Green epoxidation on Ti-mesoporous catalysts

New mesoporous catalysts with a mean pore size of 65 Å have been synthesised by grafting titanium on a mesoporous silica SBA15 (Santa BArbara) by means of titanium tetrachloride in the gas phase. These catalysts have been tested for the green epoxidation of cyclooctene, cyclohexene, (R)-limonene and -pinene by hydrogen peroxide, tert-butyl hydroperoxide or cumyl hydroperoxide. The selectivity is 100% and epoxide yields can reach almost 100% in the case of organic hydroperoxides without any leaching of titanium species. Here we show that cyclohexene epoxidation could be used as the first step of a greener synthesis of adipic acid.     

Emissions analysis on second generation biodiesel

This work investigates the effect of adding pentanol with biodiesel derived from cashew nut shell on its emissions characteristics is conducted in stationery diesel engine. The main purpose of this work is intended to reduce the emissions by fuelling biodiesel derived from cashew nut shell and the pentanol blends. Cashew nut shell biodiesel is prepared by transesterification process. Oxygenated additive used in the work is Pentanol. The experiment is conducted using four test fuels such as, biodiesel derived from cashew nut shell (CNSBD), a fuel containing 90% cashew nut shell biodiesel and 10% pentanol (CNSBD90P10), a fuel containing 80% cashew nut shell biodiesel and 20% pentanol (CNSBD80P20) and neat diesel. Experimental work concluded that by adding 10% of pentanol to cashew nut shell biodiesel 10.1%, 2.6%, 5.1%and 2.1%reduction in CO, HC, NO _x and Smoke emissions were observed respectively. Further by fueling with these blends, no modifications in engines were required.

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Biochar-derived heterogeneous catalysts for biodiesel production

Environmental Chemistry Letters - Population increase, urbanization and industrialization induce a drastic need for energy. Actually, fossil fuel resources are heavily exploited to meet the energy...     

Solvent-free mechanochemical mild oxidation method to enhance adsorption properties of chitosan

• Solvent-free chitosan oxidation is obtained by rapid mechanochemical reaction. • Different oxidants induce very diverse physicochemical changes on chitosan. • Oxidized chitosan with persulfate or percarbonate has improved adsorption capacity. • Uptake on oxidized chitosan with persulfate is 125-fold faster than on pristine one. Oxidation has been profitably utilized to improve some properties of chitosan. However, only solvent-based oxidation procedures have been proposed so far, which are hardly feasible at industrial scale in an economic way because of product recovery cost. In this study, a solvent-free, rapid, and effective oxidation method is proposed. It is based on direct solid-state reaction between chitosan and oxidant powder in a mechanochemical reactor. Results prove that by short high energy ball milling (<3 h) it is possible to achieve diverse physicochemical modifications employing different reagents. Apart from polysaccharidic chain shortening, persulfate provokes high amorphization and induces formation of ketonic groups; percarbonate heightens deacetylation degree, preserving in part crystallinity; calcium peroxide merely deprotonates amino groups and increases amorphization degree. Adsorption tests with the azo-dye reactive red 2 show that adsorption capacity of chitosan co-milled with persulfate (974 mg/g milled product), which is the best performing adsorbent, is twice that of pristine chitosan, while adsorption rate is outstandingly boosted (125 times).     

Green chemistry with process intensification for sustainable biodiesel production

Biodiesel as a renewable fuel has the potential to replace non-renewable fossil fuels and associated environmental pollution. The most commonly used method in biodiesel production is transesterification of virgin and used oil feedstock. However, the chemical reaction (transesterification) does not proceed spontaneously, which means excess reactants are required to move the reaction to completion. The biodiesel reaction efficiency can be improved by incorporating green chemistry principles and process intensification effects. Green chemistry principles can be used to design chemical products and processes that reduce or eliminate the use and generation of hazardous substances. Microwave- and ultrasound-enhanced biodiesel synthesis can improve the reaction efficiency due to higher product recovery, low by-product formation, and reduced energy consumption. In addition, utilization of green metrics such as E-factor, atom economy (utilization), mass intensity or mass productivity, and reaction mass efficiency can help design safer and highly efficient biodiesel synthesis. Green chemistry principles have been analyzed for other processes in greater details, but they are rarely discussed in the context of biodiesel production. Process intensification by microwave- and ultrasound-mediated biodiesel production was never discussed from the perspective of green chemistry and sustainable process development. This research review article discusses the role of green chemistry and process intensification in biodiesel production followed by specific examples and illustrations on green metrics of microwave- and ultrasound-enhanced biodiesel synthesis and the effect of catalysts and solvents including discussions on reaction kinetics and activation energy in detail for the first time in the literature.     

Application of heterogeneous catalysis to biodiesel synthesis using microalgae oil

• Microalgae oil application for biodiesel synthesis is discussed. • Catalytic effectiveness of ferment preparations and chemical catalyst is disputed. • Application of heterogeneous catalysts for biodiesel synthesis is reviewed. • Possibilities of catalyst regeneration is shown. Recently, there is a growing interest in the use of microalga in various fields. Microalgae have properties such as rapid reproduction and high biomass accumulation, and under certain conditions, some are able to accumulate a large amount of oil. However, microalgae oil often contains more free fatty acids than the vegetable oil and is therefore unsuitable for biodiesel synthesis using alkaline catalysts. For this reason, some authors suggest the application of heterogeneous catalysis. A particular interest in the use of immobilized enzymes has developed. Other solid substances can also be used as heterogeneous catalysts are usually metal oxides, carbonates or zeolites. The use of these catalysts results in simpler biodiesel synthesis, especially purification processes, a cleaner end product and a less polluted environment. The molar ratio of alcohol to oil is lower during enzymatic transesterification, and more than 90% ester yield is obtained using a molar ratio of alcohol to oil of 3:1 to 4.5:1. The alcohols do not have a negative effect on the effectiveness of chemical catalysts, so it is possible to use alcohols in molar ratio from 4:1 to 12:1. The optimal temperature of enzymatic process is 30℃‒50℃. An ester yield of more than 95% was obtained in 12‒48 h. Using chemical catalysts, greater than a 95% yield of esters was obtained at higher temperatures in a shorter time. Material costs of enzymatic catalysis can be reduced by reusing the catalysts directly or after regeneration.     

Efficient oxidation and epoxidation using a chromium(VI)-based magnetic nanocomposite

The oxidation of alcohols and alkenes to aldehydes, ketones and epoxides is a major reaction in organic synthesis, but is usually hard to perform due to the lack of efficient methods. The use of ultrasounds may improve yield because ultrasonic-assisted reactions are often more efficient than traditional methods. Here, we prepared a hybrid chromium(VI)-based magnetic nanocomposite catalyst by co-precipitation. This catalyst was characterized by Fourier transform infrared, solid-state ultraviolet–visible, elemental analysis, X-ray fluorescence, scanning electron microscopy, X-ray diffraction and vibrating sample magnetometer analyses. The catalytic activity was tested by the oxidation of benzyl alcohol to benzaldehyde, cyclohexanol to cyclohexanone, and epoxidation of cyclohexene, using hydrogen peroxide at room temperature under ultrasonic irradiation. Results show conversions ranging from 27 to 100 % according to gas chromatography–mass spectrometry. This is the first report of using magnetic nanocomposites with ultrasonic irradiation for oxidation reactions.     

Development of environmental sustainability for the biodiesel industry in Thailand

Wild game and other renewable resources in tropical rainforests inhabited by indigenous peoples are currently often exploited in unsustainable ways. This article shows, for a Kichwa community in the Ecuadorian Amazon, that this can to some extent be explained as a 'tragedy of the commons'. However there are also other mechanisms at work. In particular, there has been some unawareness of the impact of hunting on game populations, and the expansion of fallows at the expense of old growth forest is a result of population growth that increases the need for farmland, and thus decreases the socially optimal area of old growth forest. Whereas many resources are harvested under conditions resembling open access, there have long been established rules for the harvest of thatch leaves, and the community has recently also adopted several measures in order to regulate hunting. Obviously, experiences of resource scarcity may spark conservationist thinking and behaviour. This is a process that scientists can and should support.     

A simple and promising route for biodiesel production from low-quality lipids

High production cost is the key issue of biodiesel industry nowadays. To decrease the cost, using low-quality lipids feedstock is the most effective way. For low-quality lipids with high content of free fatty acids, a simple and promising route is proposed to produce biodiesel. Instead of the typical two-step procedure, the esterification and transesterification processes are performed continuously by simultaneously eliminating the formed water in the reaction system with CaO powder. Investigations were carried out on the synthesis of fatty acid methyl ester and fatty acid ethyl ester. The results showed that the esterification rate reached to 99.6% for fatty acid methyl ester and 99.4% for fatty acid ethyl ester within 3–4 h, and the transesterification rate reached to 89.1 and 86.2%, respectively. Over 93 w% of feedstock oil could be transformed to biodiesel. Besides, hydrophobic CaCO₃ nanorods were also synthesized as value-added by-product. Based on the new route, the production process of biodiesel could be simplified and the production cost could be reduced.     

Triacetin additive in biodiesel to reduce air pollution: a review

Environmental Chemistry Letters - Stricter environmental norms and fossil fuel pollution call for cleaner fuels such as biodiesel. However, depending on the biomass source, biodiesel combustion may...     

Metal- and ionic liquid-based photocatalysts for biodiesel production: a review

Environmental Chemistry Letters - Diminishing petroleum reserves, increasing carbon emissions, and the&nbsp;growing demand for fuels are calling for alternative fuels. Global diesel consumption...     

A new FTIR method to monitor transesterification in biodiesel production by ultrasonication

New renewable fuels are urgently needed due to increasing fossil fuel pollution. Biodiesel, which contains alkyl esters produced by transesterification of oils, is an alternative fuel. Nevertheless, the main problem of biodiesel is its high price. Costs can be reduced by replacement of the current homogeneous catalysts by heterogeneous catalysts; however, research for new catalysts is actually slowed by lengthy analytical techniques. Here, we set up a simple and rapid analytical method using Fourier transform infrared (FTIR) to monitor transesterification. Conversion of sunflower and recycled cooking oils to their corresponding methyl esters was easily measured using a linear correlation between the intensity of an infrared peak at 1,437 cm^?1 and the percent conversion. The results obtained by infrared were validated by gas chromatography. We also studied the effect of 20 kHz ultrasonic irradiation on biodiesel synthesis. Using our FTIR method, we found that replacing mechanical stirring with an ultrasonic probe leads to quality biodiesel in 10 min for sunflower oil and 20 min for recycled cooking oil.     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L^-1), pyrene (541.0 mg·L^-1), and benzo(a)pyrene (436.3 mg·L^-1). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg^-1, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

Embodied energy and emergy evaluation of a typical biodiesel production chain in China

Biodiesel from non-grain feedstock has been considered as one of the proper substitutes for fossil fuels associated with a series of activities emerging in China in order to meet the resource shortage and develop the energy crops. This paper presents an ecological accounting framework based on embodied energy, emergy, and CO₂ emission for the whole production chain of biodiesel made from Jatropha curcas L. (JCL) oil. The energy and materials invested in and CO₂ emission from the whole process, including cropping, transportation, extraction, and production, are accounted and calculated. Also, E_mCO₂, the ratio of real CO₂ released to the emergy-based sustainability indicator per joule biodiesel, is proposed in this paper to present a new goal function for low-carbon system optimization. Finally, the results are compared with those of the bioethanol (wheat) production in Henan Province, China, and bioethanol (corn) production in Italy in view of the indices of embodied energy, emergy and CO₂ emissions and E_mCO₂.     

Production of biodiesel from macroalgae by supercritical CO2 extraction and thermochemical liquefaction

We compare two different techniques for the extraction of biodiesel from macroalgae: the thermochemical liquefaction and the extraction using supercritical carbon dioxide (sc-CO₂). The first allows to use wet material, while sc-CO₂ requires dry material and uses moderate temperature and pressure so that it can be useful for the extraction of thermolabile compounds which may decompose at the temperature at which thermal methos are carried out. In both cases the extracted oil was characterized quantitatively and qualitatively. The novelty of the work is that in the literature the use of macroalgae for the production of biodiesel has not so far been described, while they are used mainly as food or other purposes.     

Spongy Ni/Fe carbonate-fluorapatite catalyst for efficient conversion of cooking oil waste into biodiesel

Environmental Chemistry Letters - Biodiesel produced from animal and plant fat oils is sustainable, but there is a need for efficient heterogeneous catalysts for transesterification of crude oils...