The Influence of Solvent on the Acidity and Activity of Supported Sulfonic Acid Catalysts

The acid strengths and catalytic activities of sulfonic acids supported on polystyrene resins and ordered mesoporous HMS and SBA-15 silicas are compared. Acid strengths are measured by acid–base titration calorimetry in terms of the molar enthalpies of neutralisation with either NaOH or n-butylamine in water, acetonitrile and cyclohexane. Catalytic activities (turnover numbers) are reported in model reactions in water, 1,2-dichlorobenzene and anisole, and compared with acid strengths. In water, sulfonated resins are both stronger acids and more active catalysts than sulfonated silicas. Catalytic activities in water correlate well with these measured acid strengths. In acetonitrile the order of acid strengths is reversed and the sulfonated silicas are the stronger acids. Catalytic measurements in 1,2-dichlorobenzene, a similar dipolar aprotic solvent, show the same reversed order of activities. In the non-polar solvent cyclohexane (where only macroporous sulfonated resins show measurable acidity) the sulfonated silicas are again the stronger acids but by a larger margin. Catalytic activities in anisole, which is also only very weakly solvating towards sulfonic acid groups, show a similar trend. The results illustrate the role of the solvent in controlling the acid strength of solid acid catalysts, and the importance of taking this into account when designing acid catalysts for liquid phase processes.     

Synthesis of Glycerol Triacetate Using a Brønsted–Lewis Acidic Ionic Liquid as the Catalyst

Brønsted–Lewis acidic ionic liquids (IL) were used in the esterification of glycerol and acetic acid to produce glycerol triacetate. The results show that the IL (3–sulfonic acid)–propyltriethylammonium chloroironinate [HO₃S–(CH₂)₃–NEt₃]Cl–[FeCl₃]_x (molar fraction of FeCl₃, x = 0.67) was an efficient catalyst for the esterification reaction. The yield of glycerol triacetate and its content were greater than 98 % when reacted under reflux for 4 h. It was observed that a synergistic effect of Brønsted and Lewis acid sites enhanced the catalytic performance of IL. The reusability of IL was good. After six reaction cycles, the glycerol triacetate yield and concentration were still greater than 98 %. Likewise, the Brønsted–Lewis acidic IL was an efficient catalyst for esterification reactions of high boiling points alcohols with acetic acid.     

Biodiesel Production Over Arenesulfonic Acid-Modified Mesostructured Catalysts: Optimization of Reaction Parameters Using Response Surface Methodology

The catalytic activity of different heterogeneous sulfonic acid-modified catalysts has been assayed in the simultaneous esterification of FFA and transesterification of triglycerides of crude palm oil (FFA content of 5.6 wt%) with methanol, demonstrating the applicability of this kind of acid solids to the one-step production of biodiesel from FFA-containing vegetable oils. The yield towards fatty acid methyl esters (FAMEs) obtained over these acid materials is enhanced when increasing the acid strength of the catalytic site. Likewise, the use of mesostructured supports has been shown as a factor improving the catalytic performance as compared with macroporous sulfonic acid-based resins, likely due to an enhancement of the mass transfer rates of large molecules, such as triglycerides, within the catalyst structure. Thus, the combination of the open mesoporous structure of a SBA-15 silica support with relatively strong arenesulfonic acid sites leads to a material able to yield high conversion of triglycerides and free fatty acids. Furthermore, a study on the transesterification reaction of crude palm oil with methanol through a surface response analysis has provided as optimal conditions the following: temperature 160 °C, catalyst loading 5.1 wt% referred to the amount of palm oil, and methanol to oil molar ratio 30. Under these conditions, almost 90% of the starting oil is converted to FAME after reacting for just 2 h of reaction. Likewise, surface response analysis has evidenced a strong interaction between temperature and methanol to oil ratio.     

磺酸基官能化介孔材料的表征及其催化性能

由高水热稳定的巯基官能化介孔硅基材料经氧化得到磺酸基官能化介孔固体酸催化剂。经过一系列的表征测试,所得固体酸具有发达的孔道结构和大量Br尴nsted酸性位。将其应用于苯甲醛与醇类缩合反应中,与传统沸石固体酸催化剂HY相比,显示了更好的催化性能,缩醛收率在90%左右。所合成的磺酸基官能化介孔固体酸催化剂的催化性能基本不受醇类分子体积影响,具有很好的重复使用性能。     

Novel Esterification of Glycerol Catalysed by Tin Chloride (II): A Recyclable and Less Corrosive Process for Production of Bio-Additives

Abstract  

In this work, a novel process based on use of a SnCl₂·2H₂O catalyst which is less corrosive, inexpensive, and a water tolerant Lewis acid was employed for synthesis of fuel bio-additives from glycerol. High yields and selectivities were achieved for glycerol esterification with acetic acid under mild reaction conditions. The SnCl₂ catalyst showed to be as active as p-toluene sulfonic and sulfuric acid, catalysts commonly used in acid-catalysed esterification reactions. However, its use has significant advantages in comparison to these Br?nsted acid catalysts, including lower reactor corrosion and unnecessary neutralization at the end reaction. The SnCl₂ catalyst can also be recovered and reused without loss of catalytic activity. Additionally, effects of reaction temperature, HOAc:glycerol molar ratio and catalyst concentration on both selectivity and yield of glycerol acetates were also investigated. The lower corrosiveness, facilitated handling, as well as potential for reuse without activity loss after simple recycle protocols are positive aspects of SnCl₂ catalysts.     

H3PW12O40 Supported on AlMCM-41 molecular sieves: An effectual catalyst for t-butylation of anisole

Mesoporous AlMCM-41 (Si/Al = 25) molecular sieves was synthesized and impregnated with different loadings (10, 20 and 30 wt% H₃PW₁₂O₄₀) of phosphotungstic acid. Their catalytic performance was examined in the vapour phase alkylation of anisole with tert-butanol. The major products were found to be 2-tert-butyl anisole (2-TBA), 4-tert-butyl anisole (4-TBA), 2,4-di-tert-butyl anisole (2,4-DTBA). 4-TBA was the major product formed with high selectivity. The influence of temperature, feed ratio, WHSV was studied and the results are discussed.     

Mesoporous molecular sieves: alkylation of anisole using tert-butylalcohol

Mesoporous aluninosilicate Al-MCM-41 molecular sieves with Si/Al ratios 25, 50, 75 and 100 have been synthesized under hydrothermal condition and these materials were characterized by XRD, FTIR, BET and pyridine adsorption techniques. The catalytic performance was examined in the vapor phase tert-butylation of anisole with tert-butanol at the temperatures between 150 and 250 °C under atmospheric pressure. The results indicate that Al-MCM-41 (25) was found to be more active than its relatives. The major products are found to be 4-tert-butyl anisole (4-TBA), 2-tert-butyl anisole (2-TBA) and 2,4 di-tert-butyl-anisole (2,4-DTBA). Maximum conversion of anisole is observed at 175 °C and decreased thereafter with increasing temperature. The influence of molar feed ratio, influence of temperature, WHSV and time on stream on the selectivity of products was investigated and the results are discussed.     

An Efficient Binary Solvent Mixture for Monoacylglycerol Synthesis by Enzymatic Glycerolysis

The present study was aimed at selecting an efficient binary solvent mixture for monoacylglycerol (MAG) synthesis by enzymatic glycerolysis of soybean oil. Solvent combinations of tert-butanol/isopropanol (v/v) at different ratios were studied. Of the investigated cases, tert-butanol:isopropanol at ratio 80:20 was the most suitable organic medium. The optimum conditions for MAG synthesis under the selected mixture were: water 10 wt% based on glycerol, Lipozyme TL IM 15 wt% based on oil and glycerol, weight ratio of solvent to oil 4:1, and molar ratio of glycerol to oil 3.5:1. Under these conditions with a 4-h reaction, the yield of MAG was 72.0% where the triacylglycerol (TAG) content was reduced to only 1.0% (based on acylglycerols). Fatty acid ester (FAE) formation from the solvents was very low in the final product (1.3% based on reaction mixture). The selected binary solvent mixture has good physical properties with low melting point (−26.5 °C), which can avoid the risk of crystallization in practical operations.     

CpMo(CO)3Cl as a precatalyst for the epoxidation of olefins

The tricarbonyl complex CpMo(CO)₃C1 was found to act as a precatalyst for the reaction of tert-butyl hydroperoxide and olefins to yield the corresponding epoxides and diols. Under the reaction conditions, oxidative decarbonylation leads to the formation of the dioxo complex CpMoO₂Cl. The catalytic recyclability and the effect of temperature on the catalytic results have been examined, and a reaction mechanism proposed, supported by kinetic modelling.     

Etherification of glycerol by isobutylene. Effects of the density of acidic sites in ion-exchange resin on the distribution of products

Etherification of glycerol by isobutylene was performed using ion-exchange resin Amberlyst 15, partially neutralized Amberlyst 15 as heterogeneous catalyst, and p-toluenesulfonic acid as a homogeneous catalyst. Amberlyst 15 exhibited strong internal diffusion limitations for the initial composition of reaction mixture. Diffusion limitations decrease in the course of reaction due to the accumulation of mono-ether having excellent solubilizing properties. Oligomerized isobutylene is a dominant by-product for high isobutylene-to-glycerol ratio and long contact time in the case of Amberlyst 15. Density reduction of acidic protons in Amberlyst 15 by partial ion exchange with sodium ions leads to considerable reduction of isobutylene affinity to Amberlyst 15, and as a result, it reduced losses of isobutylene. This partial neutralization leads to lower space-time yields of target products, but enhances selectivity to higher ethers with maintaining conversion of glycerol over 95%.     

Enzymatic synthesis and spectroscopic characterization of 1,3-divernoloyl glycerol fromVernonia galamensis seed oil

cis-12,13-Epoxy-cis-octadecenoic (vernolic) acid occurs in triglycerides of the seed oil ofVernonia galamensis. The seeds also contain a lipase capable of hydrolyzing the triglycerides. Previous investigators incubated the seed ofVernonia anthelmintica and isolated 5.6% yield of 1,3-divernoloyl glycerol. We used crude lipase extract fromV. galamensis seed to synthesize 1,3-divernoloyl glycerol from vernonia oil in pentane at 40% yield. A 94% conversion of the 1,3-divernoloyl glycerol to pure vernolic acid (5.34% oxirane = 98.9% purity) was achieved by a low-energy saponification process. The carbon-13 nuclear magnetic resonance (NMR) spectrum of the 1,3-divernoloyl glyceride indicates a potential for using carbon-13 NMR spectroscopy in the identification of isomeric diglycerides. Thus the paper describes the synthesis, spectroscopic and chemical characterization of 1,3-divernoloyl glycerol, in addition to providing quantitative carbon-13 NMR studies ofV. galamensis oil.     

Alkylation of hydroquinone with tert-butanol over AlSBA-15 mesoporous molecular sieves

A series of AlSBA-15 catalysts with different pore size and different Si/Al ratio were prepared and characterized by N₂ adsorption and NH₃-temperature programmed desorption (NH₃-TPD) methods. Their catalytic behaviors for the alkylation of hydroquinone with tert-butanol were studied and compared with that of HZSM-5, HY, HAlMCM-41. It is found that the catalytic activity correlates well with the amount of medium-strong acid sites on the surface of the catalysts, and the selectivity towards 2-tert-Butylhydroquinone has some connection with the pore size of the catalysts. The reusability of the catalyst depends on its hydrothermal stability, which needs to be improved for the AlSBA-15 catalysts.     

Dehydration of xylose into furfural over micro-mesoporous sulfonic acid catalysts

Surfactant-templated micro-mesoporous silicas possessing sulfonic acid groups (SAGs) have been prepared, characterized, and tested as catalysts in the dehydration of d-xylose to furfural. All of the materials possessed catalytic activity. In general, selectivity to furfural was lower for a poorly ordered microporous hybrid material, prepared via the co-condensation of (3-mercaptopropyl)trimethoxysilane with bis(trimethoxysilylethyl)benzene, than for mesoporous MCM-41 silica anchored with SAGs via postsynthesis modification. The MCM-41 material with the highest loading of SAGs (0.7 meq g⁻¹) displayed fairly high selectivity for furfural (ca. 82% in DMSO or water/toluene mixture) at high xylose conversion (>90% within 24 h, at 140 °C). Xylose conversion increased significantly with reaction temperature. At 170 °C, more than 85% conversion was achieved within 4 h with any of the sulfonic acid-functionalized catalysts. Furfural yield tended to increase with temperature. Xylose conversion increased with increasing amount of catalyst, and for a xylose/MCM-41-SO₃H ratio of 0.5, 76% conversion was achieved within 4 h, at 140 °C. Catalyst deactivation was observed after long residence times, possibly because of the interaction of reaction products with the acid sites, leading to surface loading.     

Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO₂. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.Catalysis by solid superacids, Part 30. For part 29, see ref.[1A].     

Solvent and oxidant effects on the Au/TiO2-catalyzed aerobic epoxidation of stilbene

Molecular oxygen can be used as the main oxidant to selectively epoxidize trans-stilbene over Au/TiO₂ catalysts, in a free-radical process. However, the nature of the radical initiator has a critical influence on the reaction selectivity. tert-Butylhydroperoxide (TBHP, catalytic amount) leads to high yields of epoxide; on the other hand, hydrogen peroxide and di-tert-butylperoxide merely cause degradation of trans-stilbene. The choice of the solvent is also critical. Amongst the selected solvents, only alkyl-substituted cyclohexanes lead to high yields of epoxide, despite the poor dispersion of the catalytic powder. Other solvents, including the more polar ones and cyclohexane, are significantly less efficient, both in terms of total activity and epoxide production. The latter does not go beyond the yield expected from the potential stoichiometric reaction between TBHP and trans-stilbene (5%). On the basis of these results, an aerobic epoxidation mechanism is proposed in which molecular oxygen is activated by a substituted cyclohexyl radical produced by abstraction of a tertiary hydrogen atom from the solvent molecule by a tert-butylperoxy radical.     

Sulfated tin oxide: An efficient catalyst for alkylation of hydroquinone with tert-butanol

Sulfated tin oxide prepared by thermal decomposition of Stannous sulfate displays high activity for the alkylation of hydroquinone with tert-butanol, over which the conversion of hydroquinone and yield of 2-tert-butylhydroquinone reach 96% and 65% at 150 °C. No obvious deactivation was observed during the first four runs. The high activity was due to its hydrophobic surface on which the acid sites were not easy to be poisoned by water during the reaction, and the high reusability may result from the weak strength of its acid sites on which less tar or polymeric compounds would be formed by the side reactions.     

Alkylation of phenols with isobutylene

The kinetics of absorption of isobutylene in molten phenol, p-cresol and pyrocatechol were studied in a stirred cell using concentrated sulphuric acid as a catalyst. The absorption of isobutylene in molten phenols was found to conform to pseudo-first-order mechanism. The products of various reactions were analysed by gas-liquid chromatography. The absorption of isobutylene in mono-t-butyl derivatives of phenols was studied in an agitated glass reactor. It was possible to eliminate the effect of diffusion. The values for the rate constant of the second-order reactions between isobutylene and p-t-butylphenol at 104°, isobutylene and 2-t-butyl-p-cresol at 70° and isobutylene and 4-t-butylpyrocatechol at 104° were 49, 40 and 56 ml/g mole/sec, respectively. Mass transfer influenced the rate of alkylation of phenol and p-cresol with isobutylene in a bubble column. However, no significant improvement was observed in the yield of the mono-derivative, which in some cases is the desired product.     

The catalytic activity of immobilized on modified silica metalloporphyrins bearing antioxidative 2,6-di-tert-butylphenol pendants

A comparative study of the catalytic activity of supported manganese(III) and iron(III) chlorides of meso-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin (R₄PMnCl, R₄PFeCl) and meso-tetraphenylporphyrin (TPPMnCl, TPPFeCl) is reported. The metalloporphyrins have been immobilized via coordination bond on the surface of two series of imidazole modified silica, imidazole propyl silica (IPS) and imidazole 3-(glycidyloxypropyl) silica (IGOPS). The heterogenised catalysts have been evaluated for hydrocarbon oxidation by sodium periodate. The critical role of 2,6-di-tert-butylphenol groups on the periphery of porphyrin ring in their catalytic activity has been evaluated and pertinent structural and mechanistic aspects are discussed.     

Organotin compounds immobilized on mesoporous silicas as heterogeneous catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide

Organotin compounds of (MeO)₂ClSi(CH₂)₃SnCl₃ have been grafted on a series of mesosporous silicas, as proved by XRD, N₂ adsorption/desorption experiments and FTIR, diffuse reflectance UV–vis and ¹³C CP/MAS NMR spectroscopies. A further substitution of Cl^? bonded to Sn⁴⁺ by CH₃O^? led to the formation of a series of active heterogeneous catalysts for the direct synthesis of dimethyl carbonate from methanol and CO₂. The catalytic properties of these catalysts depended on the structure, crystal size and surface properties of mesoporous silicas. SBA-15 as a host was superior to SBA-16 and large-pore Ia3d. In addition, the methods used for removing surfactants occluded in mesoporous silicas had strong influences on the catalytic performance as a result of significantly affecting the surface areas and the concentrations of surface hydroxyl groups of the mesoporous silicas. The extraction of surfactants by an ethanol–HCl solution should be available. An increase in the reaction time, reaction temperature, methanol amount and CO₂ pressure significantly increased the dimethyl carbonate yield before reaching thermodynamic equilibrium. The dimethyl carbonate yield could also be increased by adding dehydration agents to the reaction system. 2,2-Dimethoxypropane gave a much higher dimethyl carbonate yield than 3A molecular sieve and tetramethyl orthorsilicate. The prepared organotin/mesoporous silica catalysts were highly stable, as corroborated by the findings that the dimethyl carbonate yield obtained over the SBA-15-immoilized organotin compound did not decrease within six repeated runs with regeneration under the same reaction conditions and that the tetrahedral coordination state of Sn species was maintained after reaction.     

Ternary solubility of mono- and di-tert-butyl ethers of glycerol in supercritical carbon dioxide

Using a continuous flow apparatus, the ternary solubility of mono- and di-tert-butyl ethers of glycerol (MTBG and DTBG, respectively) in supercritical carbon dioxide was measured at the temperatures of 313.15, 333.15, and 348.15 K; a pressure range of 80-200 bar; and an expanded gas flow rate of 180 ± 10 mL min⁻¹ at average laboratory temperature of 300.15 K and pressure of 0.89 bar. The ternary solubility of the ethers at the constant temperatures of 333.15 and 348.15 K increased with increasing pressure up to the crossover point (i.e., 152 bar for MTBG and 170 bar for DTBG). MTBG exhibited a higher solubility than DTBG in scCO₂. The experimental data for the ternary solubility of MTBG and DTBG were correlated using the Bartle equation.