Selective oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins with molecular oxygen

This paper reported the oxidation of ethylbenzene catalyzed by fluorinated metalloporphyrins under mild conditions without any additives. The results showed that the cobalt(II)(5,10,15,20-tetrakis(pentafluorophenyl))porphyrin was the best catalyst among the fluorinated metalloporphyrins. The conversion of ethylbenzene reached 38.6%, the selectivity to acetophenone reached 94.0%, and the turnover number is 2719 under the optimal conditions.

Highly selective ethylbenzene production through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% （only benzene feed） and even higher than 99% （benzene plus transalkylation feed）. At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature, 1.6-2.1 MPa of pressure, 3.0-5.5 of benzene/ethylene mole ratio, 4-6 v% of transalkylation feed/（benzene＋transalkylation feed）, 0.19-0.27 h^-1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.

Solvent-free aerobic oxidation of ethylbenzene over supported Ni catalysts using molecular oxygen at atmospheric pressure

We investigated the aerobic oxidation of ethylbenzene in the absence of solvent or any additive carried out over Ni on different types of supports namely SiO2, hydroxyapatite, SBA-15, and USY Zeolites. The oxidation of ethylbenzene activities was measured in a round bottom flask immersed in oil bath at known reaction temperature. The physicochemical characteristics of the catalysts were examined by BET surface area, XRD, FT-IR and the oxidation activities were correlated with the acidities of the catalysts obtained by TPD of NH3. It was observed that both hydroxyapatite and USY （13% Na2O） supported Ni catalysts displayed higher ethylbenzene conversion and 80% selectivity towards acetophenone.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Efficient oxidation of ethylbenzene catalyzed by cobalt zeolitic imidazolate framework ZIF-67 and NHPI

Efficient catalytic oxidation of ethylbenzene to acetophenone was realized using the catalytic system of cobalt zeolitic imidazolate framework ZIF-67/N-hydroxyphthalimide （NHPI） under mild conditions. 95.2% conversion of ethylbenzene with 90.3% selectivity to acetophenone could be obtained at 373 K under 0.3 MPa 02 for 9 h. The results show that there exists synergetic effect between ZIF-67 and NHPI. 1-Phenylethyl hydroperoxide （PEHP） was generated via a radical process involving the hydrogen abstraction from ethylbenzene by phthalimide N-oxyl, and subsequently effectively decomposed to acetophenone by ZIF-67.

Bio-removal of mixture of benzene,toluene,ethylbenzene,and xylenes/total petroleum hydrocarbons/trichloroethylene from contaminated water

Four pure cultures were isolated from soil samples potentially contaminated with gasoline compounds either at a construction site near a gas station in Fai Chi Kei,Macao SAR or in the northern parts of China（Beijing,and Hebei and Shandong）.The effects of different concentrations of benzene,toluene,ethylbenzene,and three isomers（ortho-,meta-,and para-） of xylene（BTEX）,total petroleum hydrocarbons（TPH）,and trichloroethylene（TCE）,when they were present in mixtures,on the bio-removal effciencies of microbial isolates were investigated,together with their interactions during the bio-removal process.When the isolates were tested for the BTEX（50-350 mg/L）/TPH（2000 mg/L） mixture,BTEoX in BTEoX/TPH mixture was shown with higher bio-removal effciencies,while BTEmX in BTEmX/TPH mixture was shown with the lowest,regardless of isolates.The TPH in BTEmX/TPH mixture,on the other hand,were generally shown with higher bio-removal effciencies compared to when TPH mixed with BTEoX and BTEpX.When these BTEX mixtures（at 350 mg/L） were present with TCE（5-50 mg/L）,the stimulatory effect of TCE toward BTEoX bio-removal was observed for BTEoX/TCE mixture,while the inhibitory effect of TCE toward BTEmX for BTEmX/TCE mixture.The bio-removal effciency for TPH was shown lower in TPH（2000 mg/L）/TCE（5-50 mg/L） mixtures compared to TPH present alone,implying the inhibitory effect of TCE toward TPH bio-removal.For the mixture of BTEX（417 mg/L）,TPH（2000 mg/L） along with TCE（5- 50 mg/L）,TCE was shown co-metabolically removed more effciently at 15 mg/L,probably utilizing BTEX and/or TPH as primary substrates.

Disproportionation of ethylbenzene in the presence of C_8 aromatics

The selective synthesis of p-diethylbenzene （p-DEB） by disproportionation of ethylbenzene （EB） in the presence of aromatics like m- and p- xylene isomers has been studied over a pore size regulated HZSM-5 catalyst. The industrial feed having different compositions of ethylbenzene and xylene isomers was used for the experimentation. Hence, they were expected to hinder the movement of reactant molecules both on the external surface and within the zeolite channels. It was observed that irrespective of the different feed compositions the concentration of the xylene isomers was intact in the product. There is no other byproducts formation like para-ethylmethyl benzene. The effects of varying the concentration of aromatic compounds in the feed on ethylbenzene conversion and product distribution over the parent and modified H-ZSM-5 catalyst have been discussed. Ethylbenzene disproportionation reaction follows the pseudo first order reaction with an activation energy of 8.6 kcal/mol.

Influence of Addition of ZnO on Property of Fe_2O_3-K_2O System Catalyst for Ethylbenzene Dehydrogenation to Styrene

The incorporation of ZnO into Fe2O3-K2O system increases its activity, enhances its moisture stability and mechanical strength. The origin of the enhancement in activity and moisture stability is discussed in the light of experimental results obtained by BET, XRD, XPS. It was found that the addition of ZnO to Fe2O3-K2O system strengthens the interaction between Fe2O3 and K2O, reduces the formation temperature of KFe11O17 at least by 50 oC, and promotes the transformation of Fe3+ to Fe2+ further.

Boron nitride for enhanced oxidative dehydrogenation of ethylbenzene

It is demonstrated experimentally and confirmed theoretically that highly defective boron nitride showed outstanding performance for oxidative dehydrogenation of ethylbenzene.The catalyst is derived from carbon-doped hexagonal boron nitride nanosheets synthesized via a two-step reaction when participating the oxidative dehydrogenation reaction.The first step yields a polymeric precursor with the atomic positions of B,C,N relatively constrained,which is conducive for the formation of carbon atomic clusters uniformly dispersed throughout the BN framework.During the oxidative dehydrogenation of ethylbenzene to styrene,the nanoscale carbon clusters are removed and highly defective boron nitride(D-BN)is obtained,exposing boron-rich zigzag edges of BN that act as the catalytic sites.The catalytic performance of D-BN is therefore remarkably better than un-doped h-BN.Our results indicate that dispersed C-doping in h-BN is highly effective in terms of defect formation and resultant enhanced activity in oxidative dehydrogenation reactions.

Oxidative Dehydrogenation of Ethylbenzene over ZSM-5 Type Chromosilicates in the Presence of CO2

In this work, ZSM-5 type chromosilicate samples as K[Cr]ZSM-5(KCS) and Na[Cr]ZSM-5(NCS) were prepared by hydrothermal method and their catalytic properties were investigated for the oxidative dehydrogenation of ethylbenzene in the presence of CO2 as an oxidant using a fixed-bed stainless steel reactor. The prepared samples were characterized by their morphology (SEM), structural parameters (XRD), and textural parameters (BET). The performance of these catalysts was evaluated in terms of conversion, styrene yield, and selectivity. The KCSBW catalyst (potassium chromosilicate before washing with distilled water) afforded the highest styrene yield, 56.19%, with the selectivity of 96.05% in the presence of CO2 because of the coexistence of potassium ion and Cr2O3 in its structure and their synergistic effect. The influence of the presence of Cr2O3 and sodium or potassium ion on the catalytic activity of the chromosilicate samples in the catalytic EB dehydrogenation process was discussed in detail. Moreover, according to the results, the catalytic activity of the chromosilicate samples (CS) in EB dehydrogenation was increased by decreasing the surface area.

Vibrational Spectra and Quantum Calculations of Ethylbenzene

处于第一个激动的状态的 ethylbenzene 的正常颤动用反响的二光子的电离光谱学被学习了。S1S0 转变的 ethylbenzene 的乐队起源出现在 37586 cm1。在处于第一个激动的状态的乐队起源上面的 2000 cm1 的一个震动的系列被获得了。几链扭转和正常颤动在光谱被获得。第一个激动的状态的精力被时间依赖者密度功能理论和配置相互作用单身者(CIS ) 方法与各种各样的基础集合计算。优化结构和 S0 和 S1 状态的震动的频率与基础设置了的 6-311++G (2d,2p ) 用 Hartree-Fock 和 CIS 方法被计算。处于 S0 和 S1 状态的计算几何结构是乙醇组的对称的飞机对戒指飞机垂直的笨拙的符合构造。所有观察光谱乐队们成功地在我们的计算的帮助下被分配了。

Immobilization of metalloporphyrins on CeO_2@SiO_2 with a core-shell structure prepared via microemulsion method for catalytic oxidation of ethylbenzene

Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.

Measurements of the Critical Temperature and Pressure of Ethylene+Benzene+Ethylbenzene Mixture

Critical temperature (Tc) and critical pressure (pc) of the ternary mixture of ethylene+benzene+ethylbenzene (the mole ratio of ethylbenzene to benzene was fixed at 0.95:0.05) were measured by using a high=pressure view cell with direct visual observation.The interaction coefficients obtained from the critical properties of the relevant binary systems were used to predict the critical properties (Tc,pc) of the ternary mixture.The agreement between the prediction and experiments is satisfactory.

STUDY ON XPS,ESR AND MOSSBAUER SPECTRA OF FEZSM-5 WITH ADSORBED ETHYLBENZENE

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Adaptive On-line Operation Guide for Dry Gas-to-ethylbenzene Reactor

In this paper,a third-generation dry gas-to-ethylbenzene process in a factory of PetroChina is considered.For the gradual catalyst deactivation in the alkylation reactor,a model is established with the parameters estimated from the reaction rate equation of alkylation based on the on-site data and those from laboratory analysis. The real-time dynamic simulation of the alkylation process is carried out,in which the module accuracy is ensured by using OPC(Object linking and embedding for Process Control)technique and adaptive correction of model parameters.Both the current and future operation temperature can be predicted.

环状ZSM-5分子筛在苯和乙醇烷基化反应中的应用

低温下采用水热晶化法合成了环状中空ZSM-5分子筛,并以磷酸二氢铵为前体,制备了不同磷负载量的环状中空ZSM-5催化剂,采用XRD,SEM,NH_(3)-TPD,Py-FTIR等方法对催化剂进行表征,并在气相连续流动固定床反应器上对苯和乙醇烷基化制乙苯进行性能评价和稳定性考察。实验结果表明,环状中空ZSM-5催化剂进行磷改性后,催化剂的酸强度降低,随着磷负载量的增加,乙苯选择性逐渐增加,甲苯和丙苯选择性逐渐降低;当磷负载量达到3%(w)后,催化剂外表面强酸位基本消失,此时乙苯选择性最高;在n(苯)∶n(乙醇)=8∶1、340℃、1.0 MPa、WHSV=1 h^(-1)条件下,对该催化剂进行了寿命考察,在300 h反应过程中,乙醇转化率超过99.9%,苯的转化率维持在11%左右,乙基苯的选择性最高达到98.4%,二甲苯相对含量最低达到0.11%。

温度对β分子筛苯液相烷基化性能的影响

温度对β分子筛催化苯与乙烯液相烷基化反应性能的影响较大,本文从催化剂及反应角度两方面研究了温度对催化剂性能的影响。通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N_(2)物理吸附-脱附(BET)及吡啶吸附傅里叶变换红外光谱(Py-FTIR)等方法对自制的β分子筛进行表征,并考察了不同温度下β分子筛在苯与乙烯液相烷基化反应中的催化性能。结果表明,随温度升高,乙烯转化率升高,乙苯选择性降低,二乙苯选择性增加,其中,邻二乙苯选择性降低,对二乙苯选择性增加。同时,随温度升高,β分子筛上B酸量减少,主要为桥式羟基B酸和端基硅羟基B酸的减少。表明反应温度对乙烯转化率的影响主要受动力学控制;而温度对产物选择性的影响主要来源于温度对B酸量变化的影响,其中,乙苯选择性与B酸量有正相关性,邻二乙苯选择性与桥式羟基B酸量和端基硅羟基B酸量有正相关性。

基于气质联用法的鞋用胶粘剂中6种苯系物的测定

建立了气质联用法测定鞋用胶粘剂中6种苯系物的分析方法。以乙酸乙酯为萃取溶剂,提取胶粘剂中的6种苯系物,优化了仪器分析条件。结果表明,本方法6种苯系物的检出限为35~65 mg/kg,加标回收率为91.9%~98.0%,相对标准偏差为3.8%~7.8%。本方法仪器分析时间短,回收率高,重复性好,结果可靠,适用于胶粘剂中6种苯系物的检测。

SKI-320脱乙基型C_(8)芳烃异构化催化剂的工业应用

介绍了新一代脱乙基型C_(8)芳烃异构化催化剂SKI-320在中国石化上海石油化工股份有限公司600 kt/a芳烃联合装置上首次实施工业应用的情况。工业应用结果表明,催化剂生产过程控制平稳,成品质量合格;催化剂装填可控,开工操作简便,投用后周期运行情况良好;SKI-320催化剂的二甲苯异构化活性处于世界先进水平,二甲苯异构化率达到24.09%、乙苯转化率达到69.12%、单程二甲苯损失率为1.19%,性能指标全部达到合同要求,整体表现好于预期;与SKI-210催化剂相比,SKI-320催化剂的活性显著提高,选择性也有良好改进,实现了同类型催化剂应用技术的进步。