Organic reactions in ionic liquids:Gewald synthesis of 2-aminothiophenes catalyzed by ethylenediammonium diacetate

Ionic liquids based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) and 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6) were used as reusable alternatives to volatile organic solvents (VOCs) for ethylenediammonium diacetate (EDDA) catalyzed Gewald synthesis of 2-aminothiophenes. Significant rate enhancement and improvement of the yield were observed. The ionic liquids containing catalyst EDDA were recycled several times with no decreases in yields and reaction rates.

Organic reactions in ionic liquids: Knoevenagel condensation catalyzed by ethylenediammonium diacetate

The moisture and air stable ionic liquids 1-butyl-3-methylimidazonium tetrafluoroborate [bmim]BF4 and 1-butyl-3-methylimidazonium hexafluorophosphate [bmim]PF6 were used as ‘green' recyclable alternatives to volatile organic solvents (VOCs) for ethylenediammonium diacetate (EDDA) catalyzed Knoevenagel condensation between aldehydes or ketones with active methylene compounds. Both aldehydes and ketones gave satisfactory results. The ionic liquids containing catalyst EDDA were recycled several times with no decreases in yields and reaction rates. In the case of 2-hydroxybenzaldehyde, the reactions led to the formation of 3-substituted coumarins under standard reaction conditions.

Production of renewable phenolic resins by thermochemical conversion of biomass: a review

This review covers the production and utilisation of liquids from the thermal processing of biomass and related materials to substitute for synthetic phenol and formaldehyde in phenol formaldehyde resins. These resins are primarily employed in the manufacture of wood panels such as plywood, MDF, particle-board and OSB. The most important thermal conversion methods for this purpose are fast pyrolysis and vacuum pyrolysis, pressure liquefaction and phenolysis. Many feedstocks have been tested for their suitability as sources of phenolics including hard and softwoods, bark and residual lignins. Resins have been prepared utilising either the whole liquid product, or a phenolics enriched fraction obtained after fractional condensation or further processing, such as solvent extraction. None of the phenolics production and fractionation techniques covered in this review are believed to allow substitution of 100% of the phenol content of the resin without impacting its effectiveness compared to commercial formulations based on petroleum derived phenol. This survey shows that considerable progress has been made towards reaching the goal of a price competitive renewable resin, but that further research is required to meet the twin challenges of low renewable resin cost and satisfactory quality requirements. Particular areas of concern are wood panel press times, variability of renewable resin properties, odour, lack of reactive sites compared to phenol and potential for increased emissions of volatile organic compounds.

Zr-containing hybrid organic-inorganic mesoporous materials:hydrophobic acid catalysts for biodiesel production

Zirconium-containing periodic mesoporous organosilicas (Zr-PMOs) with varying framework organic content have been synthesized through a direct synthesis method. These materials display the excellent textural properties of the analogous inorganic solid acid Zr-SBA-15 material. However, the substitution of silica by organosilicon species provides a strong hydrophobic character. This substitution leads to meaningful differences in the environment surrounding the zirconium metal sites, leading the modification of the catalytic properties of these materials. Although lower metal incorporation is accomplished in the final materials, leading to a lower population of metal sites, hydrophobisation leads to an impressive beneficial effect on the intrinsic catalytic activity of the zirconium sites in biodiesel production by esterification/transesterification of free fatty acid -containing feedstock. Moreover, the catalytic activity of the highly hybridised materials is hardly affected in presence of large amounts of water, confirming their very good water-tolerance. This makes Zr-PMO materials interesting catalysts for biodiesel production from highly acidic water-containing feedstock. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental studies on the distribution of the sexes of Mercurialis perennis L.

1) In a beechwood, male shoots of Mercurialis perennis were more frequent than female shoots in canopy openings, while females were more frequent at treebases than in canopy openings. 2) Flowering shoots were more frequent than non-flowering in openings. 3) The pH, moisture and organic content of the soil were similar at treebases and openings. The light climate was similar in both habitats in April but greater in the openings in August. 4) Removal of canopies of Pteridium aquilinum and Rubus fruticosus, above populations of M. perennis, resulted in a greater increase in the numbers of male shoots than of female shoots. 5) These results suggest that male and female plants differ in numbers, or growth, in different woodland microhabitats and that these differences are correlated with the above-ground environment (e.g. light).

Thermochemical characterisation of straws and high yielding perennial grasses

The research is concerned with thermochemical characterisation of straws and high yielding perennial grasses. Crops selected for this study include wheat straw (Triticum aestivum), rape straw (Brassica napus), reed canary grass (Phalaris arundinacea) and switch grass (Panicum virgatum). Thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles during pyrolysis up to 900 °C. Utilising multi-heating rate thermogravimetric data, the Friedman iso-conversional kinetic method was used to determine pyrolysis kinetic parameters. Light and medium volatile decomposition products were investigated using pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) up to 520 °C. The 22 highest yielding identifiable cellulose, hemicellulose and lignin biomass markers were semi-quantified taking into consideration peak areas from GC chromatograms. Notable differences can be seen in butanedioic acid, dimethyl ester (hemicelluloses decomposition products), 2-methoxy-4-vinylphenol (lignin marker) and levoglucosan (intermediate pyrolytic decomposition product of cellulose) content when comparing perennial grasses with straw. From results presented in this study, perennial grasses such as switch grass, have the most attractive properties for fast pyrolysis processing. This is because of the observed high volatile yield content of 82.23%, heating value of 19.64 MJ/kg and the relatively low inorganic content.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Superior gas-sensing performance of amorphous CdO nanoflake arrays prepared at room temperature

Highly sensitive and selective detection of volatile organic compounds (VOCs) with fast response time is imperative based on safety requirements, yet often remains a challenge. Herein, we propose an effective solution, preparing a novel gas sensor comprised of amorphous nanoflake arrays (a-NFAs) with specific surface groups. The sensor was produced via an extremely simple process in which a-NFAs of CdO were deposited directly onto an interdigital electrode immersed in a chemical bath under ambient conditions. Upon exposure to a widely used VOC, diethyl ether (DEE), the sensor exhibits excellent performance, more specifically, the quickest response, lowest detection limit and highest selectivity ever reported for DEE as a target gas. The superior gas-sensing properties of the prepared a-NFAs are found to arise from their open trumpet-shaped morphology, defect-rich amorphous nature, and surface CO groups.

Pyrolysis of rice husk and corn stalk in auger reactor:Part 1. Characterization of char and gas at various temperatures

In this study, rice husk and corn stalk have been pyrolyzed in an auger pyrolysis reactor at pyrolysis temperatures of 350, 400, 450, 500, 550, and 600 °C in order to investigate the effect of the pyrolysis temperature on the pyrolysis performance of the reactor and physicochemical properties of pyrolysis products (this paper focuses on char and gas). The results have shown that the pyrolysis temperature significantly affects the mass yields and properties of the pyrolysis products. The mass yields of pyrolysis liquid and char are comparable to those reported for the same feedstocks processed in fluidized bed reactors. With the increase of the pyrolysis temperature, the pyrolysis liquid yield shows a peak at 500 °C, the char yield decreases, and the gas yield increases for both feedstocks. The higher heating value (HHV) and volatile matter content of char increase as the pyrolysis temperature increases from 350 to 600 °C. The gases obtained from the pyrolysis of rice husk and corn stalk mainly contain CO2, CO, CH4, H2, and other light hydrocarbons; the molar fractions of combustible gases increase and therefore their HHVs subsequently increase with the increase of the pyrolysis temperature.