Process Design for Separating C4 Mixtures by Extractive Distillation

C4 components are useful in industry and should be separated as individuals. A new process was proposed to separate them by extractive distillation, with the advantages of low equipment investment, energy consumption and liquid load in the columns. One principle to improve the extractive distillation process was put forward. Moreover, the analysis of operation state of the new process was done. There were eight operation states found for the whole process, but only one operation state was desirable. This work provides a way to effectively separate C4 mixtures and helps the reasonable utilization of C4 resource.

Oxidative coupling of methane:MO_x-modified (M=Ti,Mg,Ga,Zr) Mn_2O_3-Na_2WO_4/SiO_2 catalysts and effect of MO_x modification

Mn_2O_3-Na_2WO_4/SiO_2 is considered as the most promising catalyst for the oxidative coupling of methane（OCM） process; however, it only has a better catalytic performance over 800 °C. To improve its low-temperature performance, an attempt has been made to modify the Mn_2O_3-Na_2WO_4/SiO_2 catalyst using TiO_2, MgO, Ga_2O_3, and ZrO_2. Among the synthesized catalysts, the TiO_2-modified Mn_2O_3-Na_2WO_4/SiO_2 catalyst shows markedly improved low-temperature OCM performance,achieving a high CH_4 conversion of ~23% and a good C_2-C_3 selectivity of ~73% at 700 °C（the catalyst bed temperature）, along with promising stability for at least 300 h without signs of deactivation.In comparison with the unmodified Mn_2O_3-Na_2WO_4/SiO_2 catalyst, the TiO_2 modification results in significant improvement in the low-temperature activity/selectivity, whereas the MgO modification has almost no impact and the Ga_2O_3 and ZrO_2 modifications have a negative effect. The X-ray diffraction（XRD） and Raman results reveal that the formation of a MnTiO_3 phase and a MnTiO_3-dominated catalyst surface is crucial for the improvement of the low-temperature activity/selectivity in the OCM process.

Ceria in halogen chemistry

Halogen chemistry constitutes an essential part in the industrial production of polymers and gains increasing attention as an attractive strategy to activate light alkanes that constitute natural gas. CeO2-based catalysts offer an exciting potential for advances in hydrogen halide recovery that enables a high efficiency of halogen-based processes for activation of small molecules. This review provides an overview of recently developed ceria-based catalysts in the context of polymer industry(polyvinyl chloride, polyurethanes, and polycarbonates) and activation of light hydrocarbons for natural gas upgrading. In addition, mechanistic insight and the challenges of ceria catalysts are provided, aiding the design of future catalytic materials and applications.

Catalytic Cracking of Cycloparaffins Admixed with Olefins:2. Single-Event Microkinetic(SEMK) Assessment

The developed SEMK model is used to provide an insight into the contribution of individual reactions in the cracking of methylcyclohexane as well as the site coverage by various carbenium ions. The preferred reaction pathways for the conversion of methylcyclohexane are hydride transfer reactions followed by PCP-isomerizations, deprotonation and endocyclic β-scission, accounting for 61%, 22% and 12% of its disappearance, respectively, at 693 K and 30% conversion of methylcyclohexane. Protolysis plays a minor role in the cracking of methylcyclohexane. Once cyclic diolefins are formed, all of them can be instantaneously transformed to aromatics, which are easily interconverted via disproportionation. Judging from the carbenium ion concentrations it is evident that, at the investigated operating conditions, less than 5% of the acid sites are covered by carbenium ions, less than 2% of which corresponds to cyclic type species including allylic ones.

Full life cycle characterization strategies for spatiotemporal evolution of heterogeneous catalysts

The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate reactor.Therefore,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance.This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic technology.Thus far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions.In this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical examples.The research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.

Effects of Light Olefins Formation during Catalytic Pyrolysis of n-Heptane

The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.

Removal of Trace Olefins from Aromatics by Catalytic Alkylation Using 1-Alkyl-3-methylimidazolium Bromochloroaluminate Catalyst

Removal of trace olefins from aromatic liquids had been investigated in the presence of various ionic liquids like 1-ethyl-3-methylimidazoliurn bromochloroaluminate （EMIMBr-AlCl3）, 1-butyl-3-methylimidazolium bromochloroaluminate （BMIMBr-AlCl3）, l-hexyl-3-methylimidazolium bromochloroaluminate （HMIMBr-AlCl3）, and 1-octyl-3-methylimidazolium bromochloroaluminate （OMIMBr-A1C13）. It was found that the longer the alkyl chain of ionic liquid cations was, the higher the olefins conversion would be. OMIMBr-AlCl3 （with 0.67 molar fraction of AlCl3） had an obvious performance on olefins removal. The influences of various reaction parameters such as the dosage of catalyst, the reaction temperature, and the reaction time on the reaction catalyzed by OMIMBr-AlCl3 were investigated. Under optimum reaction conditions, a higher than 99% conversion of olefins was achieved. The preliminary results revealed that the process could save time, consume less energy, separate products easier, and cause less pollution to the environment.

含铁酶催化脂肪酸脱羧制备脂肪烃的微观机理研究进展

能源消耗的增加、化石资源的减少和环境问题对再生能源的研发提出了严峻挑战.近年来,烷/烯烃的生物合成是该领域的研究热点之一.因为脂肪烃类不仅是高值化学品,而且是理想的可再生燃料.人们已相继发现了一些能催化烃类合成的蛋白酶,它们可以催化脂肪酸及其衍生物脱羧生成相应的烷/烯烃,为探索化石燃料的可再生替代品提供了思路.这些蛋白酶主要包括一些含铁酶,它们利用非血红素单核铁、双核铁和血红素铁等催化脂肪酸及其衍生物的脱羧或脱甲酰基反应.本文主要以几类代表性的含铁酶为例,综述了这些酶催化脂肪酸生物合成脂肪烃的最新研究进展,重点回顾理论化学方法对酶催化微观机制的探索.

Copper(I)/Sa BOX catalyzed highly diastereo- and enantio-selective cyclopropanation of cis-1,2-disubstituted olefins with a-nitrodiazoacetates

A copper-catalyzed highly stereoselective cyclopropanation of 1,2-disubstituted olefins with α-nitrodiazo acetates has been developed, giving the desired products in up to 97 % yields, up to 〉99/1 dr and up to 98 % ee, which provides an efficient access to the synthesis of optical active cyclopropane α-amino acids and unnatural α-amino acid derivatives.

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.

When does a diblock copolymer probe the interfacial rheological effect?

Lateral diffusion of diblock copolymer residing on the interfaces between two immiscible liquids is investigated at single molecular level. Fluorescence correlation spectroscopy was used to study the diffusion of fluorescence-labeled diblock copolymer,polystyrene-b-polyisoprene, at the interface formed between two immiscible liquids. The interfaces are formed between N,N-dimethylformamide(DMF) and a few immiscible liquids, n-alkane and polyisoprene. Interfacial diffusion coefficient of the diblock copolymer probe is found to decrease monotonously with the increase of the molecular length of the interface constituting liquids. The decrease of diffusion coefficient follows the prediction by Einstein relation using the viscosity of the constituting liquids as the variables only for interfaces between DMF and very small n-alkanes. For interfaces formed between DMF and bigger alkanes and especially between DMF and polyisoprene, the diffusion coefficient is much higher than the calculated value,indicating that the probe molecule starts to probe the much less viscous interfacial region because the interfacial width gets larger,whose thickness is comparable to the molecule size of the liquids.