Alcohols Of Different Chain Lengths Research Articles

Selective and scalable catalytic dehydration of primary alcohols to linear alpha-olefins over CeO2-doped Al2O3

Catalytic dehydration of primary alcohols has been developed for selective and sustainable linear alpha-olefins (LAOs) production. While Al2O3-based catalysts with tunable Lewis acidity and thermal stability have shown promise in enhancing LAO selectivity, challenges like acidity loss and compromised selectivity persist. This study addresses the need for an efficient catalyst system, synthesizing CeO2-doped Al2O3 catalysts with varying Ce loading and assessing their performance in the dehydration of 1-hexanol. Characterization using various techniques revealed that 10 wt% CeO2–Al2O3 (10CA) catalyst exhibited the highest 1-hexene yield (88.1%) under optimized conditions. CeO2 doping enhanced both acidic and basic strength, with excess Ce (>15%) leading to acidity and basicity loss. The 10CA catalyst demonstrated effectiveness across alcohols of different chain lengths (C5 and C8) at varying temperatures, showcasing the impact of carbon chain length on product selectivity. The scalability of the process was explored, with the 10CA catalyst successfully applied from lab-scale (0.0072 L/day) to bench-scale (4.33 L/day) reactions. The bench-scale reaction yielded 79.9% 1-hexene with 90.5% conversion of 1-hexanol and 88.2% selectivity for 1-hexene. The successful scale-up of the catalytic dehydration process using the 10CA catalyst underscores its potential as a pivotal component in the green economy, promoting sustainability and environmental friendliness in producing LAO.

A Green Lipophilization Reaction of a Natural Antioxidant

A natural antioxidant, widely spread in plants, chlorogenic acid (CGA), can be lipophilized through a heterogeneous, non-enzymatic, catalytic process. Thus, sulfonic resins under no solvent conditions allow to obtain a series of esters in up to 93% yield through reaction of CGA with fatty alcohols of different chain length. The reaction takes place in one single step under mild conditions with conversions up to 96% and selectivity up to 99%. Product recovery in high purity was very easy and the esters obtained were fully characterized with spectroscopic techniques and through the DPPH test to verify the preservation of antioxidant activity. According to this test, all of them showed increased activity with respect to the parent acid and anyway higher than butylated hydroxyanisole. An in-silico method also suggested their very low toxicity. The increased lipophilicity of the esters allows their formulation in cosmetic and nutraceutic lipid-based products.

Xylose-Based Polyethers and Polyesters Via ADMET Polymerization toward Polyethylene-Like Materials

One of the challenges of developing bioderived polymers is to obtain materials with competitive properties. This study investigates the structure-properties relationships of polyesters and polyethers that can be derived from d-xylose through metathesis polymerization, in order to produce bioderived plastic materials that are sourced from sustainable feedstocks and whose properties can compete with those of polyolefins such as polyethylene. Bicyclic diol 1,2-O-isopropylidene-α-d-xylofuranose was coupled with ω-unsaturated fatty acids and alcohols of different chain lengths (C11, C5, C3), and the resulting α,ω-unsaturated esters and ethers polymerized via an acyclic diene metathesis (ADMET) polymerization using a commercial Grubbs second-generation catalyst, obtaining polymers with Mn up to 63.0 kg mol–1. Glass transition temperatures (Tg) decreased linearly with increasing chain length and were lower for polyethers (−32 to 14 °C) compared to polyesters (−14 to 45 °C). ADMET polymers could be modified postpolymerization by reacting their internal carbon–carbon double bonds. Thiol–ene reaction with methyl thioglycolate lowered the Tg while allowing insertion of additional functional groups. Alkene hydrogenation turned the polyester and polyether with C20 hydrocarbon linkers into semicrystalline polymers with Tm ≈ 50 °C. The latter, when cast into films, displayed remarkable polyethylene-like properties. Hot-pressed films proved ductile materials (Young modulus Ey 60–110 MPa, elongation at break εb 670–1000%, ultimate tensile strength σb 8–10 MPa), while uniaxially oriented films proved very strong yet flexible materials (Ey 190–200 MPa, εb 160–350%, σb 43–66 MPa). Gas barrier properties were comparable to those of commercial polyolefins. Polyethers were resistant to hydrolysis, while polyesters depolymerized under alkaline conditions.

TiO2/Cu2O/CuO Multi-Nanolayers as Sensors for H2 and Volatile Organic Compounds: An Experimental and Theoretical Investigation.

TiO2/Cu2O/CuO multi-nanolayers highly sensitive toward volatile organic compounds (VOCs) and H2 have been grown in various thicknesses by a cost-effective and reproducible combined spray-sputtering-annealing approach. The ultrathin TiO2 films were deposited by spray pyrolysis on top of sputtered-annealed Cu2O/CuO nanolayers to enhance their gas sensing performance and improve their protection against corrosion at high operating temperatures. The prepared heterostructures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ultraviolet visible (UV-vis) and micro-Raman spectroscopy. The gas sensing properties were measured at several operating temperatures, where the nanolayered sensors with oxide thicknesses between 20 and 30 nm (Cu2O/CuO nanolayers) exhibited a high response and an excellent selectivity to ethanol vapor after thermal annealing the samples at 420 °C. The results obtained at an operating temperature of 350 °C demonstrate that the CuO/Cu2O nanolayers with thicknesses between 20 and 30 nm are sensitive mainly to ethanol vapor, with a response of ∼150. The response changes from ethanol vapors to hydrogen gas as the thickness of the CuO/Cu2O nanolayers changes from 50 to 20 nm. Density functional theory-based calculations were carried out for the geometries of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) heterostructures and their sensing mechanism toward alcohols of different chain lengths and molecular hydrogen. The reconstructed hexagonal Cu2O(111) surface and the reconstructed monoclinic CuO(1̅11) and TiO2(111) facets, all of which terminate in an O layer, lead to the lowest surface energies for each isolated material. We studied the formation of the binary and ternary heteroepitaxial interfaces for the surface planes with the best-matching lattices. Despite the impact of the Cu2O(111) substrate in lowering the atomic charges of the CuO(1̅11) adlayer in the binary sensor, we found that it is the different surface structures of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) devices that are fundamental in driving the change in the sensitivity response observed experimentally. The experimental data, supported by the computational results, are important in understanding the use of the multi-nanolayered films tested in this work as reliable, accurate, and selective sensor structures for the tracking of gases at low concentrations.

Preparation and Application of Magnetic Nano-Solid Acid Catalyst Fe3O4-PDA-SO3H

A magnetic nano-solid acid catalyst Fe3O4-PDA-SO3H was synthetized through an efficient method, as an eco-friendly and more efficient catalyst. The obtained catalyst has uniform core-shell structure, appropriate particle size, and high acid density. Fe3O4-PDA-SO3H was applied to catalyze the esterification of levulinic acid (LA) with alcohols of different chain length to produce the levulinate esters. The catalytic effect was optimized from the aspects of catalyst dosage, reaction temperature, and acid-alcohol molar ratio. Furthermore, the response surface optimization method was used to obtain the optimal conditions. Verified under these conditions, the experimental results showed that the conversion rate of LA can reach 95.87%, which was much higher than common cationic exchange resin Amberlyst 36 and Amberlyst 46. Furthermore, the recovery and reuse of the Fe3O4-PDA-SO3H was demonstrated six times without obvious loss in the activity.

Impact of the Surface Properties of Cellulose Nanocrystals on the Crystallization Kinetics of Poly(Butylene Succinate)

The hydrophilicity of cellulose nanocrystals (CNCs) is a major challenge for their processing with hydrophobic polymers and matrices. As a result, many surface modifications have been proposed to hydrophobize CNCs. The authors showed in an earlier study that grafting alcohols of different chain lengths onto the surface of CNCs using toluene diisocyanate (TDI) as a linker can systematically hydrophobize CNCs to a water contact angle of up to 120° depending on the alcohol chain length. Then, the hydrophobized CNCs were used to mechanically reinforce poly(butylene succinate) (PBS), which is a hydrophobic polymer. As a result of hydrophobization, PBS/CNCs interfacial adhesion and the composite mechanical properties significantly improved with the increasing CNC contact angle. Continuing on these results, this paper investigates the impact of CNC surface properties on the crystallization behavior of PBS using differential scanning calorimetry (DSC). The results showed that the crystallization temperature of PBS increased from 74.7 °C to up to 86.6 °C as a result of CNC nucleation activity, and its value was proportionally dependent on the contact angle of the CNCs. In agreement, the nucleation activity factor (φ) estimated using Dobreva and Gutzow’s method decreased with the increasing CNC contact angle. Despite the nucleation action of CNCs, the rate constant of PBS crystallization as estimated using the Avrami model decreased in general as a result of a prevailing impeding effect. This decrease was minimized with increasing the contact angle of the CNCs. The impeding effect also increased the average activation energy of crystallization, which was estimated using the Kissinger method. Moreover, the Avrami exponent (n) decreased because of CNC addition, implying a heterogeneous crystallization, which was also apparent in the crystallization thermograms. Overall, the CNC addition facilitated PBS nucleation but retarded its crystallization, and both processes were significantly affected by the surface properties of the CNCs.

Nano-Brushes of Alcohols Grafted onto Cellulose Nanocrystals for Reinforcing Poly(Butylene Succinate): Impact of Alcohol Chain Length on Interfacial Adhesion

Despite the many interesting properties of cellulose nanocrystals (CNCs), their hydrophilicity is one of the main challenges for their processing with hydrophobic polymers and matrices. To overcome this challenge, this paper describes the preparation of brush-like CNCs with tailored surface properties by grafting alcohols of different chain lengths onto their surfaces. Ethanol, 1-butanol, 1-hexanol, and 1-octanol were grafted on the CNC surface using 2,4-toluene diisocyanate (TDI) as a linker. The CNCs were characterized for their structural, morphological, surface, and thermal properties. Because of the grafting, the water contact angle of the CNCs significantly increased from 32° to up to 120°, which was dependent on the chain length of the grafted alcohol. The thermal stability of the CNCs was also improved, mainly as a result of the reaction of TDI with the CNC hydroxyl groups. Later, the CNCs were used to reinforce films of poly(butylene succinate) (PBS), which were then characterized using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). An increase of up to two-fold in the storage modulus was observed using DMA, which was dependent on the chain length of the grafted alcohol. However, no change in the glass transition temperature or degradation temperature of PBS was detected. This approach is proved efficient for tailoring the surface properties of CNCs towards excellent interfacial adhesion in their composites.

Manganese-catalyzed ring-opening carbonylation of cyclobutanol derivatives

Herein, we report a manganese-catalyzed ring-opening carbonylation of cyclobutanol derivatives through cyclic CC bond cleavage. The reaction happens via a radical-mediated pathway to selectively generate 1,5-ketoesters. A variety of substrates with substituents on the aromatic ring reacted with linear alcohols of different chain lengths. Obtained aliphatic esters are very attractive since they are usually difficult to access.

Caffeoyl maleic fatty alcohol monoesters: Synthesis, characterization and antioxidant assessment

HypothesisCaffeoyl malate anhydride, as a good nucleophilic acceptor, can react with lipophilic fatty alcohols to yield interface-confined amphiphiles. The resulting novel molecules are hypothesized to deliver combined functionalities of parent natural building blocks, as emulsifier, stabilizer, ion chelator and free radical scavenger. ExperimentsRing-opening reactions of caffeoyl malate anhydride with fatty alcohols of different chain lengths generated a new group of antioxidant amphiphiles. Structural verification was by MS (mass spectrometry), 1H/13C NMR (nuclear magnetic resonance) and FT-IR (Fourier transform infra-red) spectroscopy. Physicochemical characterization was done by use of DSC (differential scanning calorimetry), FT-IR, determinations of critical micelle concentrations (CMC) and calculations of HLB. Antioxidant activity was assessed by DPPH (2, 2-diphenyl-1-picrylhydrazyl) and hydroxyl radical scavenging activities. Dynamic light scattering (DLS) studies demonstrated surface-activity of G8–G18. Inhibition of iron- and thermally-accelerated lipid oxidation was monitored by thiobarbituric acid reactive substances (TBARS) assay. FindingsDerivatization of caffeoyl malate anhydride with fatty alcohols maintained free radical scavenging activity, and improved hydroxyl radical scavenging activity of caffeic acid. Lipid oxidation at 22 °C was significantly inhibited (up to 3.5 times) in emulsions stabilized by G8–G18 with or without chitosan compared to emulsions stabilized by commercial emulsifiers and stabilizers. Thermal oxidation (at 80 °C) was 10 times less in emulsions facilitated by G8–G18 in combination with chitosan compared to emulsions stabilized by commercial emulsifiers and stabilizers. This study has developed a simple and straightforward approach for developing value-added compounds from underexplored fatty alcohols.

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

Telomerization of 1,3-butadiene with highly substituted alcohols using Pd/NHC-catalysts — Structure-reactivity-relationship of the O-nucleophile

Catalytic telomerization of 1,3-butadiene with alcohols is a catalytic reaction and an effective tool to synthesize 2,7-octadienyl ethers with different characteristics depending on the alcoholic substrate. While Pd/phosphine type catalysts were studied in depth, highly active Pd/NHC (=N-heterocyclic carbene) catalysts have been studied in the telomerization almost exclusively along with methanol. In the course of employing alcohols from renewables, e.g., lignin, cellulose or terpenes etc., a deeper understanding of the reactivity of these catalysts is needed.In this work, we present comprehensive investigations with linear and branched alcohols of different chain-lengths. Distinct tendencies in reaction behavior between primary and secondary alcohols were found and the lower reactivity of secondary alcohols could clearly be attributed to electronic properties, along with steric hindrance.Furthermore, the influence of double bonds in the alcohol chain has been studied. Interestingly, alcohols with double bonds that are not conjugated to the hydroxyl groups were shown to be more active than saturated alcohols. Allylic alcohols, however, are significantly less reactive than their saturated analogs.With the gathered information, we were able to deduce a structure reactivity-relationship of certain functional groups and substitution patterns. These findings were proved by employing terpenols to gain new allylic terpenol ethers.

Synthesis and Properties of Anionic Maleic Monoester Carboxylate Polymeric Surfactants

Four anionic maleic monoester carboxylate polymeric surfactants were synthesized by the reaction of maleic anhydride with linear alcohols of different chain length in the ratio of 1:1.1 under 80 °C. Then the intermediate products were neutralized by sodium hydroxide at 60 °C to produce the final monomers. The structures of products were confirmed by FTIR. The surface tension was measured at 45 °C and the thermodynamic parameters were calculated. The results show that the polymeric surfactants possess low critical micelle concentration (CMC), high adsorption affinities and good surface and interfacial activity.

Antioxidative effect of lipophilized caffeic acid in fish oil enriched mayonnaise and milk

The antioxidative effect of lipophilized caffeic acid was assessed in two different fish oil enriched food products: mayonnaise and milk. In both emulsion systems, caffeic acid esterified with fatty alcohols of different chain lengths (C1–C20) were better antioxidants than the original phenolic compound. The optimal chain length with respect to protection against oxidation was, however, different for the two food systems. Fish oil enriched mayonnaise with caffeates of medium alkyl chain length (butyl, octyl and dodecyl) added resulted in a better oxidative stability than caffeates with shorter (methyl) or longer (octadecyl) alkyl chains. Whereas in fish oil enriched milk emulsions the most effective caffeates were those with shorter alkyl chains (methyl and butyl) rather than the ones with medium and long chains (octyl, dodecyl, hexadecyl and eicosyl). These results demonstrate that there might be an optimum alkyl chain length for each phenolipid in each type of emulsion systems.

Effect of cosolvents in the presence of sodium dodecyl sulfate micelles on the rate of alkaline hydrolysis of tris(2,2′-bipyridine)iron(II) complex

The kinetics of alkaline hydrolysis of tris(2,2′-bipyridine)iron(II) complex have been studied in the presence of various alcohols of different chain lengths and number of OH groups in aqueous and SDS micellar medium. In aqueous medium, rate increases at all percentages of 1-alkanols in the following order: PrOH>EtOH>MeOH>H2O, whereas the effectiveness of glycols as inhibitors is in the following order: Gly>EG>PG>H2O. Hence PrOH has the most pronounced effect as accelerator and Gly as inhibitor on rate. In the presence of SDS micelles, rate has been inhibited because of binding of SDS with substrate, but the presence of alcohols reduces this inhibitory effect of SDS. All these results have been explained in terms of the CMC, micellar size and properties of SDS in these cosolvents, H-bonding capacity of solvents, dielectric constants of the media, etc.

Comparative study of zeolite catalyzed alkylation of benzene with alcohols of different chain length: H-ZSM-5 versus mordenite

Alkylation of benzene with light alcohols offers opportunities for a more environmental friendly gasoline by removing considerable portions of benzene. The performances of ZSM-5 and mordenite zeolites as catalysts were tested in the alkylation reaction of benzene with different light alcohols (methanol, ethanol and isopropanol). The experiments were carried out in a fluidized-bed reactor with a 1/1 mol ratio of benzene/alcohol at 200, 250, 300, 350 and 400°C for 3, 5, 7, 10, 13, 15 and 20s. The reaction temperature, nature of the alcohol molecule and the BrǾnsted to Lewis acid ratio of the catalysts, play an important role in the alkylation reactions. For benzene alkylation with methanol to toluene and xylene (XY), both mordenite and ZSM-5 are active and selective catalysts, while for benzene ethylation to ethylbenzene (EB), ZSM-5 exhibits higher EB selectivity than mordenite. Isopropanol presents higher difficulty to be activated as compared with other alcohols at the higher temperature, while the lower temperature favors benzene isopropylation to cumene over both catalysts. By studying the alkylation of benzene with alcohols of different chain length, it has been found that as the alkyl size (i.e. methyl, ethyl, and propyl) increases, the optimum temperature for alkylation reaction decreases.

Investigation of the Local Structure of Mixtures of an Ionic Liquid with Polar Molecular Species through Molecular Dynamics: Cluster Formation and Angular Distributions

In this work, we used molecular dynamics simulations to analyze in detail the spatial distributions of the different constituents in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate with three polar molecular species: water and two alcohols of different chain lengths (methanol and ethanol). In particular, we report results regarding the influence of the chosen species and its concentration on the formation of ionic and molecular clusters over the whole miscibility range, as well as on the angular distribution of polar molecules around the anion and the cation in these systems. Both analyses showed that addition of a molecular species breaks down the polar network of the pure ionic liquid in clusters whose mean size decreases progressively as more molecules are added. At very high concentrations of the molecular species, the ions are found to be isolated in mixtures with water and methanol, but they tend to form pairs in ethanol. In mixtures with water we identified large clusters that form a water network at very high water concentrations, while at low water concentrations polar molecules tend to form smaller aggregates. In contrast, in mixtures with alkanols there is no evidence of the formation of large alcohol clusters at any concentration. Spatial order in alcohol was also studied by means of the Kirkwood G factor, reaching the conclusion that the angular correlations which appear in pure alcohols due to dipole interactions are destroyed by the ionic liquid, even when present only in tiny amounts.

Dynamical Properties of Alcohol + 1-Hexyl-3-methylimidazolium Ionic Liquid Mixtures: A Computer Simulation Study

In this work, extensive molecular dynamics simulations of the dynamics of mixtures of ionic liquids (ILs) composed of the cation 1-hexyl-3-methylimidazolium and several anions of different hydrophobicity degrees (Cl(-), BF(4)(-), PF(6)(-)) with alcohols of different chain lengths (methanol and ethanol) are reported. We evaluated the influence of the nature of the anion, the length of the molecular chain of the alcohol, and the alcohol concentration on some dynamical properties of the mixtures, such as self-diffusion coefficients of all the species, mean square displacements (with an analysis of both ballistic and diffusive regimes), and velocity autocorrelation functions of alcohol molecules. The diffusivity of the mixtures was found to be highly dependent on the nature of the anion since the interaction between chloride and alcohols is greater than that with fluorinated anions and leads to slower dynamics. Additionally, our results show that self-diffusion coefficients increase with alcohol concentration. On the other hand, a subdiffusive regime over thousands of picoseconds was detected at intermediate times through analysis of the center-of-mass mean square displacements of alcohol molecules, a region that becomes narrower as alcohol concentration increases. Finally, the study of the role of the anion and of solvent concentration on velocity autocorrelation functions reflects an increase in mean collision times as the amount of alcohol increases until the value of pure alcohols is reached. These collision times are smaller in mixtures with halogenated ILs.

Influence of Chain Length of Alcohols on Stokes’ Shift Dynamics in Catanionic Vesicles

In this paper, we explore the effects of the chain length of simple monohydroxy alcohol (C(n)OH, 2 ≤ n ≤ 8) and benzyl alcohol (C(6)H(5)CH(2)OH) upon the fluorescence dynamics of a dipolar solute probe, coumarin 153 (C153), in vesicles formed in aqueous solutions of two oppositely charged (cationic and anionic) surfactants in the presence of 0.05 mol kg(-1) alcohol. The catanionic vesicles are composed of 70 mol % sodium dodecyl sulfate (SDS) and 30 mol % cetyltrimethylammonium bromide (CTAB). The presence of alcohols of different chain length improves the stability of the catanionic vesicles. Dynamic light scattering (DLS) experiments suggest a gentle increase in the hydrodynamic diameter of the catanionic vesicle with alcohol chain length up to n=4 and then an abrupt increase for the rest of the alcohols considered. The polarity and dynamics of the catanionic vesicles, probed by the steady-state and time-resolved fluorescence spectroscopy, indicate a signature of confined water. Quantities measured from fluorescence experiments of these vesicles also show a mild variation for alcohols of chain length n ≤ 4, followed by a sudden variation for alcohols with n > 4. Interestingly, pentanol and benzyl alcohol in catanionic vesicles showed roughly similar effects due to their equivalent chain length. All of these data are remarkably correlated with the recently observed depression of the solubility temperature of catanionics with alcohol chain length (Langmuir2009, 25, 12516-12521).

Improved HRGC Separation of cis, trans CLA Isomers as Diels-Alder Adducts of Alkyl Esters

This paper reports the separation of four isomers of conjugated linoleic acid (CLA), c,t/t,c-8,10; c,t/t,c-9,11; c,t/t,c-10,12; c,t/t,c-11,13, after reaction of esterification with aliphatic alcohols of different chain length and adduct formation with 4-methyl-1,2,4-triazoline-3,5-dione (MTAD). The high resolution gas chromatographic analyses were carried out using a simple 50-m cyanopropyl polysiloxane capillary column both with a flame ionization detector and a mass spectrometer. The resolution between the two pair of isomers: c,t/t,c-9,11 and c,t/t,c-10,12 and between c,t/t,c-10,12 and c,t/t,c-11,13 isomers were good for all the investigated alkyl esters and increased with the chain length of alcohol esterified to carboxylic moiety of CLA isomers. The most interesting result was relative to the c,t/t,c-8,10 and c,t/t,c-9,11 isomers, critical pair of isomers also when analyzed with a 120-m cyanopropyl polysiloxane capillary column; their resolution also increased from methyl to hexyl esters of CLA isomers and reached an acceptable value (0.8) in the case of hexyl esters. The best resolutions of the four considered CLA isomers were obtained with the hexyl esters of MTAD adducts of the isomers, without excessive analysis time. This method was useful and simple to evaluate the profile of the four main c,t isomers in commercial CLA samples.

Structure-reactivity relationship for aromatics transalkylation and isomerization process with TNU-9, MCM-22 and ZSM-5 zeolites, and their industrial implications

TNU-9 is a medium pore zeolite with a complex tridimensional channel system. Its catalytic properties have been studied in some reactions that involve the BTX fraction, such as benzene and toluene alkylation with methanol, ethanol or isopropanol. These reactions use in practice medium pore zeolites such as ZSM-5 (MFI) or MCM-22 (MWW), and the selectivities obtained with TNU-9 are compared and analyzed from the point of view of the zeolite structure and pore topology, as well as from its possible industrial application. For benzene alkylation to give ethylbenzene (EB), TNU-9 is an active and selective catalyst with selectivities to EB much higher than ZSM-5 and close to those of the industrially relevant MCM-22. However, olefin oligomerization within the pores of TNU-9 occurs in a larger extension than with MCM-22, leading not only to some lower selectivity, but also to a faster catalyst deactivation. In the case of cumene formation, again the selectivity of TNU-9 to the desired product is higher than ZSM-5 but lower than MCM-22, owing to the formation of larger amounts of n-propylbenzene in the former as a result of its pore topology. Nevertheless, TNU-9 may be worth to be studied further for the disproportionation of toluene to give xylenes. In this case, its comparison with ZSM-5 appears of interest. By studying the alkylation of toluene with alcohols of different chain length, i.e. methanol, ethanol and isopropanol, it has been found that TNU-9 has an antagonistic behaviour, closer to ZSM-5 or MCM-22 depending on the activity or selectivity parameters considered that could be explained by its complex topology, formed by 10-ring tortuous channels with crosses as in ZSM-5, and large cavities as in MCM-22.