Feedstock recycling of agriculture plastic film wastes by catalytic cracking

Feedstock recycling by catalytic cracking of a real plastic film waste from Almeria greenhouses (Spain) towards valuable hydrocarbon mixtures has been studied over several acid catalysts. The plastic film waste was mostly made up of ambient degraded low-density polyethylene (LDPE) and ethylene-vinyl acetate (EVA) copolymer, the vinyl acetate content being around 4 wt.%. Nanocrystalline HZSM-5 zeolite (crystal size 60 nm) was the only catalyst capable of degrading completely the refuse at 420 °C despite using a very small amount of catalyst (plastic/catalyst mass ratio of 50). However, mesoporous catalysts (Al-SBA-15 and Al-MCM-41), unlike it occurred with virgin LDPE, showed fairly close conversions to that of thermal cracking. Nanocrystalline HZSM-5 zeolite led to 60 wt.% selectivity towards C₁---C₅ hydrocarbons, mostly valuable C₃---C₅ olefins, what would improve the profitability of a future industrial recycling process. The remarkable performance of nanocrystalline HZSM-5 zeolite was ascribed to its high content of strong external acid sites due to its nanometer dimension, which are very active for the cracking of bulky macromolecules. Hence, nanocrystalline HZSM-5 can be regarded as a promising catalyst for a feasible feedstock recycling process by catalytic cracking.     

Vapour Phase Oxidation of Cumene by Molecular Oxygen over MCM-41 Supported Cobalt Oxide Catalyst

Si-MCM-41 and Al-MCM-41 supported cobalt oxide catalysts were prepared and characterized by XRD. The surface area, pore size and wall thickness was calculated by applying BET equation and BJH method using nitrogen sorption technique. DR UV-VIS confirm the presence of cobalt oxide as isolated particle in the framework positions of the MCM-41 mesostructure. The vapour phase oxidation of isopropyl benzene with CO₂-free air as the oxidant was studied over cobalt oxide supported unwashed and washed Si-MCM-41 and Al-MCM-41 catalyst. Isopropyl benzene conversion increased with increase in temperature from 200 to 300 °C, but at 325 °C it decreased. Formation of coke was noted at all the temperatures. Cumenehydroperoxide, 1,2-epoxyisopropylbenzene, acetophenone and styrene were the products observed in this reaction. Of the products cumenehydroperoxide was found to be more selective over all the catalysts. Both unwashed and washed catalysts were found to have nearly the same activity. Due to more dispersion, the active sites in the latter catalysts compensates its low cobalt oxide content in producing activity equal to the former catalysts. The study of time on stream indicated decrease in conversion due to coke formation.     

可循环再利用橡胶制品的制备研究

介绍以废旧轮胎或废旧橡胶制品的脱硫橡胶为主要原料、采用注射成型工艺制备可循环再利用橡胶制品的方法。废旧轮胎先经过去除钢丝、锦纶丝,粉碎、筛分预处理,再经过无污染的真空脱硫,混炼制成原料胶粒;无骨架材料的废旧橡胶制品直接经过真空脱硫处理也可以制成混炼胶颗粒;真空脱硫胶粒通过注射成型机和专门设计的模具,直接制成可以循环再利用的橡胶制品。     

Synthesis of dypnone using SO4/Al-MCM-41 mesoporous molecular sieves

The mesoporous molecular sieves Al-MCM-41 with Si/Al ratio equal to 16, was synthesized under hydrothermal conditions using cetyltrimethylammonium bromide (CTMA⁺Br⁻) as surfactant. The same ratio of Al-MCM-41 materials was impregnated using sulfuric acid, the materials as sulfated Al-MCM-41 (SO₄²⁻/Al-MCM-41). The mesoporous materials viz Al-MCM-41 and SO₄²⁻/Al-MCM-41 were characterized using several techniques e.g. ICP-AES, Nephelometer, XRD, FT-IR, TG/DTA, N₂-adsorption, solid-state-NMR, SEM and TPD-pyridine. ICP-AES studies indicated the presence of Al in the mesoporous materials. Nephelometer studies indicated the SO₄²⁻ presence of the SO₄²⁻/Al-MCM-41. XRD studies indicated that the calcined materials of Al-MCM-41 and SO₄²⁻/Al-MCM-41 had the standard MCM-41 structure. The surface area, pore diameter, pore volume and wall thickness of the mesoporous materials were calculated by BET and BJH equations, respectively. Crystallinity, surface area, pore diameter and pore volume of SO₄²⁻/Al-MCM-41 decreased except wall thickness and the expelling aluminum from the Al-MCM-41 framework increased the Lewis acidity. FT-IR studies indicated that Al-ions were incorporated in the hexagonal mesoporous structure of Al-MCM-41 and sulfuric acid was impregnated into hexagonal Al-MCM-41 materials. The thermal stability of as-synthesized Al-MCM-41 materials and SO₄²⁻/Al-MCM-41 materials were studied using TG/DTA. The environments of the Al-ions coordinated in the silica matrix were determined by ²⁷Al-MAS-NMR. The morphology of Al-MCM-41 and SO₄²⁻/Al-MCM-41 was determined by SEM. The total acidity of Al-MCM-41 and SO₄²⁻/Al-MCM-41 materials was determined by TPD-pyridine. The catalytic results were compared with those obtained by using sulfuric acid, amorphous silica–alumina, H-β, USY and H-ZSM-5 zeolites. The SO₄²⁻/Al-MCM-41 catalyst exclusively forms the product of dypnone from self-condensation of acetophenone molecules due to higher number of Lewis acid sites and has much higher yields than other catalysts except USY.     

Vapor-Phase Isopropylation of Phenol over Fe-Containing Al-MCM-41 Molecular Sieves

Al-MCM-41 and Fe-containing MCM-41 molecular sieves are hydrothermally synthesized. The low-angle XRD analysis shows that iron incorporation in Al-MCM-41 retains the hexagonal structure of MCM-41. The higher d-spacing values of Fe-Al-MCM-41 catalysts than those of Al-MCM-41 indicate the incorporation of iron into the framework. The mesoporous nature of the materials was confirmed by nitrogen adsorption isotherms. Electron paramagnetic resonance (EPR) and diffuse reflectance spectra (DRS) techniques confirm the tetrahedral coordination of iron into the Al-MCM-41 framework. Acidity of the synthesized catalysts was analyzed by both TPD of ammonia and pyridine-adsorbed FT-IR spectroscopy. The acidity measurements indicate that iron incorporation increases both Lewis and Brønsted acidity of the catalysts. Vapor-phase isopropylation of phenol with the new'alkylating agent isopropyl acetate was carried over the H-forms of the above catalysts. The phenol to isopropyl acetate ratio of 1?:?2 and the phenol space velocity of 1.1 h^-1 were found to be the optimum conditions for better phenol conversion and para isomer (4-isopropyl phenol) selectivity. On comparison, the Fe-incorporated Al-MCM-41 catalysts show significantly higher phenol conversion and selectivity toward the important product 4-isopropyl phenol (4-IPP) may be due to stronger Brønsted acid sites generated by the strengthening effect of nearby Lewis acid sites. Further, the undesired and dialkylated products selectivity are found to be lower over Fe-incorporated Al-MCM-41 than pure Al-MCM-41 catalysts.     

Effect of lanthanum addition on the thiophene hydrodesulfurization activity over Al-MCM-41 supported molybdenum catalysts

A series of Al-MCM-41 modified with 1–7% lanthanum were used as supports to prepare the Mo/La–Al-MCM-41 catalysts containing 10 wt.% molybdenum. The supports and catalysts were characterized with XRD, BET, XPS, TPD, TEM and SEM, and their catalytic activities were tested for thiophene hydrodesulfurization. The La addition did not cause any significant collapse of the structure and morphology of Al-MCM-41 samples, and increased the acidity of Al-MCM-41 samples. The Mo/La–Al-MCM-41 catalysts showed higher thiophene HDS activity than non-modified catalysts. The La-modified catalysts showed an enhanced butene selectivity but a decreased tetrahydrothiophene selectivity, indicating that the La–Al-MCM-41 supports contained a larger amount of acid sites.     

Characteristics of Al-MCM-41 supported Pt catalysts: effect of Al distribution in Al-MCM-41 on its catalytic activity in naphthalene hydrogenation

Naphthalene hydrogenation was carried out in a high-pressure batch reactor over platinum catalysts supported on Al-MCM-41 where aluminum was incorporated through two different methods: a direct sol–gel method (Pre) and post-synthetic grafting method (Post). The catalytic reaction was also performed in the presence of dibenzothiophene to investigate the sulfur tolerance. The hydrogenation activity, selectivity and the sulfur tolerance strongly depended on the acidic nature of Al-MCM-41 support. It was suggested that the acid sites of Al-MCM-41-Post be more accessible than those of Al-MCM-Pre due to different aluminum distribution within the pore wall. The naphthalene and tetralin conversion increased with the acid amount of the supports in Pt/Al-MCM-41 catalysts. The acid sites in bifunctional catalysts seemed to contribute to alternative pathway by the spillover hydrogen in the acid–metal interfacial region for naphthalene hydrogenation, since the metal dispersions were kept constant for Pt/Al-MCM-41 catalysts. The trans-decalin selectivity generally increased with temperature or acid amount. The acid sites seemed to enhance the sulfur tolerance of supported platinum catalysts due to the electron-deficient state of metal.     

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.     

Pyrolysis of biomass in the presence of Al-MCM-41 type catalysts

Al-MCM-41 type mesoporous catalysts were used for converting the pyrolysis vapours of spruce wood in order to obtain better bio-oil properties. Four Al-MCM-41 type catalysts with a Si/Al ratio of 20 were tested. The catalytic properties of Al-MCM-41 catalyst were modified by pore enlargement that allows the processing of larger molecules and by introduction of Cu cations into the structure.Spruce wood pyrolysis at 500 °C was performed and the products were analysed with the help of on-line pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). In addition, thermogravimetry/mass spectrometry (TG/MS) experiments were applied for monitoring the product evolution under slow heating conditions (20 °C/min) from 50 to 800 °C.Levoglucosan is completely eliminated, while acetic acid, furfural and furanes become quite important among cellulose pyrolysis products over the unmodified Al-MCM-41 catalyst. The dominance of phenolic compounds of higher molecular mass is strongly cut back among the lignin products. Both the increase of the yield of acetic acid and furan and the decrease of large methoxyphenols are repressed to some extent over catalysts with enlarged pores. The Cu modified catalyst performed similarly to the catalyst with enlarged pore size in converting the pyrolysis vapours of wood, although its pore size was similar to the unmodified Al-MCM-41.     

Room temperature efficacious synthesis of diphenylmethane over Fe/Al-MCM-41 catalysts

Fe/Al-MCM-41 (Si/Al = 25, 50, 75 and 100) were synthesized. Their catalytic activity was evaluated towards benzylation of benzene with benzyl chloride in liquid phase. The catalytic activity of Fe/Al-MCM-41(25) was higher than the other catalysts. Diphenylmethane(DPM) was obtained as the major product with 100% selectivity and with 100% conversion of benzyl chloride under optimum condition. The effect of temperature and the feed ratio, on the activity of Fe/Al-MCM-41(25) and selectivity towards DPM was studied and a possible reaction mechanism was proposed.     

航空煤油在不同孔径的Ag基介孔材料吸附剂上深度吸附脱硫的研究

以3种不同孔径的介孔材料MCM-41,SBA-15,大孔SBA-15(SBA-15-L)为载体,采用离子交换法制备了Ag/Al-MCM-41,Ag/Al-SBA-15和Ag/Al-SBA-15-L介孔材料吸附剂。利用XRD,N2吸附,SEM-EDS,ICP-MS等手段对所制备的吸附剂进行了表征,并在固定床上对航空煤油进行了吸附脱硫研究。结果表明,交换Ag+所制备的吸附剂依然保持介孔材料的特性,并可将含S量为150×10-6的航空煤油中的硫化物,选择性的吸附脱除到S含量低于1.0×10-6。其中,在Ag/Al-MCM-41,Ag/Al-SBA-15和Ag/Al-SBA-15-L吸附剂上,可分别得到8.0,9.0和17.0mL的清洁航空煤油(含硫量小于1.0×10-6)。实验结果也表明,所制备的吸附剂吸附脱硫性能主要取决于介孔材料载体的孔径大小,载体的孔径越大,Ag+的利用率越高,吸附剂的吸附脱硫性能越强。将吸附饱和的Ag/Al-SBA-15-L吸附剂,于空气中在350℃进行再生5h,吸附剂的吸附性能可以100%的恢复。     

Hydrocracking of heavy oil using zeolites Y/Al-SBA-15 composites as catalyst supports

A series of Y/Al-SBA-15 composites were prepared by a two-step synthesis procedure in mild acidic medium. The materials were characterized by powder X-ray diffraction (XRD), N₂ sorption isotherms and TEM techniques. Catalytic cracking of cumene and 1,3,5-tri-isopropylbenzene was carried out as the probing reactions on these composites. The XRD results showed that these materials are composites of Al-SBA-15 and Y zeolite. N₂ sorption isotherms and TEM displayed that these composites were abundant in micropores and mesopores. At the same time, the mesopores may communicate with the␣micropores in some domains, which may result in the high catalytic activities of Y/Al-SBA-15 composites for the␣cracking of both small-molecule (cumene) and large-molecule (1,3,5-tri-isopropylbenzene) hydrocarbons. The existence of mesopores may also make the acid sites easily accessible for reactants. Catalysts of W–Ni supported on Y/Al-SBA-15 and modified Y zeolites with mesopores were prepared by impregnation method, and the hydrocracking of heavy oil was performed on these catalysts. The catalyst using zeolite Y/mesoporous Al-SBA-15 composites as support gave higher yield of diesel compared to the catalysts using modified zeolite Y as support. In addition, the higher aromatics potential of heavy naphtha and the significantly lower BMCI (U.S. Bureau of Correlation Index) of tail oil revealed Y/Al-SBA-15 composite catalyst possessed integrated performance in the hydrocracking of heavy oil. These results proved that the combination of Y zeolites and mesoporous Al-SBA-15 plays a great role in improving the performance of catalysts for hydrocracking heavy oils.     

Unique vapor phase synthesis of 1,2,3,5,6,7-hexahydrodicyclopenta[b,e]pyridine selectively over Co–Al-MCM-41

Cyclization of cyclopentanone, formaldehyde and ammonia in vapor phase gives 1,2,3,5,6,7-hexahydrodicyclopenta[b,e]pyridine (HHDCP) and spiro[cyclopentane-1,8′-(1′,2′,3′,5′,6′,7′,8′,8′a) octahydrodicyclopenta[b,e]]pyridine (SCOHDCP) over zeolites HY, HZSM-5, Hβ and mesoporous Al-MCM-41 molecular sieves. The preliminary screening of catalysts clearly shows that Al-MCM-41 is more suitable for the vapor phase synthesis of HHDCP. As the NH₃-TPD profiles of Al-MCM-41 show wide range distribution of acid sites in the temperature range of 200–600 °C (weak–medium–strong), Al-MCM-41 is further modified with transition metal ions like V(V), Mn(II), Fe(III), Co(III), Cu(II), La(III) and Ce(III) to fine tune the acid sites. Correlation of activity and selectivity of transition metal modified Al-MCM-41 with the NH₃-TPD profiles show that though the conversions are high, selectivity of either HHDCP or SCOHDCP is a preference of acid site strength formed on metal ion modification. Interestingly Co²⁺ ion modification of Al-MCM-41 resulted distinctly into two sets of acid sites with T_max around 218 °C (weak–medium) and 673 °C (strong). The reaction is studied on Co–Al-MCM-41 by adsorbing pyridine at 300 °C. The typical acidity available on pyridine adsorbed Co–Al-MCM-41 around 300 °C is showing cyclization activity forming only HHDCP indicating that weak–medium acid sites are responsible for the formation of HHDCP. Based on the product distribution plausible reaction mechanism is proposed.     

Synthesis of highly stable mesoporous aluminosilicates from commercially available zeolites and their application to the pyrolysis of woody biomass

Ordered mesoporous aluminosilicates have been successfully obtained via the simple combination of top–down and bottom–up approaches, using commercially available zeolites as the framework sources. The mesoporous aluminosilicates are characterized by XRD, N₂ sorption, SEM, TEM, ICP, and NMR, and have proven to have controllable aluminium contents, well-developed mesoporosity, and excellent hydrothermal stability. The hydrothermally stable mesoporous aluminosilicates, which possess the proper distribution of weak and strong acid sites, are applied as reusable heterogeneous catalysts for the pyrolysis of woody biomass. The mesoporous aluminosilicates in the present work showed good activity, selectivity, and even stability for the production of desirable organic compounds such as phenolics, in comparison to conventional HZSM-5 and Al-MCM-41.     

t-Butylation of p-cresol with t-butyl alcohol over mesoporous Al-MCM-41 molecular sieves

Selective liquid-phase t-butylation of p-cresol with t-butyl alcohol (t-BuOH) to produce 2-t-butyl-p-cresol (TBC) has been conducted over Al-MCM-41 catalysts with different Si/Al ratios. The effects of various reaction parameters such as temperature, reaction time and n_t-BuOH:n_p-cresol ratio on the conversion of p-cresol and the selectivity of TBC have been systematically investigated as well. When the Si/Al ratio of Al-MCM-41 catalysts is increased from 21 to 104 (respectively yielding Al-MCM-41(21), Al-MCM-41(42), Al-MCM-41(62), Al-MCM-41(83) and Al-MCM-41(104)), both the conversion of p-cresol and the yield and selectivity of TBC decrease due to the decrease of the number of Brønsted acid sites of the Al-MCM-41 catalysts. Al-MCM-41(21) catalyst is found to give the highest conversion of p-cresol (88.2%) and the highest selectivity of TBC (90.40%) under the optimal n_t-BuOH:n_p-cresol mole ratio of 2:1, the optimal reaction temperature of 90 °C and the optimal reaction time of 2 h. Furthermore, Al-MCM-41(21) can be recycled up to at least four times without losing its catalytic performance for butylation reaction.     

Efficient catalysis of mesoporous Al-MCM-41 for Mukaiyama aldol reactions

Mesoporous aluminosilicates, Al-MCM-41 (Si/Al = 20 and 50), efficiently catalyzed Mukaiyama aldol reaction of benzaldehyde with 1-(trimethylsiloxy)cyclohexene in CH₂Cl₂ at 0 °C to afford the corresponding β-trimethylsiloxy ketone in quantitative yield. On the other hand, mesoporous silica (MCM-41), amorphous SiO₂–Al₂O₃, and H–Y and H-ZSM-5 zeolites barely catalyzed the reaction. Additionally, the less ordered Al-MCM-41 prepared by mechanical compression exhibited much lower catalytic activity compared with Al-MCM-41, indicating that the presence of the ordered mesoporous structure in aluminosilicates is crucial for the catalysis. The Al-MCM-41 catalyzed Mukaiyama aldol reaction was applicable to a wide range of aldehydes and silyl enol ethers. Furthermore, the Al-MCM-41 catalyst could be recycled at least three times without any loss in the yield. Thus, mesoporous aluminosilicates are promising heterogeneous catalysts for fine chemicals synthesis.     

Transesterification of diethyl malonate with n-butanol over HPWA/MCM-41 molecular sieves

Mesoporous Si-MCM-41 and Al-MCM-41 (Si/Al = 100) materials were synthesized via a hydrothermal method. Three different ratios (10, 20 and 30 wt%) of heteropoly tungstic acid (HPWA) was loaded on Si-MCM-41 by wet impregnation techniques. The characteristic structural features of the prepared materials were studied by various physico-chemical techniques such as X-ray diffraction (XRD), Nitrogen physisorption (BET), temperature programmed desorption of ammonia (TPD) and transmission electron microscopy (TEM). Transesterification of diethyl malonate (DEM) with n-butanol under autogeneous conditions in a temperature range from 50 to 125 °C was selected as the test reaction for the as synthesized materials. The reactants were fed with various mole ratios in order to determine the optimal feed composition leading to maximum yields of transesterified products. The results indicated that the conversion of diethylmalonate depends on the HPWA concentration on the support, temperature, reaction time and mole ratio of the reactants. Further, the catalytic efficiency of HPWA/MCM-41 was compared with that of Al-MCM-41. The solid acid HPWA/MCM-41 catalysts have several advantages in comparison to conventional mineral acid catalysts which are heterogeneous, eco-friendly, highly active and selective in the formation of transesters.     

Evaluation of various types of Al-MCM-41 materials as catalysts in biomass pyrolysis for the production of bio-fuels and chemicals

MCM-41, is one of the latest members of the mesoporous family of materials. They possess a hexagonal array of uniform mesopores (1.4–10 nm), high surface areas (>1000 m²/g) and moderate acidity. Due to these properties the MCM-41 materials are currently under study in a variety of processes as catalysts or catalyst supports. The objective of this study was to evaluate different types of MCM-41 materials as potential catalysts in the catalytic biomass pyrolysis process. We expected that the very high pore size and the mild acidity of these materials could be beneficial to reformulate the high molecular weight primary molecules from biomass pyrolysis producing useful chemical (and especially phenolic compounds) and lighter bio-oil with less heavy molecules. Three different samples of Al-MCM-41 materials (with different Si/Al ratio) and three metal containing mesoporous samples (Cu–Al-MCM-41, Fe–Al-MCM-41 and Zn–Al-MCM-41) have been synthesised, characterized and tested as catalysts in the biomass catalytic pyrolysis process using a fixed bed pyrolysis combined with a fixed catalytic reactor and two different types of biomass feeds. Compared to conventional (non-catalytic) pyrolysis, it was found that the presence of the MCM-41 material alters significantly the quality of the pyrolysis products. All catalysts were found to increase the amount of phenolic compounds, which are very important in the chemical (adhesives) industry. A low Si/Al ratio was found to have a positive effect on product yields and composition. Fe–Al-MCM-41 and Cu–Al-MCM-41 are the best metal-containing catalysts in terms of phenols production. The presence of the Al-MCM-41 material was also found to decrease the fraction of undesirable oxygenated compounds in the bio-oil produced, which is an indication that the bio-oil produced is more stable.     

Efficient catalysis of mesoporous Al-MCM-41 for Mukaiyama aldol reactions

Mesoporous aluminosilicates, Al-MCM-41 (Si/Al = 20 and 50), efficiently catalyzed Mukaiyama aldol reaction of benzaldehyde with 1-(trimethylsiloxy)cyclohexene in CH₂Cl₂ at 0 °C to afford the corresponding β-trimethylsiloxy ketone in quantitative yield. On the other hand, mesoporous silica (MCM-41), amorphous SiO₂–Al₂O₃, and H–Y and H-ZSM-5 zeolites barely catalyzed the reaction. Additionally, the less ordered Al-MCM-41 prepared by mechanical compression exhibited much lower catalytic activity compared with Al-MCM-41, indicating that the presence of the ordered mesoporous structure in aluminosilicates is crucial for the catalysis. The Al-MCM-41 catalyzed Mukaiyama aldol reaction was applicable to a wide range of aldehydes and silyl enol ethers. Furthermore, the Al-MCM-41 catalyst could be recycled at least three times without any loss in the yield. Thus, mesoporous aluminosilicates are promising heterogeneous catalysts for fine chemicals synthesis.     

Activation of ethyl acetate over metal substituted MCM-41: application to alkylation and acylation

Al-MCM-41, Fe,Al-MCM-41 and Zn,Al-MCM-41 materials with different silicon to metal ratios were synthesized hydrothermally and characterized by XRD, BET, FT-IR, Acidity measurement by pyridine adsorbed FT-IR spectroscopy, ²⁹Si and ²⁷Al MAS NMR and ESR techniques. The orderly arrangement of mesoporous materials was clearly revealed from the XRD patterns. ²⁹Si and ²⁷Al MAS NMR established the co-ordination environment of silicon and aluminium. Electron paramagnetic resonance (EPR) study confirmed the co-ordination environment of Fe in Fe,Al-MCM-41 framework. The catalytic activity of these materials was evaluated in the vapour phase alkylation and acylation of ethylbenzene with ethyl acetate in the temperature range between 250 and 400 °C. The products were found to be 1,3-diethylbenzene (1,3-DEB), 1,4-diethylbenzene (1,4-DEB), 1,2-diethylbenzene (1,2-DEB), 4-ethylacetophenone (4-EAP) and acetophenone (AP). The reaction products revealed that activation of ethyl acetate is a convenient route for both alkylation and acylation reactions. The order of the catalysts activity for the reaction is found to be Fe,Al-MCM-41 (50) > Fe,Al-MCM-41 (100) > Zn,Al-MCM-41 (50) > Zn,Al-MCM-41 (100) > Al-MCM-41 (50) > Al-MCM-41 (100). In addition to the density of acid sites, the strength of acid sites is also important for this reaction. The effects of temperature, feed ratio, WHSV and time on stream were also examined and the results are discussed.