Removal of single and dual ring thiophene's from dodecane using cavitation based processes.

Utilising cavitation for enhancing oxidative desulphurization has been investigated for nearly-two decades with recent investigations shifting focus from low-capacity acoustic cavitation (AC) to scalable hydrodynamic cavitation (HC). This work focuses on developing a viable means for removing thiophene's from fuels. In the first phase of this work, use of vortex based HC devices for removal of single and dual ring thiophenes from dodecane was investigated. HC was shown to be able to remove single ring thiophene from dodecane without using any external catalyst or additives. However, in absence of catalyst or additives, it was not possible to remove dual ring thiophenes such as dibenzothiophene using HC. Therefore, in the second phase of this work, various strategies based on use of catalyst or additives to augment cavitation based process were investigated. AC based experiments were opted for shortlisting suitable catalysts and additives for intensifying cavitation based processes. The influence of using oxidant (H2O2) and carboxylic acid catalysts on efficacy of removal of dual ring thiophenes is presented. Several conditions were tested, and the optimal volumetric ratios of 0.95 v/v % H2O2 and 6.25 v/v % HCOOH was identified and utilised throughout the remainder of the study. Regeneration of extractant which accumulates oxidised sulphur species from dodecane was also investigated using AC. The additives and process conditions reported in this work are useful for enhancing desulphurization performance.

Insights into selective hydrogenation of levulinic acid using copper on manganese oxide octahedral molecular sieves.

Selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied using copper on manganese oxide octahedral molecular sieve (OMS-2) as catalysts. A range of copper supported on OMS-2 catalysts was prepared using the modified wet-impregnation technique and characterized thoroughly using powder X-ray diffraction, inductively coupled plasma optical emission spectroscopy metal analysis, Fourier transform infrared, high-resolution transmission electron microscopy and N2 sorption analyses. Process parameters for selective hydrogenation of LA to GVL were optimized using the design of experiment (DoE) approach with response surface methodology comprising a central composite design. Using the optimized conditions (190°C reaction temperature, 20 bar H2 pressure and 20 wt% Cu loading on OMS-2), up to 98% yield of GVL could be achieved in water as a solvent. Based on DoE, H2 pressure had the most influence on GVL selectivity followed by catalyst loading used for the hydrogenation of LA. The response surface methodology model also showed synergistic effect of reaction temperature and H2 pressure on the yield of GVL. 20 wt% Cu/OMS-2 catalysts were re-used up to four cycles and showed noticeable loss of activity after the first cycle due to observed leaching of loose Cu species, thereafter the activity loss diminished during subsequent recycles.

Role of Sulfation of Zirconia Catalysts in Vapor Phase Ketonization of Acetic Acid.

The effect of the sulfation of zirconia catalysts on their structure, acidity/basicity, and catalytic activity/selectivity toward the ketonization of organic acids is investigated by a combined experimental and computational method. Here, we show that, upon sulfation, zirconia catalysts exhibit a significant increase in their Brønsted and Lewis acid strength, whereas their Lewis basicity is significantly reduced. Such changes in the interplay between acid-base sites result in an improvement of the selectivity toward the ketonization process, although the measured conversion rates show a significant drop. We report a detailed DFT investigation of the putative surface species on sulfated zirconia, including the possible formation of dimeric pyrosulfate (S2O7 2-) species. Our results show that the formation of such a dimeric system is an endothermic process, with energy barriers ranging between 60.0 and 70.0 kcal mol-1, and which is likely to occur only at high SO4 2- coverages (4 S/nm2), high temperatures, and dehydrating conditions. Conversely, the formation of monomeric species is expected at lower SO4 2- coverages, mild temperatures, and in the presence of water, which are the usual conditions experienced during the chemical upgrading of biofuels.

Transition Metal Exchanged Hydroxyapatite/Fluorapatite Catalysts for C-C and C-N Bond Forming Reactions.

Transition metal (Cu, Zn, Rh, Pd) exchanged hydroxyapatite (HAP)/fluorapatite (FAP) materials have been synthesized by ion-exchange method resulting in incorporation of the metal ions in the HAP/FAP structure. C-C and C-N bond forming reactions are important in synthetic organic chemistry as these organic transformations are very critical. Transition metal exchanged FAP provides an efficient catalytic system for N-arylation of haloarenes and Suzuki and Heck coupling of haloarenes. By designing such catalytic materials, our group has developed synthetic methods which allow higher product yields and easy separation with the use of a small amount of catalyst in a shorter reaction time. This account addresses the work carried out in last two decades in the area of C-C and C-N bond forming reactions using transition metal exchanged fluorapatite.

Copper Catalyzed C-H Activation.

Activation of C-H bonds and their application in cross coupling chemistry has received a wider interest in recent years. The conventional strategy in cross coupling reaction involves the pre-functionalization step of coupling reactants such as organic halides, pseudo-halides and organometallic reagents. The C-H activation facilitates a simple and straight forward approach devoid of pre-functionalization step. This approach also addresses the environmental and economical issues involved in several chemical reactions. In this account, we have reported C-H bond activation of small organic molecules, for example, formamide C-H bond can be activated and coupled with ß-dicarbonyl or 2-carbonyl substituted phenols under oxidative conditions to yield carbamates using inexpensive copper catalysts. Phenyl carbamates were successfully synthesized in moderate to good yields by cross dehydrogenative coupling (CDC) of phenols with formamides using copper catalysts in presence of a ligand. We have also prepared unsymmetrical urea derivatives by oxidative cross coupling of formamides with amines using copper catalysts. Synthesis of N,N-dimethyl substituted amides, 5-substituted-γ-lactams and α-acyloxy ethers was carried out from carboxylic acids using recyclable CuO nanoparticles. Copper nanoparticles afforded N-aryl-γ-amino-γ-lactams by oxidative coupling of aromatic amines with 2-pyrrolidinone. Reusable transition metal HT-derived oxide catalyst was used for the synthesis of N,N-dimethyl substituted amides by the oxidative cross-coupling of carboxylic acids and substituted benzaldehydes. Overview of our work in this area is summarized.