Kinetic Study on Microwave-Assisted Oligomerization of 1-Decene over a HY Catalyst

A promising production route for a high-quality base stock for lubricants is the oligomerization of high molecular-weight olefins in a high energy efficiency system. Oligomerization of 1-decene (C10) was conducted in a microwave-assisted system over a HY zeolite catalyst at different reaction temperatures and times. Higher reaction temperature resulted in increasing formation of dimers and trimers. The oligomerization reaction yielded 80% conversion, 54.2% dimer product, 22.3% trimer product and 3.4% heavier product at 483 K for a reaction time of 3 h. The best fit kinetic model for the dimerization reaction was formulated from an assumption of no vacant reaction sites. For the trimerization reaction, a molecule of dimer (C20) formed on the active site, interacted with a molecule of 1-decene in the bulk solution to form a molecule of trimer (C30). Apparent activation energies for the dimerization and trimerization reactions were 70.8 ± 0.8 and 83.6 ± 0.9 kJ/mol, respectively. The C13-NMR spectrum indicated that the oligomer product contained a significant portion of highly branched hydrocarbons, causing a substantial reduction in the viscosity index compared to conventional poly-alpha olefin lubricant (PAO).

Spektrometria masowa i analiza izotopowa biomarkerów frakcji nasyconej

GC-IRMS analysis extends and confirms (or not) the interpretation based on the results of GC-MS analyses. For example, it is very useful in determining the sedimentation environment of organic matter. GC-MS analysis of biomarkers and the results are reliable, but only GC-IRMS studies can confirm it. In this study, the origin of BNH (28,30-bisnorhopane from chemoautotrophic bacteria) and origin of higher carotenoids and their derivatives from Chlorobiaceae or Chromotiaceae bacteria were confirmed through isotopic analyzes. Biomarkers were analyzed using the GC-IRMS and EA-IRMS apparatus. The obtained chromatograms from the IRMS analyses were compared with the archival GC-MS analyses for the same samples in order to identify individual chemical compounds. In addition to the existing methodology of sample preparation for analyses, a non-standard method was also used, consisting in the separation of n-alkanes from branched hydrocarbons. The repeatability of the method was determined on the GC-IRMS and the values of δ13C for selected biomarkers from the saturated fraction were determined. It was found that samples with low biomarker content are not suitable for analysis. On the other hand, too high concentration of the analyte causes an increase of the chromatogram baseline and worse separation of the peaks, which is also a problem. For the crude oils the δ13C values were initially determined for the biomarkers of the saturated fraction from the hopanes group: bisnorhopane (BNH), oleanane, C29 norhopane, C30 hopane, moretane and the C31-C35 homohopane series. Relatively small differences in δ13C values were found between BNH/hopanes and BNH/crude oils, which suggests the same source of origin for all biomarkers (including BNH). Determining biomarkers in the aromatic fraction using the GC-IRMS method was not successful. In the future, a special methodology for preparing samples for carbon isotopic analyses of aromatic fraction will be required.

Influence of the Feedstock on the Process Parameters, Product Composition and Pilot-Scale Cracking of Plastics

Chemical recycling of polymers can lead to many different products and play a significant role in the circular economy through the use of plastic waste as a feedstock in the production of valuable materials. The polyolefins: polyethylene (PE) and polypropylene (PP), together with polystyrene (PS), can be chemically recycled by the thermal cracking (pyrolysis) process. In this study, continuous cracking of polyolefins and polystyrene in different proportions and with the addition of other polymers, like polyethylene terephthalate (PET) and polyvinyl chloride (PVC), was investigated at the pilot scale in terms of the process parameters and product yields. Gas chromatography with mass spectrometry (GC-MS) was used for the detailed analysis of the products’ compositions. The boiling temperature distribution and the bromine number were used for additional characterization of products. It was found that an increase of PP share caused a decrease in the process temperature, an increase of the product yield and a shift of the boiling range towards lighter products, increasing the content levels for unsaturates and branched hydrocarbons. It was observed that the addition of 5% PS, PET and PVC reduced the overall product yield, resulting in the creation of a lower-boiling product and increasing the conversion of polyethylene. An addition of 10% polystyrene increased the PP conversion and resulted in a higher product yield, without significant change in the boiling temperatures distribution.

Biocrude from Nannochloropsis gaditana by Hydrothermal Liquefaction: An Experimental Design Approach

The aim of the present work was focused on optimising the yield and quality of the biocrude obtained by hydrothermal liquefaction (HTL) of Nannochloropsis gaditana. Temperature, reaction time and microalga concentration were the variables used to carry out an experimental factorial design with a central composite design. The responses chosen were the biocrude yield and the nitrogen and oxygen content in the biocrude phase. A second-order model was obtained to predict the responses as a function of these variables. Temperature is the most determining factor with a positive influence on biocrude yield. The maximum biocrude yield (42.3 ± 0.8 wt%) was obtained at 320 °C, 10 min of reaction and 10 wt% microalgae concentration, and the nitrogen and oxygen content significantly decreased with respect to their corresponding levels in the initial microalgal biomass. The HHV value of the biocrude was 35.7 MJ/kg. The biocrude was composed of 30% of linear and branched hydrocarbons.

Chemical Ecology, Biochemistry, and Molecular Biology of Insect Hydrocarbons

Insect cuticular hydrocarbons (CHCs) consist of complex mixtures of straight-chain alkanes and alkenes, and methyl-branched hydrocarbons. In addition to restricting water loss through the cuticle and preventing desiccation, they have secondarily evolved to serve a variety of functions in chemical communication and play critical roles as signals mediating the life histories of insects. In this review, we describe the physical properties of CHCs that allow for both waterproofing and signaling functions, summarize their roles as inter- and intraspecific chemical signals, and discuss the influences of diet and environment on CHC profiles. We also present advances in our understanding of hydrocarbon biosynthesis. Hydrocarbons are biosynthesized in oenocytes and transported to the cuticle by lipophorin proteins. Recent work on the synthesis of fatty acids and their ultimate reductive decarbonylation to hydrocarbons has taken advantage of powerful new tools of molecular biology, including genomics and RNA interference knockdown of specific genes, to provide new insights into the biosynthesis of hydrocarbons.

Temporal Changes in Cuticular Hydrocarbons During Worker-Reproductive Transition in the Eastern Subterranean Termite (Blattodea: Rhinotermitidae)

In social insects, the reproductive division of labor is often regulated through communication using cuticular hydrocarbons (CHCs) that indicate caste identity and reproductive status. In many termites, workers retain reproductive potential and can differentiate into ergatoid reproductives, and this process is mediated by the presence of reproductives in sex- and age-specific patterns. However, little is known about the variation of CHCs profiles during this transition. In this study, we analyzed the CHC profiles of workers in comparison with ergatoids of different age, sex, and mating status in the eastern subterranean termite, Reticulitermes flavipes (Kollar) (Blattodea: Rhinotermitidae), one of the most widely distributed termite species in the world. Both female and male ergatoids were characterized by the presence of tricosane and a group of long-chain and methyl-branched hydrocarbons (chain length ≥ 33), which were found in significantly lower quantities from workers. In addition, CHC profiles differed between newly differentiated (3–4 d) and old (20–25 d) ergatoids, but no difference in CHC signatures was found between females and males based on identified compounds. Heneicosane, a previously reported royal recognition pheromone in R. flavipes, was not detected in ergatoids examined in this study. The results of caste- and age-dependent variations suggest that CHCs may act as releaser pheromones that mediate caste recognition and age-related interactions between reproductives, but analytical results of identified compounds in this study do not support CHCs as sex-specific primer pheromones that regulate nestmate fertility. Royal pheromones in termites may involve complex hydrocarbon blends and non-hydrocarbon substances that await further investigation.

The Recent Development in Gasoline Upgrading Additives (Octane Boosters)

Gasoline is one of the essential propulsion fuels used for motor cars. Specified characteristics are essential for the product application. Octane grade is one of the essential characteristics of gasoline. Gasoline commonly contains additives to prevent knocking in the combustion chamber; these additives rated as an octane number to indicate gasoline quality grades. Enhancing octane numbers was the goal of the fuel industry for the last several decades. Bosting octane of gasoline is either: (i) by varying the composition via increasing the aromatic content, branched hydrocarbons, unsaturated hydrocarbons, and their combination. (ii) Another trend for upgrading the octane number is by using additives. This paper represents a review on the gasoline upgrading by using octane booster additives for 2010-2020 sourced from a literature survey of patents, publications, books, and conferences. The review covers recent development in octane boosting additives obtained from sustainable and environmentally friendly additives to replace highly polluting organometallic carbonyl compounds, including tetraethyl lead. This review finding highlights the development of new types of octane boosting additives based on oxygenated organic hydrocarbons such as alcohols, esters, ethers, acetals, and other derivatives, mainly those obtained from natural resources such as cellulose, lignin, sugars, and plant/ animal oils. The review also covers the publications on environmental safety and economic aspects.

LIPOPHILIC CONSTITUENTS OF PEDICULARIS STRIATA PALLAS И PEDICULARIS FLAVA PALLAS

Some species of Pedicularis have been widely applied in traditional Chinese medicine. Some plants of Pedicularis genus have a great potential for the discovery of new drugs because most of them have not been studied in detail. Extracts from the plants of genus Pedicularis have been found to possess antitumor, hepatoprotective, anti-oxidative, antihaemolysis, antibacterial activity, fatigue relief of skeletal muscles, nootropic effect and other activitiesin vivo and in vitro. A wide range of chemical components including iridoid glycosides, phenylpropanoid glycosides, lignans glycosides, flavonoids, alkaloids and other polar compounds have been isolated and identified from the genus Pedicularis. Information about lipophilic constituents is too poor. The results of our investigations of aliphatic and triterpenoic substances by GC-MS are identification of 25 neutral and 18 acid compounds including sterols, triterpenoids and unusual branched hydrocarbons. Main components of neutral fraction are β-sitosterol and phytol. Triterpenol fraction is found to content cycloartenol, 24-methylene-cycloartanol, obtusifoliol, stigma-7-en-3-ol and citrostadienol. Cycloartenol prevails in both types of row material. The main components of acids are palmitic, linoleic and linolnic acids. Pedicularis striata contains significant amount of melissic and montanic acids. All compounds were found for the first time in these row materials. Identified compounds could be potential chemotaxonomic markers for the Pedicularis species.