Kinetics and mechanisms of transalkylation and disproportionation of meta‐diethylbenzene by triflic acid catalyst

The kinetics of transalkylation and isomerization of meta‐diethylbenzene in the presence of benzene using triflic acid as a catalyst has been investigated. High catalytic activity of the triflic acid catalyst was observed in homogeneous liquid‐phase reactions. On the basis of the product distribution obtained, transalkylation, disproportionation, and isomerization reactions have been considered and the main product of the reaction was ethylbenzene. These reactions are conducted in a closed liquid batch reactor with continuous stirring under dry nitrogen and atmospheric pressure over the temperature range of 288–308 K. The main transalkylation, disproportionation, and isomerization reactions occurred simultaneously and were considered as elementary reactions. The apparent activation energy of the transalkylation reaction was found to be 35.5 kJ/mol, while that of disproportionation reaction was 42.3 kJ/mol. The reproducibility of the experimental product distribution occurred with an average relative error of ±2%. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 555–563, 2003     

Kinetic modeling of the ethylbenzene/xylene isomerization reaction over HZSM-5 zeolites revisited

In this article, a binderless dealuminated HZSM-5 zeolite (Si/Al = 41.4) was used as a catalyst for the isomerization of a mixture of ethylbenzene and xylene. The experimental results indicated that at low residence times the catalyst is effective to isomerize the ethylbenzene into xylenes. A comprehensive kinetic model considering chemisorption, surface chemical reactions, and diffusional processes was developed for this reaction. The intrinsic activation energy (71.99 kJ mol⁻¹) for the surface reaction of ethylbenzene into m-xylene was calculated for the first time, and the corresponding intrinsic activation energies for o-xylene to m-xylene and m-xylene to p-xylene surface reactions were calculated to be 59.45 and 50.68 kJ mol⁻¹, respectively. Lower apparent values have been reported in the literature, and we rationalize that they correspond to multistep processes and intrinsically include a negative activation energy pertaining to chemisorption. The results also revealed that the ethylbenzene diffusion within the zeolite channels was four orders of magnitude smaller than p-xylene.     

Design and Development of Zeolite-Based Catalytic Processes for Aromatics Production

Processes for the production of xylenes, which occur in an integrated aromatic complex, are discussed. A brief overview of the work carried out at Indian Petrochemicals Corporation Limited for the development of zeolite-based catalytic processes for the production of aromatics is presented. This includes xylene isomerization, transalkylation and disproportionation of C₇ and C₉ aromatics for maximization of xylenes, selective disproportionation of toluene and selective alkylation of mono-alkylaromatics to p-dialkylbenzene. Achievements in the commercialization of zeolite-based catalysts and processes for isomerization of m-xylene to p- and o-xylene along with dealkylation of ethylbenzene, and for selective ethylation of ethylbenzene to produce p-diethylbenzene are highlighted.     

Influence of Metallic Modification on Ethylbenzene Dealkylation over ZSM‐5 Zeolites

A series of metal‐modified HZSM‐5 catalysts were prepared by impregnation and were used for ethylbenzene dealkylation of the mixed C8 aromatics (ethylbenzene, m‐xylene and o‐xylene). The effects of different supported metals (Pt, Pd, Ni, Mo) on catalytic performance, including reaction conditions, were investigated. The physicochemical properties of catalysts were characterized by means of XRD, BET, TEM and NH₃‐TPD. Experimental results showed that metallic modification obviously increased the ethylbenzene conversion and reduced the coke deposition, greatly improving the catalyst stability. The distinction of ethylbenzene conversion depended on the interaction between hydrogenation reactivity and acidic cracking of bifunctional metal‐modified zeolites. Compared with Pt and Ni, Pd and Mo were easier to disperse into HZSM‐5 micropores during loading metals. The acidic density of different metal‐modified HZSM‐5 declined in the following order: HZSM‐5>Pt/HZSM‐5>Pd/HZSM‐5>Ni/HZSM‐5>Mo/HZSM‐5. The activity of ethylene hydrogenation decreased with Pt/HZSM‐5>Pd/HZSM‐5>Ni/HZSM‐5>Mo/HZSM‐5. In comparison, Pd/HZSM‐5 showed the best catalytic performance with both high activity and high selectivity, with less cracking loss of m‐xylene and o‐xylene. Moreover, the following reaction conditions were found to be preferable for ethylbenzene dealkylation over Pd/HZSM‐5: 340°C, 1.5 MPa H₂, WHSV 4 h^?1, H₂/C8 4 mol/mol.     

Catalytic properties of zeolites MCM-22 and NU-87 in disproportionation of toluene

The catalytic properties of MCM-22 and NU-87 were investigated for the disproportionation of toluene to produce benzene and xylene, and the results were compared with those obtained over mordenite, beta and ZSM-5. It turns out that dealumination of MCM-22 removes selectively the acid sites from the external surface and thus suppresses the secondary isomerization of p-xylene, enhancing the para-selectivity. This indicates that the dealuminated MCM-22 is a promising catalyst for the selective formation of p-xylene from toluene disproportionation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Catalytic Conversion of 1,2,3-Trimethylbenzene Over HY Zeolite

The reaction of 1,2,3-trimethylbenzene (1,2,3-TMB) over HY zeolite was investigated in a fixed-bed flow reactor at 200-300 °C under atmospheric pressure. The reaction products include toluene, pentamethylbenzene and isomers of xylene, 1,2,3-TMB and tetramethylbenzene. Based on the time-on-stream theory, the types and initial selectivities of these products were determined from plots of product selectivity. 1,2,4-TMB is initially produced from 1,2,3-TMB via isomerization whereas o-xylene, m-xylene, 1,2,3,4- and 1,2,3,5-tetramethylbenzene were primarily formed by disproportionation of 1,2,3-TMB. Isomerization and disproportionation obeyed first- and second-order kinetics, respectively; both reactions proceeded via a carbonium ion mechanism with the former occurring by methyl transfer on the benzene ring whereas the latter proceeded through the diphenylmethane transition state. The activation energies are 31.6 and 37.2 kJ mol^?1 for isomerizaion and disproportionation, respectively.     

Vapour phase alkylation of ethylbenzene with t -butyl alcohol over mesoporous Al-MCM-41 molecular sieves

The alkylation of ethylbenzene witht-butyl alcohol was studied over Al-MCM-41 (Si/Al = 50 and 90) and Al, Mg-MCM-41 (Si/(Al+Mg) = 50) in the vapour phase from 200 to 400°C. The products werep-t-butylethylbenzene (p-t-BEB),p-t- butylvinylbenzene (p-t-BVB) andm-t-butylethylbenzene (m-t-BEB). Ethylbenzene conversion decreased with increase in temperature and increase in the ethylbenzene content of the feed. The reaction between the freely diffusing ethylbenzene in the channel and thet-butyl cations remaining as charge compensating ions yieldedp-t- BEB.p-t-BVB, an unexpected product in this investigation, was produced by dehydrogenation ofp-t-BEB over alumina particles present in the channels of the molecular sieves. Adsorption of ethylbenzene on Br?nsted acid sites and its subsequent reaction with very closely adsorbedt-butyl cations proved to be necessary to obtainm-t-BEB. Thoughm-t-BEB was obtained, the correspondingm-t-butylvinylbenzene was not observed in this study. Study of time durations indicated rapid and slow catalyst deactivation at lower and higher streams respectively.     

Catalytic Performance of Modified HMCM‐22 Catalysts in Xylene Isomerization

HMCM‐22 catalysts modified with La₂O₃ (5% La) and MgO (≈0.87% Mg) were prepared respectively by impregnation method, and were characterized by scanning electron microscopy, X‐ray diffraction, N₂ physical adsorption‐desorption and temperature‐programmed desorption of NH₃. The effect of supported metallic oxides (La₂O₃, MgO) on catalytic performance in xylene isomerization of C8 aromatics (ethylbenzene, m‐xylene and o‐xylene) was investigated in detail. The experimental results showed that 5% La/HMCM‐22 catalyst had higher isomerization activity and stronger shape‐selectivity than 0.87% Mg/HMCM‐22 catalyst, owing to its more acid sites and smaller pore size. And the loading amount of La was optimized to be about 7%. Moreover, supporting metal over 7% La/HMCM‐22, respectively with 0.3% Pt, 3% Ni and 3% Mo, was carried out to prepare bifunctional isomerization catalysts. In comparison, 3% Mo/7% La/HMCM‐22 showed the best catalytic performance with both high activity and high selectivity, with the low hydrocracking of m‐xylene and o‐xylene. Besides, the optimal reaction conditions were found: 340°C, 1.5 MPa H₂, WHSV 4 h^?1 and H₂/C8 4 mol/mol. Under the above conditions, ethylbenzene conversion was up to 20%, para‐selectivity was over 23% with low xylene loss of 2.9%.     

3,5-二甲基苯溴化镁修饰的ZSM-5催化剂乙苯歧化反应

采用尺寸较大的有机分子格式试剂（3,5-二甲基苯溴化镁）修饰ZSM-5催化剂,用乙苯歧化反应研究了修饰催化剂的择形性,并利用探针分子动力学扩散测试结合探针分子吸附红外等手段研究分子筛孔径和内外表面酸性性质等。结果表明,少量的3,5-二甲基苯溴化镁精确地中和了ZSM-5分子筛外表面的酸性中心,导致乙苯歧化反应中极高的对二乙苯选择性。而探针分子动力学结果表明,这种修饰并未引起分子筛孔道结构的变化。     

3，5-二甲基苯溴化镁修饰的ZSM-5催化剂乙苯歧化反应

采用尺寸较大的有机分子格式试剂（3,5-二甲基苯溴化镁）修饰ZSM-5催化剂,用乙苯歧化反应研究了修饰催化剂的择形性,并利用探针分子动力学扩散测试结合探针分子吸附红外等手段研究分子筛孔径和内外表面酸性性质等。结果表明,少量的3,5-二甲基苯溴化镁精确地中和了ZSM-5分子筛外表面的酸性中心,导致乙苯歧化反应中极高的对二乙苯选择性。而探针分子动力学结果表明,这种修饰并未引起分子筛孔道结构的变化。     

Pyrolysis of polyisoprenes. I. Differentiation between natural and synthetic cis-1,4-polyisoprenes

Two methods of differentiating between natural rubber and synthetic cis-1,4-polyisoprenes have been examined. Both techniques depend on the presence of Ziegler-Natta catalyst residues in the synthetic polymers. The major pyrolysis product of cis-1,4-polyisoprenes at 350°C is 1-methyl-4-(1-methylethenyl)cyclohexene. This can undergo disproportionation to yield 1-methyl-4-(1-methylethyl)benzene and methyl-(1-methylethyl)cyclohexenes. It is this disproportionation reaction, catalyzed by Ziegler-Natta catalyst residues or by carbon black, that is responsible for the different product ratios obtained on pyrolysis of natural rubber and Ziegler-Natta catalyzed cis-1,4-polyisoprenes. Lithium alkyl-polymerized polyisoprenes undergo this secondary disproportionation reaction only in the presence of carbon black. Derivative thermogravimetric traces of black-filled sulfur vulcanizates of natural rubber and synthetic polyisoprenes are significantly different because polymerization catalyst residues promote cyclization of the polymer.     

High selective ethylbenzene obtainment through alkylation of dilute ethene 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 °C 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.     

Comparison ofn-decane hydroconversion with Pt/SAPO-5 and Pt/SAPO-11 catalysts

The product distributions from bifunctional conversion ofn-decane over Pt/SAPO-5 and Pt/SAPO-11 catalysts are compared in detail. Selectivities in decane reaction vary largely with the catalyst employed: Pt/SAPO-11 produces high yields of feed isomers, whereas Pt/SAPO-5 gives high yields of cracked products and only under mild reaction conditions are isodecanes the main products obtained. These selectivities seem to be determined by the structure of the catalyst.     

The kinetics of polycondensation of α,α′‐dichloro‐p‐xylene with 4,4′‐isopropylidenediphenol using benzyltriethylammonium chloride as a phase‐transfer catalyst

The phase‐transfer catalyzed polycondensation of α,α′‐dichloro‐p‐xylene with 4,4′‐isopropylidenediphenol was carried out using benzylethylammonium chloride in a two‐phase system of an aqueous alkaline solution and benzene at 60 °C under nitrogen atmosphere. The rate of polycondensation was expressed as the combined terms of quaternary onium cation and 4,4′‐isopropylidenediphenolate anion rather than the feed concentration of catalyst and 4,4′‐isopropylidenediphenol. The measured concentrations of hydroxide and chloride anion in the aqueous solution and α,α′‐dichloro‐p‐xylene in the organic phase were used to obtain the reaction rate constant with the integral method, and to analyze the polycondensation mechanism with a cyclic phase‐transfer initiation step in the heterogeneous liquid–liquid system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3059–3066, 2000     

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.     

Mechanisms of Xylene Isomer Oxidation by Non-thermal Plasma via Paired Experiments and Simulations

Xylene is a widely used solvent and industrial chemical, but it is also considered to be a volatile organic compound (VOC) pollutant. Meanwhile, non-thermal plasma (NTP) is a potential method for remediating VOC contaminants, especially aromatic hydrocarbons. During NTP degradation of xylene, the different oxidation mechanisms of three isomers, p-xylene, o-xylene and m-xylene, have attracted lots of attention but not been studied at the molecular level. In this study, the individual degradation rates of xylene isomers in a NTP system are measured. The results show the oxidation degradation rates have the following order: o-xylene?>?p-xylene?≈?m-xylene. Molecular dynamics simulations with an applied external electric field were adopted to examine the oxidation process of xylene isomers, as well. The oxidation rates from the simulations were calculated, the order of which is in a good agreement with the experimental results. The oxidation pathways of xylene isomers were analyzed more thoroughly to explain the rate differences. The external electrical field is found to have two effects: one is to speed up the oxidation rate of xylene isomers overall, and the other is to alter the oxidation pathways to increase the probability of the faster ring cleavage pathways of o-xylene.

     

Partial oxidation of toluene with nitrous oxide under supercritical conditions

The partial oxidation of toluene with nitrous oxide over the H-ZSM-5 catalyst under supercritical conditions at temperatures of 370–420°C and pressures of 70–160 atm has been investigated for the first time. The maximum cresol selectivity under these conditions is 32%. The amounts of the resulting cresol isomers form the following decreasing sequence: m-cresol > o-cresol > p-cresol. The partial oxidation of toluene is accompanied by disproportionation and biphenyl formation.     

Isomerization and Disproportionation of 1,2,4-Trimethylbenzene over HY Zeolite

The conversion of 1,2,4-trimethy]benzene (1,2,4-TMB) over HY zeolite was studied at atmosoheric pressure and 200–300 °C by using a fixed-bed, integral-flow reactor. The types and initial selectivities of various products were obtained from plots of product selectivity according to the time-on-stream theory. The primary reaction included the isomerization and the disproportionation; the former led to the simultaneous formation of 1,2.3- and 1,3,5-TMB whereas the latter produced all isomers of xylene and tetramethylbenzene. The relative initial rate of disproportionation to isomerization decreased from 12.6 at 200 °C to 5.47 at 300 °C. The activation energies for the primary reactions were estimated and compared with those in the reaction of 1,2,3-TMB.     

Effects of adsorption-induced microstructural changes on separation of xylene isomers through MFI-type zeolite membranes

Various factors were found to affect the performance of MFI-type zeolite membranes in separating xylene isomers (p-xylene, PX; o-xylene, OX) by pervaporation. In this work the effect of membrane microstructure, membrane quality, and pervaporation operating conditions were investigated using three membrane microstructures: random, c-oriented, and h,0,h-oriented. Operation under pervaporation conditions means that high loadings of PX will be present in the framework; therefore, the role of PX–framework and PX–OX interactions needs to be taken into consideration. Single component experiments demonstrated that the order of experimentation with OX and PX will affect the ideal selectivity. Multi-component studies showed that membrane performance is highly dependent on the relative concentration of the isomers in the feed; the higher the PX concentration the lower the selectivity observed. However, although high selectivity (18) was observed at low PX concentrations in the feed, it was not stable over time. Similar trends were observed for all membrane microstructures but differences in the selectivity values occurred. The structural deformation caused by high loadings of PX into the silicalite crystal affects each microstructure differently, ultimately leading to differences in performance.     

Effects of structure and composition on the titration curves of some synthetic copolymers in nonaqueous media

p-Aminobenzoic acid, p-hydroxybenzoic acid, and formaldehyde were condensed in various molar proportions in the presence of acid catalyst to obtain copolymers of various compositions. Conductometric and potentiometric titrations were carried out on seven copolymers having different feed compositions in nonaqueous solvents with acid as well as base. The titration curves indicated a large number of additional breaks inflections before the complete neutralization of COOH, OH, or NH₂ groups. These observations have been interpreted in terms of degree of polymerization, composition, and structure of the copolymers.