site comprehensive mathematical model was developed to simulate the steady-state behavior of industrial slurry polymerization of ethylene in multistage continuous stirred tank reactors. More specifically, the e...A five-site comprehensive mathematical model was developed to simulate the steady-state behavior of industrial slurry polymerization of ethylene in multistage continuous stirred tank reactors. More specifically, the effects of various operating conditions (i.e., inflow rates of catalyst, hydrogen and comonomer) on the molecular structure and properties of polyethylene (i.e.,Mw,Mn, polydispersity index (IPD), melt index, density, etc.) are fully assessed. It is shown that the proposed comprehensive model is capable of simulating the steady-state operation of an industrial slurry stirred tank reactor series. It is demonstrated that changing the catalyst flow rate, changes simultaneously the mean residence-time in both reactors, which plays a significant role on the establishment of polyethylene architecture properties such as molecular mass and IPD. The melt index and density of polyethylene are mainly controlled by hydrogen and comonomer concentration, respectively.展开更多
The oxidation kinetics, surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 °C for 20 h were investigated. The anti-coking performance and resist...The oxidation kinetics, surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 °C for 20 h were investigated. The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit. The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage. The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters, while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels. In the pyrolysis tests, the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere. The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10% of that in the air-H2O atmosphere. The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests, while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere. The ethylene, propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.展开更多
SnO2 hollow spheres and rod bundles were prepared using SnSO4 as raw material and sodium dodecyl benzenesulfonate and poly(vinyl pyrrolidone)as templates at room temperature through oxidation-crystallization of colloi...SnO2 hollow spheres and rod bundles were prepared using SnSO4 as raw material and sodium dodecyl benzenesulfonate and poly(vinyl pyrrolidone)as templates at room temperature through oxidation-crystallization of colloidal spheres in different systems.The products were characterized with X-ray diffractometer,X-ray photoelectron spectrometer,transmission electron microscope and scanning electron microscope.Meanwhile,the catalytic performance of the SnO2 hollow spheres and rod bundles toward CO oxidation was studied.The result indicates that SnO2 hollow spheres with the uniform size exhibit a better catalytic activity toward CO oxidation,suggesting that the morphology of the materials has exerted a noticeable influence on the catalytic performance.展开更多
This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected...This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.展开更多
An accurate and complete geometric model was constructed to simulate the combustion, flow and temperature environment in the radiant section of the steam cracking furnace. Simulation of flow and radiation status has u...An accurate and complete geometric model was constructed to simulate the combustion, flow and temperature environment in the radiant section of the steam cracking furnace. Simulation of flow and radiation status has utilized the standard k-ε model and P1 model. The finite-rate/eddy-dissipation (finite-rate/ED) combustion model and non-premixed combustion model were both used to simulate accurately the combustion and the operation status of the steam cracking furnace. Three different surfaces of the steam cracking furnace were obtained from the simulation, namely:the flue gas temperature field of the entrance surface in long flame burners, the central surface location of tubes, and the crossover section surface. Detailed information on the flue gas temperature and the mass concentration fraction of these different surfaces in the steam cracking furnace can also be obtained by the simulation. This paper analyzed and compared the simulation results with the two combustion models, estimated the operation status of the steam cracking furnace, and reported that the finite-rate/ED model is appropriate to simulate the steam cracking furnace by comparing key simulation data with actual test data. This work has also provided a theoretical basis for simulating and operating the steam cracking furnace.展开更多
Pd-Ag bimetallic alloy nanoparticles were synthesized by the reverse microemulsion method,and then deposited on Al2O3 to form the supported catalyst.The nanoparticles of Pd-Ag and Pd-Ag/Al2O3 samples were characterize...Pd-Ag bimetallic alloy nanoparticles were synthesized by the reverse microemulsion method,and then deposited on Al2O3 to form the supported catalyst.The nanoparticles of Pd-Ag and Pd-Ag/Al2O3 samples were characterized by UV/Vis,HRTEM,EDX,XRD,and XPS.The test results indicated that Pd-Ag bimetallic alloy nanoparticles with a size of about 2 nm and a face-centered cubic(fcc) structure were formed in the measured area of microemulsion.The growth of nanoparticles was effectively limited within the droplet of micoremulsion.TEM image exhibited that the Pd-Ag alloy nanoparticles were well-dispersed on the Al2O3 support.The catalytic performance of various catalysts for selective hydrogenation of acetylene showed that a higher acetylene conversion and selectivity to ethylene upon acetylene hydrogenation was achieved on a nano-sized Pd-Ag bimetallic catalyst with a Pd/Ag alloy supported molar ratio of 1:1.5.展开更多
Li4Si O4 has been regarded as one of the most promising high-temperature CO2 sorbents.However,for practical applications,its CO2sorption kinetics,cycling stability and sorption properties at lower temperatures or lowe...Li4Si O4 has been regarded as one of the most promising high-temperature CO2 sorbents.However,for practical applications,its CO2sorption kinetics,cycling stability and sorption properties at lower temperatures or lower CO2 concentrations have to be improved.In this contribution,four Li4Si O4 sorbents were synthesized from zeolite precursors MCM-41,MCM-48,TS-1,and ZSM-5.The CO2 uptake,cycling stability and the optimal CO2 sorption conditions were investigated.Among the samples,MCM-41-Li4Si O4 showed the best cycling stability at 650°C,with a stable reversible CO2 uptake of 29.1 wt%under 100 vol%CO2 during 20 cycles.But its sorption kinetics and CO2 uptakes at lower temperatures and lower CO2 concentrations need to be improved.We then demonstrated that the sorption kinetics can be improved by modifying the MCM-41 precursor with metals such as Al,Ti,Ca,and Na.The Na-MCM-41-Li4Si O4 sample exhibited the highest sorption rate,and reached the equilibrium sorption capacity close to the theoretical value of 36.7 wt%within 20 min.In addition,we proved that coating the MCM-41-Li4Si O4with Na2CO3and K2CO3can significantly increase the CO2uptakes at lower temperatures(e.g.550℃)and lower CO2concentrations(10–20 vol%).At 550℃ and under 20 vol%CO2,15 wt%K2CO3-MCM-41-Li4Si O4 and 10 wt%Na2CO3-MCM-41-Li4Si O4 sorbents resulted in a CO2 uptake of 32.2 wt%and 34.7 wt%,respectively,which are much higher than that of MCM-41-Li4Si O4(11.8 wt%).These two sorbents also showed good cycling stability.The promoiting mechasnim by alkali carbonate coating was discussed by a doubleshell model.展开更多
Styrene-isoprene-butadiene terpolymer(SIBR)is prepared with styrene(St),isoprene(Ip)and butadiene(Bd)as monomers through molecular design,control of chemical composition and microstructure of polymer.It possesses an e...Styrene-isoprene-butadiene terpolymer(SIBR)is prepared with styrene(St),isoprene(Ip)and butadiene(Bd)as monomers through molecular design,control of chemical composition and microstructure of polymer.It possesses an excellent combination of low rolling resistance and wet skid resistance and could be applied to making high performance tires.展开更多
With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (but...With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (butylene terephthalate) (PBT) blends containing athermotropic LCP. The blend has zero entrance pressure loss, although the LCP has rather largeone. The viscosity curve of the blend lies between those of the LCP and PBT. The crystallizationof PBT is not affected by the presence of the LCP together with no indication oftransesterification between the two ingredients. LCP spheres and ellipsoids with the size of 0. 5--1. 5 μm disperse in PBT matrix uniformly, which is related to the viscosity ratio of the twocomponents.展开更多
In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribu...In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribution of the third composition in two phases plays avery important role in controlling viscosity ratio and particle size. When DOP was used asthe plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduceddue to the transference of DOP into PS phase. When polycaprolactone (PCL) was usedas the plasticizer of PVC in the same blends, the particle size of PVC could be descreasedobviously because PCL does not migrate to PS phase.展开更多
This paper reports the synthesis of methoxyoligo （oxyethylene） methacrylate （MEO<sub>n</sub> , n is the repeating unit number of （CH<sub>2</sub>CH<sub>2</sub>O） in the macromon...This paper reports the synthesis of methoxyoligo （oxyethylene） methacrylate （MEO<sub>n</sub> , n is the repeating unit number of （CH<sub>2</sub>CH<sub>2</sub>O） in the macromonomer）, and its polymerization in different solvents. MEO<sub>n</sub> is prepared through such two independent reactions as （1） anionic polymerization of oxirane initiated by potassium alkoxide and （2） end-capping of methoxy oligo（oxyethylene） by methacrylic group. The n value can be conveniently controlled over the range of 5 ～30 by varying the molar ratio of oxirane to initiator and the molecular weight distribution of MEO<sub>n</sub> be narrowed by increasing reaction time only in step （1）. MEO<sub>n</sub> thus obtained shows a rapid polymerization in water and benzene respectively, and both give water-soluble polymers as long as suitable conditions are used.展开更多
By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was as...By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.展开更多
This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure...This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.展开更多
The title complex,6,6-(3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl)bis(oxy)di-di-benzo[d,f]-[1,3,2] dioxaphosphepine(C52H56O6P2·C6H14,Mr = 881.99),was synthesized,and the structure was determined by X-ray single-cr...The title complex,6,6-(3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl)bis(oxy)di-di-benzo[d,f]-[1,3,2] dioxaphosphepine(C52H56O6P2·C6H14,Mr = 881.99),was synthesized,and the structure was determined by X-ray single-crystal diffraction.The crystal belongs to the orthor-hombic system,space group Pbca,with a = 11.8400(13),b = 25.381(3),c = 34.243(4) ,V = 10290(2)3,Z = 8,Dc = 1.139 g/cm3,μ = 0.131 mm-1,T = 152(2) K,F(000) = 3768,the final R = 0.0773 and wR = 0.1820 for 9721 observed reflections with I > 2σ(I).The neighboring two molecules form a dimmer by face-to-face π…π interactions.展开更多
文摘Recent advances in technologies of reactive distillation(RD) offer various design concepts for chemical processes.For separation of cracking C5 fraction, one of the main challenges is improving the conversion of cyclopentadiene(CPD) and the recovery of isoprene(IP). In the current work, a novel reactive distillation column with several liquid-holdup regions was designed, since it allows long residence time and provides flexibility for narrowing the efficiency gap between reaction and distillation. By use of Aspen Plus, a corresponding mathematic model was established and verified to be accurate. Following that, comprehensive studies were carried out for the design of liquid-holdup regions position. Details and principles about the separation performance with the liquid-holdup regions were revealed and optimized parameters were determined with 100 theoretical plates,feed position of 35 th plate, and four liquid-holdup regions at 25 th, 60 th, 75 th and 90 th plate. The designed RD column could well meet the technical requirement, and influence of other important factors including residence time, operating pressure and reflux ratio was further investigated.
文摘Olefin solution polymerization can be used to obtain high-performance polyolefin materials that cannot be obtained via other polymerization processes.Polyolefin elastomers(POE)are a typical example.Due to cost,only a few linear a-olefins(e.g.,1-butene,1-hexene,and 1-octene)are used as comonomers in solution polymerization in industry.However,a-olefin comonomers with other structures may have different effects on polymerization in comparison with common linear ones.Moreover,the properties of the corresponding materials may differ significantly.In this work,copolymers of ethylene with linear and endcyclized a-olefins are synthesized using a metallocene catalyst.The copolymerization of ethylene with linear a-olefins results in a higher turn-over frequency(TOF)and lower incorporation than copolymerization with end-cyclized a-olefins,which may indicate that end-cyclized a-olefins have a higher coordination probability and lower insertion rate.In this reaction,the comonomer is distributed randomly in the polymer chain and efficiently destroys crystallization.End-cyclized a-olefins exhibit a much stronger crystallization destructive capacity(CDC)in the copolymer than linear a-olefins,possibly because linear a-olefins act mainly in the radial direction of the main chain of the polymer,while end-cyclized a-olefins act mainly in the axial direction of the main chain.
基金the scientific research project of China Petroleum&Chemical Corporation(Grant No.411048).
文摘Anti-coking oxide films were prepared on a 25Cr35Ni and 35Cr45Ni alloy surface under the low oxygen partialpressure atmosphere of a H2-H2O mixture. The composition and phase structure of the oxide films were analyzed by energydispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The anti-cokingperformance of a mini tube made of a HP40 (25Cr35Ni) alloy was evaluated on a bench scale pyrolysis and coking test unit.The results showed that the surface Fe and Ni content decreased after the oxidation of the two alloys in a low oxygen partialpressure atmosphere. The oxide films were mainly composed of MnCr_(2)O_(4) and Cr_(2)O_(3). The average mass of coke in the minitube with oxide film decreased by 87% relative to that of a tube without an oxide film when the cracking temperature was 900℃. The ethylene, propylene, and butadiene yields in the pyrolysis tests were almost the same for the mini tubes withand without an oxide film. The oxide film on the alloy surface effectively inhibited catalytic filamentous coke formation.An industrial test showed that the run length of the cracking furnace with the in-situ coating technology was significantlyextended.
基金This work was financially supported by the Special Funds for Major State Basic Research Projects of China (No. G1999064800).
文摘According to the present theories of plastic toughening, it is impossible to enhance the toughness, stiffness and/or heat resistance of plastics simultaneously by using rubber. A series of novel nano-rubber particles (UFPR) were introduced, which were prepared through irradiating common rubber lattices and spray drying them. Epoxies toughened with UFPR showed a much better toughening effect than those with CTBN, and the heat resistance of epoxy was unexpectedly elevated. For polypropylene toughening, UFPR can improve the toughness, stiffness and heat resistance of PP simultaneously. These special toughening effects overcome the deficiencies in rubber toughening technology and are worth further investigating.
文摘In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.
文摘A five-site comprehensive mathematical model was developed to simulate the steady-state behavior of industrial slurry polymerization of ethylene in multistage continuous stirred tank reactors. More specifically, the effects of various operating conditions (i.e., inflow rates of catalyst, hydrogen and comonomer) on the molecular structure and properties of polyethylene (i.e.,Mw,Mn, polydispersity index (IPD), melt index, density, etc.) are fully assessed. It is shown that the proposed comprehensive model is capable of simulating the steady-state operation of an industrial slurry stirred tank reactor series. It is demonstrated that changing the catalyst flow rate, changes simultaneously the mean residence-time in both reactors, which plays a significant role on the establishment of polyethylene architecture properties such as molecular mass and IPD. The melt index and density of polyethylene are mainly controlled by hydrogen and comonomer concentration, respectively.
基金financially supported by the scientific research project of China Petroleum and Chemical Corporation(No.409075)
文摘The oxidation kinetics, surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 °C for 20 h were investigated. The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit. The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage. The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters, while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels. In the pyrolysis tests, the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere. The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10% of that in the air-H2O atmosphere. The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests, while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere. The ethylene, propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.
文摘SnO2 hollow spheres and rod bundles were prepared using SnSO4 as raw material and sodium dodecyl benzenesulfonate and poly(vinyl pyrrolidone)as templates at room temperature through oxidation-crystallization of colloidal spheres in different systems.The products were characterized with X-ray diffractometer,X-ray photoelectron spectrometer,transmission electron microscope and scanning electron microscope.Meanwhile,the catalytic performance of the SnO2 hollow spheres and rod bundles toward CO oxidation was studied.The result indicates that SnO2 hollow spheres with the uniform size exhibit a better catalytic activity toward CO oxidation,suggesting that the morphology of the materials has exerted a noticeable influence on the catalytic performance.
文摘This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.
基金supported by the technology development fund of China Petroleum & Chemical Corporation (Sinopec 409045)
文摘An accurate and complete geometric model was constructed to simulate the combustion, flow and temperature environment in the radiant section of the steam cracking furnace. Simulation of flow and radiation status has utilized the standard k-ε model and P1 model. The finite-rate/eddy-dissipation (finite-rate/ED) combustion model and non-premixed combustion model were both used to simulate accurately the combustion and the operation status of the steam cracking furnace. Three different surfaces of the steam cracking furnace were obtained from the simulation, namely:the flue gas temperature field of the entrance surface in long flame burners, the central surface location of tubes, and the crossover section surface. Detailed information on the flue gas temperature and the mass concentration fraction of these different surfaces in the steam cracking furnace can also be obtained by the simulation. This paper analyzed and compared the simulation results with the two combustion models, estimated the operation status of the steam cracking furnace, and reported that the finite-rate/ED model is appropriate to simulate the steam cracking furnace by comparing key simulation data with actual test data. This work has also provided a theoretical basis for simulating and operating the steam cracking furnace.
文摘Pd-Ag bimetallic alloy nanoparticles were synthesized by the reverse microemulsion method,and then deposited on Al2O3 to form the supported catalyst.The nanoparticles of Pd-Ag and Pd-Ag/Al2O3 samples were characterized by UV/Vis,HRTEM,EDX,XRD,and XPS.The test results indicated that Pd-Ag bimetallic alloy nanoparticles with a size of about 2 nm and a face-centered cubic(fcc) structure were formed in the measured area of microemulsion.The growth of nanoparticles was effectively limited within the droplet of micoremulsion.TEM image exhibited that the Pd-Ag alloy nanoparticles were well-dispersed on the Al2O3 support.The catalytic performance of various catalysts for selective hydrogenation of acetylene showed that a higher acetylene conversion and selectivity to ethylene upon acetylene hydrogenation was achieved on a nano-sized Pd-Ag bimetallic catalyst with a Pd/Ag alloy supported molar ratio of 1:1.5.
基金supported by the National Natural Science Foundation of China (51622801, 51572029)Beijing Excellent Young Scholar (2015000026833ZK11)the Beijing Natural Science Foundation (2184114)
文摘Li4Si O4 has been regarded as one of the most promising high-temperature CO2 sorbents.However,for practical applications,its CO2sorption kinetics,cycling stability and sorption properties at lower temperatures or lower CO2 concentrations have to be improved.In this contribution,four Li4Si O4 sorbents were synthesized from zeolite precursors MCM-41,MCM-48,TS-1,and ZSM-5.The CO2 uptake,cycling stability and the optimal CO2 sorption conditions were investigated.Among the samples,MCM-41-Li4Si O4 showed the best cycling stability at 650°C,with a stable reversible CO2 uptake of 29.1 wt%under 100 vol%CO2 during 20 cycles.But its sorption kinetics and CO2 uptakes at lower temperatures and lower CO2 concentrations need to be improved.We then demonstrated that the sorption kinetics can be improved by modifying the MCM-41 precursor with metals such as Al,Ti,Ca,and Na.The Na-MCM-41-Li4Si O4 sample exhibited the highest sorption rate,and reached the equilibrium sorption capacity close to the theoretical value of 36.7 wt%within 20 min.In addition,we proved that coating the MCM-41-Li4Si O4with Na2CO3and K2CO3can significantly increase the CO2uptakes at lower temperatures(e.g.550℃)and lower CO2concentrations(10–20 vol%).At 550℃ and under 20 vol%CO2,15 wt%K2CO3-MCM-41-Li4Si O4 and 10 wt%Na2CO3-MCM-41-Li4Si O4 sorbents resulted in a CO2 uptake of 32.2 wt%and 34.7 wt%,respectively,which are much higher than that of MCM-41-Li4Si O4(11.8 wt%).These two sorbents also showed good cycling stability.The promoiting mechasnim by alkali carbonate coating was discussed by a doubleshell model.
基金Supported by China Petrochemical Corporation(409083)
文摘Styrene-isoprene-butadiene terpolymer(SIBR)is prepared with styrene(St),isoprene(Ip)and butadiene(Bd)as monomers through molecular design,control of chemical composition and microstructure of polymer.It possesses an excellent combination of low rolling resistance and wet skid resistance and could be applied to making high performance tires.
基金Supported by the National Natural Science Foundation of China
文摘With the help of differential scanning calorimetry, cone-plate and capillary rheometry andscanning electron microscopy, a research has been conducted on rheological behavior,crystallization and morphology of poly (butylene terephthalate) (PBT) blends containing athermotropic LCP. The blend has zero entrance pressure loss, although the LCP has rather largeone. The viscosity curve of the blend lies between those of the LCP and PBT. The crystallizationof PBT is not affected by the presence of the LCP together with no indication oftransesterification between the two ingredients. LCP spheres and ellipsoids with the size of 0. 5--1. 5 μm disperse in PBT matrix uniformly, which is related to the viscosity ratio of the twocomponents.
文摘In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribution of the third composition in two phases plays avery important role in controlling viscosity ratio and particle size. When DOP was used asthe plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduceddue to the transference of DOP into PS phase. When polycaprolactone (PCL) was usedas the plasticizer of PVC in the same blends, the particle size of PVC could be descreasedobviously because PCL does not migrate to PS phase.
文摘This paper reports the synthesis of methoxyoligo （oxyethylene） methacrylate （MEO<sub>n</sub> , n is the repeating unit number of （CH<sub>2</sub>CH<sub>2</sub>O） in the macromonomer）, and its polymerization in different solvents. MEO<sub>n</sub> is prepared through such two independent reactions as （1） anionic polymerization of oxirane initiated by potassium alkoxide and （2） end-capping of methoxy oligo（oxyethylene） by methacrylic group. The n value can be conveniently controlled over the range of 5 ～30 by varying the molar ratio of oxirane to initiator and the molecular weight distribution of MEO<sub>n</sub> be narrowed by increasing reaction time only in step （1）. MEO<sub>n</sub> thus obtained shows a rapid polymerization in water and benzene respectively, and both give water-soluble polymers as long as suitable conditions are used.
文摘By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.
基金the Sinopec Beijing Research Institute of Chemical Industry for its financial support (No. 5-12ZS0419, 5-10ZS0245, 5-12ZS0270)
文摘This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.
基金supported by the SINOPEC project (G6001-2-11ZS0460)
文摘The title complex,6,6-(3,3,5,5-tetra-tert-butylbiphenyl-2,2-diyl)bis(oxy)di-di-benzo[d,f]-[1,3,2] dioxaphosphepine(C52H56O6P2·C6H14,Mr = 881.99),was synthesized,and the structure was determined by X-ray single-crystal diffraction.The crystal belongs to the orthor-hombic system,space group Pbca,with a = 11.8400(13),b = 25.381(3),c = 34.243(4) ,V = 10290(2)3,Z = 8,Dc = 1.139 g/cm3,μ = 0.131 mm-1,T = 152(2) K,F(000) = 3768,the final R = 0.0773 and wR = 0.1820 for 9721 observed reflections with I > 2σ(I).The neighboring two molecules form a dimmer by face-to-face π…π interactions.
