Hc Greenwell

Catalytic upgrading of tri-glycerides and fatty acids to transport biofuels

Fuels derived from the lipid fraction of biomass have recently received much attention for carbon neutral substitution of fossil fuels for transport use. In this article we review the current routes to catalytic upgrading of the biomass derived lipid fractions. The history and motivation for biofuels are discussed, including the link to current market trends amongst fuel prices. The sources of lipids and their chemical composition are considered. We review the current literature detailing the use of trans-esterification reactions (heterogeneous and homogeneous) which lead to oxygenated “Biodiesel”, and also decarboxylation, which leads to deoxygenated “Green Diesel”. Traditional methods are covered, as well as more recent novel research aiming to produce commercially viable fuels.

Thermochemical processing of macroalgae: a late bloomer in the development of third-generation biofuels?

This article offers a critical overview of the recent developments in thermochemical processing of macroalgae, a field that has been comparatively neglected when viewed against the vast wealth of research into alternative biofuel production methods and feedstocks. However, advances in thermochemical techniques have led to a flurry of activity into the applicability and use of macroalgae. Recent research has demonstrated that macroalgae may be used to produce bioresources in a similar way to many conventional terrestrial feedstocks and, indeed, may also possess a number of advantages (notably by not competing for land that could be used for food and forestry, nor requiring extensive use of nitrogenous fertilizers). With this in mind, it is suggested that many of the criticisms that have led to previous disinterest in thermal processing of macroalgae are not valid. Nevertheless, only through the continuation of these recent endeavors can macroalgal biomass, via broader and successively larger scale experimentation, demonstrate itself to be a competitive source of renewable energy.

Rule based design of clay-swelling inhibitors

In oil and gas drilling operations, drilling fluids perform essential tasks such as lubricating the drill bit, providing hydrostatic pressure and removing drill cuttings. One important function of the drilling fluid is to stop compacted clay minerals, commonly encountered in drilling operations, from taking up water from the drilling fluids and consequently swelling. Such a scenario can have an adverse impact on drilling operations and may lead to significantly increased oil well construction costs. With increasingly stringent environmental guidelines determining which swelling inhibitors are available for use in the oilfield as drilling fluid additives, there is a need to fully understand the mechanisms of clay hydration in order to design new swelling inhibitors which conform to evolving regulations. Using a range of computational techniques and analysis, combined with known experimental results, we have devised a set of “rule-based” design criteria for clay-swelling inhibitors. To achieve this, we have formulated a hydration energy parameter, which assesses the changes in energy during the step-wise progression from mono- to bi- to trilayers of water in the clay sheet galleries. This parameter can be used to rationalise and predict the swelling profiles for clays containing both cationic and neutral clay swelling inhibitors. The rules we have devised are as follows: (i) Cationic inhibitors should be able to replace sodium ions in the interlayer. (ii) Cationic inhibitors should possess a water soluble, hydrophobic backbone. (iii) Cationic inhibitors should have primary di-amine or mono-quaternary amine functionality. (iv) Cationic inhibitors should have little alcohol functionality. (v) The hydrophobic backbone of the cationic inhibitor should be long enough to form a dense monolayer in the interlayer. (vi) For neutral inhibitors, the inhibitor should be a water soluble organic molecule of low molecular weight with well defined domains of relatively high hydrophobicity and small domains of hydrophobicity. Our “rule-based” criteria will facilitate the rational design of improved—and more environmentally acceptable—clay swelling inhibitors for oilfield drilling operations.

Monster potential meets potential monster: pros and cons of deploying genetically modified microalgae for biofuels production.

Biofuels production from microalgae attracts much attention but remains an unproven technology. We explore routes to enhance production through modifications to a range of generic microalgal physiological characteristics. Our analysis shows that biofuels production may be enhanced ca fivefold through genetic modification (GM) of factors affecting growth rate, respiration, photoacclimation, photosynthesis efficiency and the minimum cell quotas for nitrogen and phosphorous (N : C and P : C). However, simulations indicate that the ideal GM microalgae for commercial deployment could, on escape to the environment, become a harmful algal bloom species par excellence, with attendant risks to ecosystems and livelihoods. In large measure, this is because an organism able to produce carbohydrate and/or lipid at high rates, providing stock metabolites for biofuels production, will also be able to attain a stoichiometric composition that will be far from optimal as food for the support of zooplankton growth. This composition could suppress or even halt the grazing activity that would otherwise control the microalgal growth in nature. In consequence, we recommend that the genetic manipulation of microalgae, with inherent consequences on a scale comparable to geoengineering, should be considered under strict international regulation.

Influence of surface chemistry and charge on mineral-RNA interactions.

We present the results of large-scale molecular simulations, run over several tens of nanoseconds, of 25-mer sequences of single-stranded ribonucleic acid (RNA) in bulk water and at the surface of three hydrated positively charged MgAl layered double hydroxide (LDH) minerals. The three LDHs differ in surface charge density, through varying the number of isomorphic Al substitutions. Over the course of the simulations, RNA adsorbs tightly to the LDH surface through electrostatic interactions between the charged RNA phosphate groups and the alumina charge sites present in the LDH sheet. The RNA strands arrange parallel to the surface with the base groups aligning normal to the surface and exposed to the bulk aqueous region. This templating effect makes LDH a candidate for amplifying the population of a known RNA sequence from a small number of RNAs. The structure and interactions of RNA at a positively charged, hydroxylated LDH surface were compared with those of RNA at a positively charged calcium montmorillonite surface, allowing us to establish the comparative effect of complexation and water structure at hydroxide and silicate surfaces. The systems were studied by computing radial distribution functions, atom density plots, and radii of gyration, as well as visualization. An observation pertinent to the role of these minerals in prebiotic chemistry is that, for a given charge density on the mineral surface, different genetic sequences of RNA adopt different configurations.

Role of Clay Minerals in Oil-Forming Reactions

Mineral-catalyzed decarboxylation reactions are important in both crude oil formation and, increasingly, biofuel production. In this study we examined decarboxylation reactions of a model fatty acid, propionic acid, C(2)H(5)COOH, to an alkane, C(2)H(6), in a model of pyrophillite with an isomorphic substitution of aluminum in the tetrahedral layer. We model a postulated reaction mechanism (Almon, W. R.; Johns, W. D. 7th International Meeting on Organic Geochemistry 1975, Vol. 7) to ascertain the role of Al substitution and a counterion in decarboxylation reactions. We employ a periodic cell, planewave, ab initio DFT computation to examine the total energies and the frontier orbitals of different model sets, including the effects of charge on the reaction, the effect of Al substitution, and the role of Na counterions. The results show that an uncharged system with a sodium counterion is most feasible for catalyzing the decarboxylation reaction in an Al-substituted pyrophillite and, also, that analysis of the orbitals is a better indicator of a reaction than charge alone.

Copper(II)-mediated thermolysis of alginates : a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae.

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams.

DFT+U investigation of the catalytic properties of ferruginous clay

Abstract The formation of fossil oil within clay minerals i.e., mineral-catalyzed decarboxylation, is a mechanism awaiting a thorough chemical explanation. To contribute to such an explanation, the study presented here investigates this mechanism at the level of first-principles, electronic structure computations, employing density functional theory (DFT plus Hubbard-U), planewaves, pseudopotentials, and periodic cells of two types of ferruginous clay minerals, specifically two types of nontronite [Fe2 (Si,Al)4O10(OH)2]. The formation of the fossil oil is modeled as a decarboxylation pathway, converting the fatty acid propionic acid, C2H5COOH to an alkane, C2H6 and the intermediate stages along this conversion pathway are represented by five configurations of interlayer species within the clay minerals. In this study, we test both the effect of the presence of iron on the theoretical stages of decarboxylation, together with the effect of two different density functionals: with and without strong correlations of the d-orbital electrons of iron. We have found that inclusion of the d-orbital electron correlations in the guise of a Hubbard parameter results in the introduction of three new intermediate configurations (one of which is potentially a new transition state), alters the location of the occupied Fermi level orbitals, and changes the band gaps of the clay mineral/interlayer species composites, all of which serves to inform the chemical interpretation of mineral-catalyzed decarboxylation.

Biofuels, science and society

The International Energy Agencys New Policies Scenario projects a world demand of 99 million barrels of crude oil per day by 2035, but peak oil production at 68–69 million bpd ([http://www.iea.org/press/pressdetail.asp?press\_rel\_id=402][1]). Something has to fill this gap, even if there are