Benzene selective hydrogenation over supported Ni (nano-) particles catalysts: Catalytic and kinetics studies

This report aims to reduce the benzene in a mixture of benzene and toluene as a model reaction using catalytic hydrogenation. In this research, we developed a series of catalysts with different supports such as Ni/HMS, Ni/HZSM-5, Ni/HZSM5-HMS, Ni/Al_2O_3 and Ni/SiO_2. Kinetic of this reaction was investigated under various hydrogen and benzene pressures. For more study, two kinetic models have also been selected and tested to describe the kinetics for this reaction. Both used models, the power law and Langmuir–Hinshelwood, provided a good fit toward the experimental data and allowed to determine the kinetic parameters. Among these catalysts, Ni/Al_2O_3 showed the maximum benzene conversion(99.19%) at 130 °C for benzene hydrogenation. The lowest toluene conversion was observed for Ni/SiO_2. Furthermore, this catalyst presented high selectivity to benzene(75.26%)at 130 °C. The catalytic performance(activity, selectivity and stability) and kinetics evaluations were shown that the Ni/SiO_2 is an effective catalyst to hydrogenate benzene. It seems that the surface properties particularly pore size are effective parameter compared to other factors such as acidity and metal dispersion in this process.     

高纯度精馏过程的集成控制与在线优化策略

For high-purity distillation processes, it is difficult to achieve a good direct product quality control using traditional pro-portional-integral-differential (PID) control or multivariable predictive control technique due to some difficulties, such as long re-sponse time, many un-measurable disturbances, and the reliability and precision issues of product quality soft-sensors. In this paper, based on the first principle analysis and dynamic simulation of a distillation process, a new predictive control scheme is proposed by using the split ratio of distillate flow rate to that of bottoms as an essential controlled variable. Correspondingly, a new strategy with integrated control and on-line optimization is developed, which consists of model predictive control of the split ratio, surrogate model based on radial basis function neural network for optimization, and modified differential evolution optimization algorithm. With the strategy, the process achieves its steady state quickly, so more profit can be obtained. The proposed strategy has been successfully applied to a gas separation plant for more than three years, which shows that the strategy is feasible and effective.     

非理想多组分混合物中质量传递过程基于Maxwell-Stefan扩散理论的建模及数值分析(英文)

The Intalox metal tower packing was used to simulate an industrial relevant extractive distillation column for purifying azeotropic multicomponent mixture.In order to explain the inconsistencies in the modeling of transfer process in nonideal multicomponent distillation column,a method was developed with equilibrium stage models(EQ)and non-equilibrium model(NEQ)incorporated with Maxwell-Stefan diffusion equations in the framework of AspenONE  simulator.Dortmund Modified UNIFAC(UNIFAC-DMD)thermodynamic model was employed to estimate activity coefficients.In addition,to understand the reason for the diffusion against driving force and the different results by EQ and NEQ models,explicit investigations were made on diffusion coefficients, component Murphree efficiency and mass transfer coefficients.The results provide valuable information for basic design and applications associated with extractive distillation.     

反应与精馏耦合水解醋酸甲酯(英文)

A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The results show that at the molar ratio of water to methyl acetate about 4.0-5.0 in the feed stream and the volume ratio of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5% (by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process we proposed before, this process can cut down 47.6% energy consumption and a distillation column.     

Process intensification and energy saving of reactive distillation for production of ester compounds

Reactive distillation(RD) process is an innovative hybrid process combining reaction with distillation, which has recently come into sharp focus as a successful case of process intensification. Considered as the most representative case of process intensification, it has been applied for many productions, especially for production of ester compounds. However, such problems existing in the RD system for ester productions are still hard to solve,as the removal of the water which comes from the esterification, and the separation of the azeotropes of ester–alcohol(–water). Many methods have been studying on the process to solve the problems resulting in further intensification and energy saving. In this paper, azeotropic–reactive distillation or entrainer enhanced reactive distillation(ERD) process, reactive extractive distillation(RED) process, the method of co-production in RD process, pressure-swing reactive distillation(PSRD) process, reactive distillation–pervaporation coupled process(RD–PV), are introduced to solve the problems above, so the product(s) can be separated efficiently and the chemical equilibrium can be shifted. Dividing-wall column(DWC) structure and novel methods of loading catalyst are also introduced as the measures to intensify the process and save energy.     

催化精馏塔中乙酸甲酯水解的研究

A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage eiliciencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calcuiations. A good operating mode was then obtained, which is helpful to the development of a new process.     

Study on Hydrolysis of Methyl Acetate in a Catalytic Distillation Column

A nonequilibrium stage model was used to simulate countercurrent multicomponent catalytic distillation processes for methyl acetate hydrolysis. Computations of stage efficiencies or height equivalent to a theoretical plate (HETP) were entirely avoided by this model. The consistency of simulated results and experimental data in conversions and concentration of each component along a column indicates that the model predicts the actual process well. The influences of operating parameters on hydrolytic conversions, such as feed molar ratios, feed locations, feed and reflux rates, heights of reactive and stripping sections, were analyzed adequately by simulating calculations. A good operating mode was then obtained, which is helpful to the development of a new process.     

内部热耦合精馏塔基于非理想物系的最优评价

Internal thermally coupled distillation column(ITCDIC) is a frontier in energy saving distillation research. In this paper, the optimal assessment on the energy saving and the operating cost for ITCDIC of nonideal mixture is explored. An evaluating method is proposed, and the pertinent optimization model is then derived. The ethanol-water system is studied as an illustrative example. The optimization results show that the maximum energy saving in ITCDIC process is about 35% and the maximum operating cost saving in ITCDIC process is about 30%,as compared with a conventional distillation column(CDIC) under the minimum reflux ratio operating; the optimal operating pressure of the rectifying section is found to be around 0.25 MPa; the effects of the feed composition,operating pressure and the heat transfer rate on operation are also found and analyzed. It is revealed that ITCDIC process possesses high energy saving potential and promising economical prospect.     

拟稳态模型用于间歇萃取精馏的数值模拟

Batch extractive distillation (BED) is a special method used in the distillation process by adding a solvent into the batch distillation column to alter the relative volatility of the components and improve the separation. A comprehensive design and simulation method is required due to the complexity of BED. In this study, a quasi-steady-state model for BED is proposed, the derivation and solution of the model are presented. This shortcut model can be used to simulate the composition and temperature of the reboiler, the top and other plates of the column in a batch extractive distillation operation. The calculated values are in good agreement with the experi-mental data. The results show that the quasi-steady-state model is a practical method because of some advantages such as high precision and fast calculation.     

沸石催化环己烯水合的反应精馏过程动力学热力学分析(英文)

Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analy-sis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3 or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allo-cated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation process in comparison with the inert cyclohexane.     

乙烯酮(双乙烯酮)下游产品废水的治理技术

乙烯酮(双乙烯酮)是十分重要的化工中间体,其下游产品较多。江苏某化工厂开发生产乙烯酮(双乙烯酮)下游产品三十多个,年生产规模三万多吨,是国内以乙烯酮(双乙烯酮)为中间体生产精细化学品的综合骨干企业。针对乙烯酮(双乙烯酮)下游产品废水特点,该厂结合企业实际,开展了产品优化,结构调整,清洁生产,资源循环利用,节水降耗等工作,从源头削减了污染物的生产。同时投资二千多万元新建预处理装置三套,6000m3/d废水生化处理装置一套,使全厂乙烯酮(双乙烯酮)下游产品的废水得到了有效的治理。     

Semi-empirical equation of state of metals. Equation of state of aluminum

A semi-empirical equation of state for metals is described. Its capabilities are demonstrated by the example of the equation of state for aluminum. New experimental data are presented on the location of the isentrope of aluminum for unloading from the state at p = 229.71 GPa on the shock adiabat to an aerogel (SiO₂) of density 0.08 g/cm³. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 2, pp. 61–75, March–April, 2008.     

水泥水化热测定方法综述

水泥水化热是中、低热水泥和核电工程用水泥的一项关键的技术指标。全球范围内测定水泥水化热的方法有溶解法、直接法/半绝热法、等温传导量热法三种。本文总结了中、美、欧相关方法标准,对其测试原理、仪器设备、试验过程等方面进行了比对,并对其在领域的应用做了简单的概括。     

几种乙炔加压设备性能的比较

阐述并比较了几种加压设备在乙炔加压清净过程中的性能和特点。     

三种煤样燃烧热的测定

本文通过三个厂家提供的三种煤样燃烧热的测定,由测定结果综合得出3号煤样燃烧最完全、燃烧热也最大,是三个煤样中最好的一种。     

Calorimetric and Computational Study of Enthalpy of Formation of Diperoxide of Cyclohexanone

A thermochemical rather simple experimental technique is applied to determine the enthalpy of formation of Diperoxide of ciclohexanone. The study is complemented with suitable theoretical calculations at the semiempirical and ab initio levels. A particular satisfactory agreement between both ways is found for the ab initio calculation at the 6–311G basis This set level. Some possible extensions of the present procedure are pointed out.     

气化给煤系统故障分析

气化给煤装置自投运以来,出现了气化煤仓堵煤、称重给煤机输送皮带因跑偏而损伤以及清扫装置故障频繁等问题,多次造成气化系统减负荷运行。通过对出现的各种问题进行分析,找到了产生这些问题的原因,并有针对性地采用配煤和改进清扫链等措施,使出现的问题得到了极大的改善。     

小议汽车涂装工艺设计对涂装成本的影响

论述了涂装工艺设计对涂装设备投资、涂装生产成本的影响。     

Measurement of the gradient of viscosity with composition of mixtures of non-ideal gases

A perturbation viscometer is a differential capillary viscometer that measures the logarithmic viscosity gradient of the viscosity-composition curve for gas mixtures. Measurements are made at different gas mixture compositions. Integration of the logarithmic viscosity gradients measured over the full composition range gives the mixture viscosity relative to the viscosity of one of the pure components of the gas mixture. This method is attractive because, for measurements of equal precision, integration of the gradients is potentially an order of magnitude more precise than measurement of the viscosities directly. It can also work at high and low temperatures and perhaps high pressures.The perturbation viscometer has been used to make measurements on ideal gas mixtures at ambient and elevated temperatures. The situation is more complicated when the gas mixtures are non-ideal. Extra effects due to density differences, molar volume change on mixing and differential thermal expansion may be measured in addition to the desired viscosity change producing systematic errors in the results. Thus, a more sophisticated apparatus is required. The standard perturbation viscometer has been modified to separate out the extra effects to permit measurement of the true change in viscosity. In addition, the theoretical operation of the modified apparatus has been revised to account for the design changes to permit calculation of the viscosity-composition profiles from the results.The apparatus has been tested using helium-HFC-125 mixtures and two new viscosity-composition profiles are presented for these mixtures at 23 and . Internal consistency tests have been used to confirm that the data produced are of high quality with an estimated uncertainty in the viscosity ratio data at of 0.9% and at of 1.5%.     

醋酸纤维素取代基分布与性质的关系

分析了以吡啶为溶剂的醋酸纤维素的13C-NMR核磁共振谱,得出了三种不同位置羟基的取代度。结合X—射线和DSC分析,初步说明具有相同取代度但未经水解和经过水解的醋酸纤维素(CA) 性质上的差异是由于三个羟基上的取代度分布不同及消晶程度差异所致。