Octyl co-grafted PrSO3H/SBA-15:tunable hydrophobic solid acid catalysts for acetic acid esterification

Propylsulfonic acid (PrSO3H) derivatised solid acid catalysts have been prepared by post modification of mesoporous SBA-15 silica with mercaptopropyltrimethoxysilane (MPTMS), with the impact of co-derivatisation with octyltrimethoxysilane (OTMS) groups to impart hydrophobicity to the catalyst investigated. Turn over frequencies (TOF) for acetic acid esterification with methanol increase with PrSO3H surface coverage across both families suggesting a cooperative effect of adjacent acid sites at high acid site densities. Esterification activity is further promoted upon co-functionalisation with hydrophobic octyl chains, with inverse gas chromatography (iGC) measurements indicating increased activity correlates with decreased surface polarity or increased hydrophobicity

A review of advanced catalyst development for Fischer-Tropsch synthesis of hydrocarbons from biomass derived syn-gas

Fischer-Tropsch synthesis (FTS) is a process which converts syn-gas (H2 and CO) to synthetic liquid fuels and valuable chemicals. Thermal gasification of biomass represents a convenient route to produce syn-gas from intractable materials particularly those derived from waste that are not cost effective to process for use in biocatalytic or other milder catalytic processes. The development of novel catalysts with high activity and selectivity is desirable as it leads to improved quality and value of FTS products. This review paper summarises recent developments in FT-catalyst design with regards to optimising catalyst activity and selectivity towards synthetic fuels

Mesoporous sulfonic acid silicas for pyrolysis bio-oil upgrading via acetic acid esterification

Propylsulfonic acid derivatised SBA-15 catalysts have been prepared by post modification of SBA-15 with mercaptopropyltrimethoxysilane (MPTMS) for the upgrading of a model pyrolysis bio-oil via acetic acid esterification with benzyl alcohol in toluene. Acetic acid conversion and the rate of benzyl acetate production was proportional to the PrSO3H surface coverage, reaching a maximum for a saturation adlayer. Turnover frequencies for esterification increase with sulfonic acid surface density, suggesting a cooperative effect of adjacent PrSO3H groups. Maximal acetic acid conversion was attained under acid-rich conditions with aromatic alcohols, outperforming Amberlyst or USY zeolites, with additional excellent water tolerance

Correlation between Fischer-Tropsch catalytic activity and composition of catalysts

This paper presents the synthesis and characterization of monometallic and bimetallic cobalt and iron nanoparticles supported on alumina. The catalysts were prepared by a wet impregnation method. Samples were characterized using temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), CO-chemisorption, transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM-EDX) and N2-adsorption analysis. Fischer-Tropsch synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/CO = 2 v/v and space velocity, SV = 12L/g.h. The physicochemical properties and the FTS activity of the bimetallic catalysts were analyzed and compared with those of monometallic cobalt and iron catalysts at similar operating conditions

Formation of H2 and CH4 by weathering of olivine at temperatures between 30 and 70°C

Hydrocarbons such as CH4 are known to be formed through the Fischer-Tropsch or Sabatier type reactions in hydrothermal systems usually at temperatures above 100°C. Weathering of olivine is sometimes suggested to account for abiotic formation of CH4 through its redox lowering and water splitting properties. Knowledge about the CH4 and H2 formation processes at low temperatures is important for the research about the origin and cause of early Earth and Martian CH4 and for CO2 sequestration. We have conducted a series of low temperature, long-term weathering experiments in which we have tested the CH4 and H2 formation potential of forsteritic olivine

Catalytic upgrading of bio-oils by esterification

Biomass is the term given to naturally-produced organic matter resulting from photosynthesis, and represents the most abundant organic polymers on Earth. Consequently, there has been great interest in the potential exploitation of lignocellulosic biomass as a renewable feedstock for energy, materials and chemicals production. The energy sector has largely focused on the direct thermochemical processing of lignocellulose via pyrolysis/gasification for heat generation, and the co-production of bio-oils and bio-gas which may be upgraded to produce drop-in transportation fuels. This mini-review describes recent advances in the design and application of solid acid catalysts for the energy efficient upgrading of pyrolysis biofuels

FORMATION OF ACTIVE CATALYTIC SITES IN HYDROCARBON SYNTHESIS AND REACTION

Acid and metal catalysis are considerably important in the chemical industry especially, for the production of transportation fuels. Since a serious concern on the world environment has infringed on the restriction of aromatics contained in gasoline, the demand for clean high-octane branched alkanes for gasoline upgrading has significantly increased. This process involves acid catalyzed n-butane isomerization in which n-butane is converted to isobutane, a primary feedstock for the production of high-octane species. In addition, due to the unpredictable price and the limited resource of petroleum fuel derived crude oil, the attention has shifted to synthetic liquid fuels derived from other abundant energy sources such as coal and biomass. This process requires a metal catalyzed Fischer-Tropsch synthesis (FTS) to upgrade low-value coal and biomass to high value liquid fuels. However, the cost of its production is not as competitive as those obtained from oil refineries. Therefore, a highly active and durable FTS catalyst is needed. Understanding the behavior and form of active catalytic reaction sites for hydrocarbon reaction (n-butane isomerization) and synthesis (FTS) on their respective solid acid and metal catalysts will allow us to a design of better catalysts. Sulfated zirconia (SZ) and bulk Fe catalysts have been chosen to catalyze n-butane isomerization and FTS, respectively. The present research has gained in-depth details of the constitution of the active sites of SZ at 100oC and the reaction mechanism operating for n-butane isomerization which is able to explain all apparent contradictory results reported in the literature by using olefin as a molecular probe. A highly active and stable bulk Fe FTS catalyst containing Cu and SiO2 has been also developed upon the promotion of various transition metals such as Cr, Mn, Mo, Ta, V and Zr. Cr-, Mn- and Zr-promoted Fe FTS exhibited considerable activity for both CO hydrogenation and water-gas-shift (WGS) reaction at 280oC allowing them to catalyze FTS under low H2/CO ratio syngas derived from biomass or coal. In this present work, steady-state isotopic transient kinetic analysis (SSITKA) has also been utilized to investigate the surface kinetic information about reaction on the catalysts under real reaction conditions in order to obtain how promoters influence the reactivity of catalysts at the site level