Sulfated fibrous ZrO2/Al2O3 core and shell nanocomposites : a novel strong acid catalyst with hierarchically macro-mesoporous nanostructure

A series of solid strong acid catalysts were synthesised from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2 % to 50 %. The ZrO2/Al2O3 nanocomposites and their solid strong acid counterparts were characterised by a variety of techniques including 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR), scanned electronic microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Nitrogen adsorption and infrared emission spectroscopy (IES). NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained solid acids was tested by using them as catalysts for the benzolyation of toluene. It was found that a sample with a 50 % zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia.

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

Epoxide ring opening in a zinc(II) complex in water without any Lewis acid catalyst: formation of only one diastereomer out of 2

The epoxide ring in 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) opens up in its reaction with 4-methylaniline and 4-methoxyaniline in water in equimolar proportion at room temperature without any Lewis acid catalyst to give a monohydrate of 6-(4-methyl-phenylamino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L′·H2O) and 6-(4-methoxyphenyl-amino)-5,6-dihydro-1,10-phenanthrolin-5-ol (L″) respectively. Reaction time decreases from 72 to 14 h in boiling water. But the yields become less. Reaction of L with Zn(ClO4)2·6H2O in methanol in 3:1 molar ratio at room temperature affords white [ZnL3](ClO4)2·H2O. The X-ray crystal structure of the acetonitrile solvate [ZnL3](ClO4)2·MeCN has been determined which shows that the metal has a distorted octahedral N6 coordination sphere. [ZnL3](ClO4)2·2H2O reacts with 4-methylaniline and 4-methoxyaniline in boiling water in 1:3 molar proportion in the absence of any Lewis acid catalyst to produce [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, respectively in 1–4 h time in somewhat low yield. In the 1H NMR spectra of [ZnL′3](ClO4)2·4H2O and [ZnL″3](ClO4)2·H2O, only one sharp methyl signal is observed implicating that only one diastereomer out of the 23 possibilities is formed. The same diastereomers are obtained when L′·H2O and L″ are reacted directly with Zn(ClO4)2·6H2O in tetrahydrofuran at room temperature in very good yields. Reactions of L′·H2O and L″ with Ru(phen)2Cl2·2H2O (phen = 1,10-phenanthroline) in equimolar proportion in methanol–water mixture under refluxing condition lead to the isolation of two diastereomers of [Ru(phen)2L′](ClO4)2·2H2O and [Ru(phen)2L″](ClO4)2·2H2O.

Effect of presence of an acid catalyst on structure and properties of iron-doped siloxane-polyoxyethylene nanocomposites prepared by sol-gel

In this work we investigate the effect of hydrochloric acid (HC) addition on the structure and thermal and magnetic properties of iron-doped siloxane-polyoxyethylene (POE) hybrids prepared by the sol-gel route. X-ray powder diffraction (XRD) and X-ray absorption near edge structure (XANES) results reveal the dominance of ferrihydrite nanoparticles and a mixture of this phase with FeCl4- species in the hybrid prepared without and with HCl, respectively. Thermal analysis reveals the existence of two crystalline polymeric phases in the hybrid prepared with HCl whereas hybrids prepared without HCl are amorphous. The 105 and 60 Angstrom sized ferrihydrite nanoparticles were detected by SAXS analysis of the composite prepared without and with HCl, respectively. The magnetic results suggest that in both samples antiferromagnetic nanoparticles coexist with small clusters/isolated ions. In the sample without HCl addition, larger particles dominate the magnetic behavior, while the opposite occurs for the sample prepared using HCl catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Kinetics of acetic acid esterification with 2-ethoxyethanol over an Al-pillared clay catalyst

The Al-pillared clay catalyst obtained by exposing activated clay powder to sulfuric acid and aluminium salts and calcining in air at 373-673 K, was found to be highly active for the title reaction. The results indicated that pillared layer clay of the mixed oxide has been employed as parent catalysts for their definite structure and special properties which can be modified by the substitution of L and B acid sites cations. Solid acid catalyst of Supported aluminium was found to be highly active and selective at the 373-473 K temperature range for heterogeneous esterification. The activity is mainly attributed to the Lewis (and a considerably small number of Bronsted) acid sites whose number and strength increased due to pillaring. The water produced in the esterification can be induced by Al3+, which makes the catalyst surface to form strong B acid. Their acidities are obtained by pH measurement. If only B acid sites are > 70%, and pH < 1 in the 2-ethoxyethanol, there exists an activity of esterification. The used catalyst gave identical results with that of the fresh one. X-ray diffraction spectra show that the composition and active phase of the used catalysts are the same as the fresh ones. The kinetic study of the reaction was carried out by an integral method of analysis. The kinetic equation of surface esterification is y = 2.36x - 0.98.

Production of levulinic acid and other chemicals from sugarcane fibre

Lignocellulosics represent a renewable resource for producing fuels and chemicals as an alternative to fossil resources. This study utilised an organic acid catalyst and a co-solvent to develop an environmentally friendly processing technology for the production of levulinic acid and furfural from a waste material, sugarcane fibre.

Production of biodiesel from soapstock using an ion-exchange resin catalyst

The feasibility of biodiesel production from soapstock containing high water content and fatty matters by a solid acid catalyst was investigated. Soapstock was converted to high-acid acid oil (HAAO) by the hydrolysis by KOH and the acidulation by sulfuric acid. The acid value of soapstock-HAAO increased to 199.1 mg KOH/g but a large amount of potassium sulfate was produced. To resolve the formation of potassium sulfate, acid oil was extracted from soapstock and was converted to HAAO by using sodium dodecyl benzene sulfonate (SDBS). The maximum acid value of acid oil-HAAO was 194.2 mg KOH/g when the mass ratio of acid oil, sulfuric acid, and water was 10:4:10 at 2% of SDBS. In the esterification of HAAO using Amberylst-15, fatty acid methyl ester (FAME) concentration was 91.7 and 81.3% for soapstock and acid oil, respectively. After the distillation, FAME concentration became 98.1% and 96.7% for soapstock and acid oil. The distillation process decreased the total glycerin and the acid value of FAME produced a little.

A study on the catalytic behaviors of concentrated heteropolyacid solution - I. A novel catalyst for isobutane alkylation with butene

The catalytic behaviors of a novel liquid acid catalyst (composed of heteropolyacid and acetic acid) for alkylation of isobutane with butene was investigated. As a solvent acetic acid had a synergistic effect. It enhanced the acid strength of HPA and its stability. The conditions for the formation of the catalytically active phase were studied systematically. The content of crystal water of HPA and the quantity of solvent affect the formation of active phase and the catalytic activity. Catalytically active phase consists of HPA, acetic acid and hydrocarbon produced from the reaction, as well as traces of water from the crystal water of HPA. This catalyst system is comparable to the sulfuric acid in catalytic activity.

Study of the catalytic behaviors of concentrated heteropolyacid solution. I. A novel catalyst for isobutane alkylation with butenes

A novel liquid acid catalyst, composed of heteropolyacid and acetic acid for the alkylation of isobutane with butenes is reported. The conditions for the formation of catalytic active phase as well as its catalytic behaviors in alkylation of isobutane with butenes have been studied. It was found that acetic acid, as a solvent, exerts a synergistic effect on the acid strength of heteropolyacid, and the contents of crystal water in HPAs have influence over the formation of active phase and the catalytic activity. This novel catalyst is comparable to the sulfuric acid in catalytic activity.

Heterogenization of heteropolyacids: A general discussion on the preparation of supported acid catalysts

Heteropolyacids (HPAs) possess both acidic and redox catalytic properties and held extensive promise of practical application. These type of compound display a great potential of specific synthesis reactions for replacing sulfuric acid to satisfy the requirements of environmental protection. Heterogenizing HPAs would not only make them more useful in liquid phase oxidation with oxygen and in acid-catalyzed reaction, as the catalyst is often difficult to separate from the reaction products, but also create favorable factors for realizing heterogenization of homogeneous reaction and even utilizing new technology of catalytic distillation. In this paper, different kinds of porous materials which are well characterized, including oxides such as Al2O3, SiO2, TiO2, diatomite, bentonite, and active carbon of different sources, were used as support for heterogenizing HPAs (in different media), and the obtained results, the intrinsic characters of supports which may influence both the nature of the interaction between HPAs and supports in the heterogenization and the activity in the catalytic reaction, are explored. It is expected that these can provide a referential model for preparing supported acid catalyst used in liquid phase.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis

Hierarchical macroporous-mesoporous SBA-15 silicas have been synthesised via dual-templating routes employing liquid crystalline surfactants and polystyrene beads. These offer high surface areas and well-defined, interconnecting macro- and mesopore networks with respective narrow size distributions around 300 nm and 3-5 nm for polystyrene:tetraethoxysilane ratios ≥2:1. Subsequent functionalisation with propylsulfonic acid yields the first organized, macro-mesoporous solid acid catalyst. The enhanced mass transport properties of these new bi-modal solid acid architectures confer significant rate enhancements in the transesterification of bulky glyceryl trioctanoate, and esterification of long chain palmitic acid, over pure mesoporous analogues. This paves the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion. © 2010 The Royal Society of Chemistry.