Effect of nano-particle size on product distribution and kinetic parameters of Fe/Cu/La catalyst in Fischer-Tropsch synthesis

Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.

Kinetics and product distribution studies on ruthenium-promoted cobalt/alumina Fischer-Tropsch synthesis catalyst

Hydrocarbon production rates and distributions on ruthenium promoted alumina supported cobalt Fischer-Tropsch synthesis （FTS） catalyst were studied by the concept of two superimposed Anderson-Schulz-Flory （ASF） distributions.The results indicated that the characterizing growth probabilities α1 and α2 were strongly dependent on reaction conditions.By increasing the H2 /CO partial pressure ratios and reaction temperatures,deviation from normal ASF distribution decreases and the double-α-ASF distribution changes into a straight line.Based on the concept of double-α-ASF distribution,a useful rate equation for the production of hydrocarbons under industrial reaction conditions is obtained.

Product distributions of Fischer-Tropsch synthesis over Co/AC catalyst

The product distributions of Fischer-Tropsch synthesis over Co/AC catalyst are investigated under different reaction conditions in an integral fixed bed reactor.It is found that the product distributions deviate from the ASF distribution.The deviation from ASF distribution is analyzed by taking the readsorption of alkenes and the following secondary reaction into consideration.It is noted that the contents of alcohol,alkene and alkane decline with the increasing carbon number,showing a slighter declining tendency of alkanes than those of alkenes and alcohols.It is also found that high temperature,space velocity,H2/CO in feed gas and low pressure are preferential for light hydrocarbons and alcohols while against the chain propagation.The effect of space velocity on the product distributions especially on the light products is not obvious.It is noticed that low temperature,space velocity,H2/CO and high pressure lead to high contents of alcohols;high temperature,H2/CO and low space velocity lead to high contents of alkanes.The effect of pressure on the amounts of alkanes is not significant;high space velocity and low temperature,pressure,H2/CO are preferential for alkenes.

Studies on product distribution of alkali promoted iron catalyst in Fischer-Tropsch synthesis

The dependencies of hydrocarbon product distributions of alkali promoted iron catalyst in Fischer-Tropsch synthesis have been studied. The concept of two superimposed Anderson-Schulz-Flory distributions has been applied for the representation of the effects of Mg, La and Ca promoters on product distributions. The FTS performance of the catalysts was tested in a fixed bed reactor under the conditions 563 K, 1.7 MPa, H2/CO = 1 and space velocities 4.86 and 13.28 nl·h^-1·gFe^-1. The results indicate that appropriate amounts of these promoters enhance the break in ASF distributions in the order Ca 〉 Mg 〉 La because of the rising of the catalyst surface basicity.

Mechanical property and deformation mechanism of gold nanowire with non-uniform distribution of twinned boundaries:A molecular dynamics simulation study

The mechanical property and deformation mechanism of twinned gold nanowire with non-uniform distribution of twinned boundaries(TBs)are studied by the molecular dynamics(MD)method.It is found that the twin boundary spacing(TBS)has a great effect on the strength and plasticity of the nanowires with uniform distribution of TBs.And the strength enhances with the decrease of TBS,while its plasticity declines.For the nanowires with non-uniform distribution of TBs,the differences in distribution among different TBSs have little effect on the Young's modulus or strength,and the compromise in strength appears.But the differences have a remarkable effect on the plasticity of twinned gold nanowire.The twinned gold nanowire with higher local symmetry ratio has better plasticity.The initial dislocations always form in the largest TBS and the fracture always appears at or near the twin boundaries adjacent to the smallest TBS.Some simulation results are consistent with the experimental results.

SUPPORTED ZIEGLER-NATTA CATALYSTS FOR ETHYLENE SLURRY POLYMERIZATION AND CONTROL OF MOLECULAR WEIGHT DISTRIBUTION OF POLYETHYLENE

The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-supported catalyst affect of MWD of PE produced in broad range:Vanadium-magnesium catalyst(VMC)produce PE with broad and bimodal MWD(M_w/M_n=14-21).MWD of PE,produced over titanium-magnesium catalyst(TMC)is narrow or medium depending on Ti content in the catalyst(M_w/M_n=3.1-4.8).The oxidation ...

EFFECTS OF EXTERNAL DONOR ON ACTIVE CENTER DISTRIBUTION OF SUPPORTED ZIEGLER-NATTA CATALYST

The composition distribution (CD) and microisotacticity distribution (ID) of propene/1-hexene copolymer synthesized by MgCl2/DIBP/TiCl4 (DIBP: diisobutyl phthalate) were determined by fractionating the copolymers according to crystallinity and characterizing the fractions by (CNMR)-C-13. The effects of two alkoxysilane donors, triethoxyphenylsilane (PTES) and dimethoxydi-tert-butylsilane (TBMS), on CD and ID of the copolymers were compared. Three main parts in the CD diagram of each copolymer were distinguished, which were correlated to active center distribution (ACD) based on three groups of different active centers. By studying the changes in l-hexene content, microisotacticity and reactivity ratio product of three typical fractions, the effects of external donor on ACD were better elucidated. It was found that TBMS shows much stronger effects on ACD than PTES. In the former system, most fractions were produced on active centers with relatively lower r(1)r(2), higher reactivity to I-hexene, and higher stereospecificity as compared to the system without external donor. It is concluded that the observed very extensive changes in ACD are mainly resulted by the formation of new types of active centers, possibly by coordination of external donor to certain positions on the catalyst.

RELOCATION ALGORITHM FOR NON-UNIFORM DISTRIBUTION IN MOBILE SENSOR NETWORK

Energy is the determinant factor for the survival of Mobile Sensor Networks(MSN).Based on the analysis of the energy distribution in this paper,a two-phase relocation algorithm is proposed based on the balance between the energy provision and energy consumption distribution.Our main objectives are to maximize the coverage percentage and to minimize the total distance of node movements.This algorithm is designed to meet the requirement of non-uniform distribution network applications,to extend the lifetime of MSN and to simplify the design of the routing protocol.In ad-dition,test results show the feasibility of our proposed relocation algorithm.

Study on the distribution of active centers in novel low Ti-loading MgCl2-supported Ziegler-Natta catalyst

Novel MgCl2-supported Ziegler-Natta (Z-N) catalysts prepared using a new one-pot ball milling method can effectively control the amounts of Ti-loading in the catalysts. Complex GPC data on polypropylene synthesized by these novel catalysts were analyzed using the method of fitting the molecular weight distribution (MWD) curves with a multiple Flory-Schulz function. It was found that multiple active centers exist in these novel catalysts. Detailed study of the effects of the Ti-loadings in the catalysts on the distribution of the active centers showed that the Ti-loadings in the novel MgCl2-supported Z-N catalysts might affect the proportion of each type of active centers; and might be the main factor responsible for the effect of the Ti-loadings on the microstructure, the molecular weight and molecular weight distribution width of the resultant polymer, the catalytic activity and polymerization kinetics.

Alternative Optimal Activity Distribution to the Classical Optimal Distribution in Catalyst Pellets with Exergy and Entropy Consideration

It is generally recognized that the optimal distribution of catalyst activity in a spherical catalyst is a Dirac d-function. However, catalyst with other alternative distribution may accomplish the same reaction task without necessarily concentrating the catalyst activity in an inside thin layer. Moreover, the alternative with activity on catalyst surface may offer higher reaction rate and better utilization of reaction heat (higher exergy output). Simple cases of first-order exothermal reactions, in particular when the catalyst is limited by the maximum working temperature, are presented to demonstrate the above advantages and to show the importance of studying the optimal activity distribution with the consideration on exergy maximization and entropy production minimization.

Distribution and State of Ni Contaminants on Resid Fluid Catalytic Cracking Catalysts—Characterization by AEM, EPMA, UV-Vis and TPR

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SUPPORTED CATALYST WITHOUT EXTERNAL ELECTRON DONOR FOR PROPYLENE POLYMERIZATION Ⅱ. TACTICITY DISTRIBUTION AND MICROSTRUCTURE OF POLYPROPYLENE

Propylene was polymerized with a novel supported Ziegler-Natta catalystcontaining 2,2-di-iso-butyl-1,3-dimethoxy-propane (DIBDMP) as internal donor and in theabsence of external donor. The tacticity distribution of polypropylene was obtained by usingtemperature rising elution fractionation (TREF) technique and microstructure of fractionswas studied with ^(13)C-NMR. Compared with the catalyst without electron donor, this cat-alyst gives a considerably narrower tacticity distribution. Fractionation data demonstratethat DIBDMP shows better performance than aromatic diester DNBP (di-n-butyl phtha-late). Chemically inverted propylene units and less stereoblockiness are found in the firstfraction. Possible reasons for these were presented.

EFFECT OF Ni CRYSTAL SIZE DISTRIBUTION ON THE ANTICOKING BEHAVIOR OF La-MODIFIED Ni/α-Al_2O_3 CATALYSTS

The crystal size distribution（CSD）was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reactor.The results of this study show that the rate of coking on the supported Ni-catalysts depends main-ly on the percentage content of the large size fraction（25-70nm）of Ni-crystallites,and that the dispersion ofNi-crystallites and the anticoking property of the Ni/α-Al2O3 catalysts were promoted obviously by theLa2O3-modification method.The variation of the Ni-CSD and the anticoking property of the catalysts were fur-ther tested through different periods of hydrothermal treatment.It is found that the content of the largeNi-crystal size fraction and the coking rate pass correspondingly through a maximum.

Improving the Performance of Fixed-Bed Catalytic Reactors by Innovative Catalyst Distribution

A comprehensive mathematical model is developed to simulate the interactions of the complex processes that take place in typical catalytic chemical reactors. This mathematical model includes correlations representing various modes of mass transport and chemical reactions. To illustrate the application and value of this approach for reactor optimizations, the model is applied to the case of series reactions with a desirable intermediate compound and the risk of degradation of this compound if the process conditions are not optimized. The modeling results show that in such cases, which are very common in practice, replacing the conventional uniform catalyst distribution with a novel non-uniform distribution will significantly improve the performance of the reactor and the production of the desirable compound. Various catalyst distribution options are compared, and a novel non-uniform loading of catalyst is identified that gives a much better performance compared to the conventional approach. The model is versatile and useful for both the design as well as the optimization of the catalytic fixed-bed reactors in a wide variety of reactor and reaction conditions.

DEPENDENCE OF THE DISTRIBUTION OF ACTIVE CENTERS ON MONOMER IN SUPPORTED ZIEGLER-NATTA CATALYSTS

Distribution of active centers(ACD)of ethylene or 1-hexene homopolymerization and ethylene-1-hexene copolymerization with a MgCl_2/TiCl_4 type Z-N catalyst were studied by deconvolution of the polymer molecular weight distribution into multiple Flory components.Each Flory component is thought to be formed by a certain type of active center. ACD of ethylene-1-hexene copolymer with very low 1-hexene incorporation was compared with that of ethylene homopolymer to see the effect of introducingα-olefin on ethyle...

Study of the Non-Uniform Distribution of Earthquake Risk Within Potential Sources

Potential sources are aggregates of probable future epicenters.In this area,for source models currently,in common use for seismic risk analysis in China,the mean area of each potential source is about 3000-4000 km2.It is assumed that seismic risk has a uniform distribution within the range of each potential source,but studies have shown that the uniform distribution model to a large extent may give an underestimation of the seismic risk.In this paper,the relative distribution of historical epicenters in space within potential sources is discussed,a method is proposed to quantitatively describe the non-uniform distribution of strong earthquakes within potential sources,and some preliminary results are given.By using the results of this paper,seismic risk analysis and seismic zonation can be made more scientific and more reasonable.

Stress analytical solution for plane problem of a double-layered thick-walled cylinder subjected to a type of non-uniform distributed pressure

The stress state around circular openings,such as boreholes,shafts,and tunnels,is usually needed to be evaluated.Solutions for stresses,strains and ultimate bearing capacities of pressurized hollow cylinder are common cases.Stress analytical method for plane problem of a double-layered thick-walled cylinder subjected to a type of non-uniform pressure on the outer surface and uniform radial pressure on the inner surface is given.The power series method of complex function is used.The stress analytical solution is obtained with the assumption that two layers of a cylinder are fully contacted.The distributions of normal and tangential contact stress along the interface,tangential stress on the inner boundary and stresses in the radial direction at θ=0°,45° and 90°,are obtained.An example indicates that,when the elastic modulus of the inner layer of a double-layered thick-walled cylinder is smaller than that of the outer layer,the tangential stress is smaller than that in the corresponding point for a traditional cylinder composed of homogeneous materials.In that way,stress concentration at the inner surface can be alleviated and the stress distribution is more uniform.This is a capable way to enhance the elastic ultimate bearing capacity of thick-walled cylinder.

Downlink SINR and Rate Distribution of Ultra-Dense Het Nets with Burst Traffic

SINR distribution and rate overage distribution are crucial for optimization of deployment of Ultra-dense Het Nets.Most existing literatures assume that BSs have full queues and full-buffer traffic.In fact,due to ultra-dense deployment of small cells,traffic in small cell varies dramatically in time and space domains.Hence,it is more practical to investigate scenario with burst traffic.In this paper,we consider a two-tier non-uniform ultra-dense Het Net with burst traffic,where macro BSs are located according to Poisson Point Process(PPP),and pico BSs are located according to Poisson Hole Process(PHP).The closed-form expressions of SINR distribution and rate distribution are derived,and then validated through simulation.Our study shows that different from the result of full buffer case,the SINR distribution and rate distribution of users depend on the average transmission probabilities of BSs in burst traffic case.

The Evolution of the Charge Density Distribution Function for Spherically Symmetric System with Zero Initial Conditions

The evolution of the charge density distribution function is simulated for both the case of a uniformly charged sphere with zero initial conditions and for the case of a non-uniform charged sphere. For the case of a uniformly charged sphere the comparison of a numerical result and an exact analytical demonstrated the agreement between the results. The process of “scattering” of a charged system under the influence of its own electric field has been illustrated on the basis of both the particle-in-cell method and the solution of the Cauchy problem for vector functions of the electric field and vector velocity field of a charged medium.

Correlation between hydrocarbon distribution and water-hydrocarbon ratio in Fischer-Tropsch synthesis

In order to shorten the evaluation cycle of cobalt catalyst before the optimized catalyst is fixed on, a mathematical method is proposed to calculate weight percentage of C5＋ hydrocarbons. Based on the carbide polymerization mechanism and the main hydrocarbons being linear alkanes and α-olefins, the correlation between hydrocarbon distribution and the molecular mass ratio of water to hydrocarbons is discussed. The result shows the ratio was within the range of 1.125-1.286 and the lower the ratio, the more gaseous hydrocarbons were obtained. Moreover, a linear equation between the weight percentage of C5＋ hydrocarbons and the weight ratio of C5＋ hydrocarbons to the total water is established. These results are validated by corresponding experiments. The weight percentage of C5＋ hydrocarbons could be immediately calculated by this linear equation without detailed gas chromatography （GC） analysis of them.