Molecular weight distribution of raw and catalytic fast pyrolysis oils: comparison of analytical methodologies

Comprehensive analysis of the molecular weight distribution of raw and catalytic fast pyrolysis oils derived from biomass remains a key technical hurdle to understanding oil quality as it relates to downstream use and multiple methods may be necessary to accurately represent all components present. Here, we report the molecular weight distribution metrics of fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) oils as determined by gel permeation chromatography (GPC) combined with UV-diode array (UV), differential refractive index (RI), and multi-angle laser light scattering (MALS) detection. The measured molar mass distributions revealed that FP oil consisted of a higher proportion of larger products relative to the low molecular weight products contained in the CFP oil. GPC/RI and UV methods showed FP oil to have higher weight-average molecular weight (M_w) and number-average molecular weight (M_n) than CFP oil based on elution time. However, GPC/MALS, determined the two oils to have similar overall molecular weight distribution metrics (M_w and M_n) and yielded values significantly higher than those determined by RI and UV detectors relative to external standards. Overall, the use of a multiple detection GPC method could enable a more accurate comparison and determination of true molecular weight metrics of bio-oils.

Comprehensive analysis of the molecular weight distribution of raw and catalytic fast pyrolysis oils remains a key technical hurdle to understanding oil quality and multiple methods may be necessary to accurately represent all components present.     

Catalytic pyrolysis of coconut oil with Ni/SBA-15 for the production of bio jet fuel

Catalytic pyrolysis of vegetable oil is one of the potential routes to convert oil to drop-in biofuels, known as renewable hydrocarbons. In this paper, we explored catalytic pyrolysis of coconut oil using SBA-15 impregnated with Ni in proportions of 1% to 5% to produce sustainable aviation fuel. The catalysts were synthesized, calcined and then characterized by XRD, FTIR, SEM, and EDS. In order to better understand the behavior of this process, thermal and kinetic studies were carried out by thermogravimetry. The TG curves of vegetable oil with (10%) and without catalysts were obtained at heating rates of 5, 15 and 20 °C min⁻¹, in the temperature range between 30 and 600 °C. The kinetic parameters were calculated by the Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS) methods. In the kinetic study, lower heat rates promoted higher conversions and the KAS model suits the process. The results calculated for the OC sample using the two kinetic models showed an increase in the E_a energy as the conversion progressed to a certain point. Catalytic pyrolysis experiments were performed in a one-stage tubular reactor at 500 °C with a catalyst loading of 10 wt% on the basis of mass of oil. The catalyst with 5% Ni showed greater presence of hydrocarbons and greater formation of water, indicating that the deoxygenation process occurred through decarbonylation. With this, the present study was successful in the development of methodologies for obtaining hydrocarbons with a composition close to that of drop-in fuels, compared to the process carried out with vegetable oil in the absence of catalysts.

Catalytic pyrolysis of vegetable oil is one of the potential routes to convert oil to drop-in biofuels, known as renewable hydrocarbons.     

The selective recognition mechanism of a novel highly hydrophobic ion-imprinted polymer towards Cd(ii) and its application in edible vegetable oil

Edible vegetable oils are easily contaminated by heavy metals, resulting in the oxidative degradation of oils and various health effects on humans. Therefore, it is very important to develop a rapid and efficient method to extract trace heavy metals from vegetable oils. In this work, a highly hydrophobic ion-imprinted polymer (IIP) was synthesized on a novel raspberry (RS)-like particle surface. The synthesized IIP@RS was characterized and used in solid-phase extraction (SPE) for the selective and fast adsorption of Cd(ii) from vegetable oils. The results showed that IIP was successfully coated onto RS particles with a high specific surface area (458.7 m² g⁻¹) and uniform porous structure. The contact angle (θ) value (141.8°) of IIP@RS was close to the critical value of super-hydrophobic materials, which is beneficial to their adsorption in hydrophobic vegetable oils. The IIP@RS also exhibited excellent adsorption ability and selectivity to Cd(ii) with a maximum adsorption capacity of 36.62 mg g⁻¹, imprinting factor of 4.31 and equilibrium adsorption rate of 30 min. According to isothermal titration calorimetry results, the recognition behavior of IIP@RS for Cd(ii) was mainly contributed by Cd(ii)-induced cavities during gel formation and coordination between Cd(ii) and –SH groups in imprinted cavities. Furthermore, the adsorption process driven by entropy and enthalpy was spontaneous at all temperatures. In real vegetable oil samples, IIP@RS-SPE adsorbed approximately 96.5–115.8% of Cd(ii) with a detection limit of 0.62 μg L⁻¹. Therefore, IIP@RS has wide application prospects in enriching and detecting Cd(ii) from vegetable oil.

Edible vegetable oils are easily contaminated by heavy metals, resulting in the oxidative degradation of oils and various health effects on humans.     

Catalytic developments in the epoxidation of vegetable oils and the analysis methods of epoxidized products

Functionalization of vegetable oils (VOs) including edible, non-edible, and waste cooking oil (WCOs) to epoxides (EVOs) is receiving great attention by many researchers from academia and industry because they are renewable, versatile, sustainable, non-toxic, and eco-friendly, and they can partially or totally replace harmful phthalate plasticizers. The epoxidation of VOs on an industrial scale has already been developed by the homogeneous catalytic system using peracids. Due to the drawbacks of this method, other systems including acidic ion exchange resins, polyoxometalates, and enzymes are becoming alternative catalysts for the epoxidation reaction. We have reviewed all these catalytic systems including their benefits and drawbacks, reaction mechanisms, intensification of each system in different ways as well as the physicochemical properties of VOs and EVOs and new findings in recent years. Finally, the current methods including titrimetric methods as well as ATR-FTIR and ¹H NMR for determination of conversion, epoxidation, and selectivity of epoxidized vegetable oils (EVOs) are also briefly described.

Epoxidation of vegetable oils by different means to improve their functional properties and to replace the harmful phthalate plasticizers along with their analysis are shown.     

Expression of phosphotransacetylase in Rhodosporidium toruloides leading to improved cell growth and lipid production

Microbial lipids (MLs) are potential alternatives to vegetable oils and animal fats for production of biofuels and oleochemicals. It remains critical to improve ML production efficiency and costs for further commercial development. In the present study, we overexpressed a gene encoding phosphotransacetylase (Pta) in the oleaginous yeast Rhodosporidium toruloides for enhanced cell growth and lipid production. Compared with the parental strain R. toruloides NP11, the engineered strain NP-Pta-15 showed significant improvement in glucose consumption, cell growth and lipid accumulation when cultivated under nitrogen limited conditions in an Erlenmeyer flask as well as a stirred tank bioreactor. The introduction of Pta may establish an additional acetyl-CoA formation route by utilization of acetylphosphate. Our results should inspire more engineering efforts to facilitate the economic viability of ML technology.

Microbial lipids (MLs) are potential alternatives to vegetable oils and animal fats for production of biofuels and oleochemicals.     

Bio-oils from vacuum ablative pyrolysis of torrefied tobacco residues

Fast pyrolysis, in combination with torrefaction pretreatment, was used to convert tobacco residues to value-added bio-fuels and chemicals. Tobacco plant residues were torrefied at 220, 260, and 300 °C, before being pyrolyzed at 450, 500, 550, and 600 °C in a rotating blade ablative reactor under vacuum conditions to test the effects on product yields. With torrefaction, tobacco residues thermally decomposed 20–25% w/w at low temperatures. Torrefaction and pyrolysis temperatures were found to markedly affect pyrolytic product yields of bio-chars and bio-oils, while having no effect on gas-phase products. Bio-oil yields exhibited a direct relation with pyrolysis temperature and an inverse relation with torrefaction temperature. Bio-oils produced were separated into light and heavy oils and analyzed by GC-MS, and ¹H and ¹³C NMR. Nicotine was found to be the main compound in the light and heavy oils along with several phenols and cresols in the heavy oil.

Thermochemical conversion of tobacco residues to value-added bio-fuels and chemicals via fast pyrolysis, in combination with torrefaction pretreatment, in a rotating blade ablative reactor under vacuum conditions.     

Baseline fatty acids,food groups,a diet score and 50-year all-cause mortality rates. An ecological analysis of the Seven Countries Study

Objectives: This analysis deals with the ecologic relationships of dietary fatty acids, food groups and the Mediterranean Adequacy Index (MAI, derived from 15 food groups) with 50-year all-cause mortality rates in 16 cohorts of the Seven Countries Study.

Material and methods: A dietary survey was conducted at baseline in cohorts subsamples including chemical analysis of food samples representing average consumptions. Ecologic correlations of dietary variables were computed across cohorts with 50-year all-cause mortality rates, where 97% of men had died.

Results: There was a 12-year average age at death population difference between extreme cohorts. In the 1960s the average population intake of saturated (S) and trans (T) fatty acids and hard fats was high in the northern European cohorts while monounsaturated (M), polyunsaturated (P) fatty acids and vegetable oils were high in the Mediterranean areas and total fat was low in Japan. The 50-year all-cause mortality rates correlated (r=??0.51 to ?0.64) ecologically inversely with the ratios M/S, (M?+?P)/(S?+?T) and vegetable foods and the ratio hard fats/vegetable oils. Adjustment for high socio-economic status strengthened (r=??0.62 to ?0.77) these associations including MAI diet score.

Conclusion: The protective fatty acids and vegetable oils are indicators of the low risk traditional Mediterranean style diets.

• KEY MESSAGES

• We aimed at studying the ecologic relationships of dietary fatty acids, food groups and the Mediterranean Adequacy Index (MAI, derived from 15 food groups) with 50-year all-cause mortality rates in the Seven Countries Study.

• The 50-year all-cause mortality rates correlated (r?=??0.51 to ?0.64) ecologically inversely with the ratios M/S [monounsaturated (M)?+?polyunsaturated (P)]/[saturated (S)?+?trans (T)] fatty acids and vegetable foods and the ratio hard fats/vegetable oils. After adjustment for high socio-economic status, associations with the ratios strengthened (r?=??0.62 to ?0.77) including also the MAI diet score.

• The protective fatty acids and vegetable oils are indicators of the low risk traditional Mediterranean style diets.

     

Catalytic pyrolysis (Ni/Al-MCM-41) of palm (Elaeis guineensis) oil to obtain renewable hydrocarbons

The present work aims to evaluate the potential of Al-MCM-41 and Ni/Al-MCM-41 catalysts for the production of renewable hydrocarbons through the fast pyrolysis of palm oil. Al-MCM-41 mesoporous material was synthesized by the hydrothermal route. The Ni/Al-MCM-41 catalyst was obtained by the wet impregnation method of the Al-MCM-41 material (support) previously synthesized with 2.3% metal in relation to the support mass. The thermal pyrolysis of palm oil yielded many oxygenated compounds with a very high molecular mass. The pyrolysis of the oil under the action of Al-MCM-41 presented greater selectivity when compared to thermal pyrolysis, obtaining 63% of hydrocarbons in the C11–C15 region. The catalytic pyrolysis of the oil with Ni/Al-MCM-41 showed a high deoxygenation rate, obtaining a hydrocarbon percentage equal to 78%, in addition to obtaining a percentage of hydrocarbons equal to 46% in the region of interest, viz., C11–C15, demonstrating the potential of the Ni/Al-MCM-41 catalyst for renewable hydrocarbons production (bio-jet fuel) from palm oil.

The potential of the Al-MCM-41 and Ni/Al-MCM-41 catalysts applied to pyrolysis for the production of renewable hydrocarbons (bio-jet fuel) has been studied and has been shown to be efficient.     

Characterization of endogenous antioxidant attributes and its influence on thermal stability of canola oil

Difference in thermal stability of two commercially available canola oils prepared by either expeller-extraction (EE) or solvent-extraction (SE) method was investigated. After 5 days consecutive deep-fry, content of oxidized-triacylglycerols (oxTAGs) in SE oil increased by 250.0% compared to its original status. However, 62.5% increase of oxTAGs in EE oil occurred, indicating that EE oil exhibits superior thermal stability to SE oil. Antioxidant capacity of EE oil was highly retained and loss rate of tocopherols in EE oil was much slower than in SE oil during deep-fry. Lipidomics showed that although there was no significant difference in molecular profile of either triacylglycerols or diacylglycerols between two oils, EE oil was characterized with 19 times higher phosphatidylcholine contents than SE oil. Considering no difference in antioxidant capacity between the two oils in their original status, it is proposed that synergetic mechanism is simultaneously initiated by antioxidant compounds and phosphatidylcholines, which plays key roles for maintaining better thermo-stability of vegetable oil during deep-fry.

Difference in thermal stability of two commercially available canola oils prepared by either expeller-extraction (EE) or solvent-extraction (SE) method was investigated.     

Solid fat content and bakery characteristics of interesterified beef tallow-palm mid fraction based margarines

Palm mid fraction (PMF) was interesterified with edible beef tallow (BT) catalyzed using sodium methoxide to investigate the effects on the solid fat content (SFC) of these palmitic rich plastic fats. Interesterified blends crystallize more slowly than BT. Conversely, the crystallization rates of PMF-BT-based interesterification (IE) products were compared with the starting mixture and IE products prepared with non-PMF triglycerides. The SFC PMF-based IE products increased significantly at temperatures between 25 and 40 °C. The SFC profiles became smoother and the products had potential to serve as base oils for preparing specialty fats with a wider range of plasticity. Further exploration of triacylglycerol (TAG) compositional changes revealed that PMF interesterified products had greater saturated/saturated/saturated (S/S/S)-type TAGs compared with soybean oil interesterified products. Moreover, in subsequent evaluations of BT-PMF-based IE fats as a margarine replacement effects in a baked cake model system showed that the material was a suitable functional oil base with acceptable aeration properties and plasticity during baking. Therefore, it is a potential alternative to IE-BT based and traditional IE-BT-palm oil based margarines. The physical-characteristics of bakery products prepared with this fat exhibited improved cake volume with fine structure and clear lifting properties, which affirmed the potential for its application in bakery fats.

Palm mid fraction (PMF) was interesterified with edible beef tallow (BT) to investigate the effects on the solid fat content (SFC) and the bakery characteristics.     

Engineering phytosterol-based oleogels for potential application as sustainable petrolatum replacement

Phytosterol-based oleogels have been engineered in edible oils for potential applications as sustainable replacements for petrolatum. Oleogels have emerged with a crystal network structure with oil molecules trapped inside. In addition, the viscosity of highly thixotropic oleogels could be tuned by manipulating the concentration of phytosterols and monoglycerides, and the type of surface-active small molecules and bulk vegetable oils. Furthermore, viscous soft matter could also be tunably made with 8–20% oleogelators in olive oil with favourable water vapour occlusive and wettability properties, in addition to having good texture, and outstanding thixotropic and thermal reversibility properties. These properties are quite similar to those of commercial petrolatum. This work demonstrates that the natural phytosterol-oleogels in edible oils can be a novel source of sustainable and green replacements for petrolatum.

Phytosterols, as a family of plant-produced molecules, are recognized for their natural health benefits. Phytosterol-based oleogels have been engineered in edible oils to be potential applicable as sustainable petrolatum replacements.     

Catalytic pyrolysis of plastic waste for the production of liquid fuels for engines

Catalytic pyrolysis of waste plastics using low cost binder-free pelletized bentonite clay has been investigated to yield pyrolysis oils as drop-in replacements for commercial liquid fuels such as diesel and gasohol 91. Pyrolysis of four waste plastics, polystyrene, polypropylene, low density polyethylene and high density polyethylene, was achieved at a bench scale (1 kg per batch) to produce useful fuel products. Importantly, the addition of binder-free bentonite clay pellets successfully yielded liquid based fuels with increased calorific values and lower viscosity for all plastic wastes. This larger scale pyrolysis study demonstrated that use of a catalyst in powder form can lead to significant pressure drops in the catalyst column, thus slowing the process (more than 1 hour). Importantly, the use of catalyst pellets eliminated the pressure drop and reduced pyrolysis processing time to only 10 minutes for 1 kg of plastic waste. The pyrolysis oil composition from polystyrene consists of 95% aromatic hydrocarbons, while in contrast, those from polypropylene, low density polyethylene and high density polyethylene, were dominated by aliphatic hydrocarbons, as confirmed by GC-MS. FTIR analysis demonstrated that low density polyethylene and high density polyethylene oils had functional groups that were consistent with those of commercial diesel (96% similarity match). In contrast, pyrolysis-oils from polystyrene demonstrated chemical and physical properties similar to those of gasohol 91. In both cases no wax formation was observed when using the bentonite clay pellets as a catalyst in the pyrolysis process, which was attributed to the high acidity of the bentonite catalyst (low SiO₂ : Al₂O₃ ratio), thus making it more active in cracking waxes compared to the less acidic heterogeneous catalysts reported in the literature. Pyrolysis-oil from the catalytic treatment of polystyrene resulted in greater engine power, comparable engine temperature, and lower carbon monoxide (CO) and carbon dioxide (CO₂) emissions, as compared to those of uncatalysed oils and commercial fuel in a gasoline engine. Pyrolysis-oils from all other polymers demonstrated comparable performance to diesel in engine power tests. The application of inexpensive and widely available bentonite clay in pyrolysis could significantly aid in repurposing plastic wastes.

Catalytic pyrolysis of waste plastics using low cost binder-free pelletized bentonite clay has been investigated to yield pyrolysis oils as drop-in replacements for commercial liquid fuels such as diesel and gasohol 91.     

Study of the effect of in situ minerals on the pyrolysis of oil shale in Fushun,China

Herein, the effect of Fushun oil shale minerals on its kerogen has been investigated. The samples were obtained under non-isothermal conditions at different final temperatures. Scanning electron microscope (SEM) analysis revealed that the silicates were layered and the carbonates were tightly bound to each other. The combination of silicates and carbonates led to close combination of minerals and organic matter and the organic matter was contained in the minerals. The Brunner–Emmet–Teller (BET) experiments conclude that during the non-isothermal pyrolysis process, the specific surface area increased, and then, decreased, which proves the adsorption effect of silicates on oil shale pyrolysis products and the adsorption effect of carbonates was weak. The activation energy of four samples was calculated via Flynn–Wall–Ozawa (FWO) and Friedman kinetic analysis under different heating rates in a non-isothermal process, wherein the average activation energy of the sample containing silicate was 177.60 kJ mol⁻¹ at minimum while that of carbonate was 250.45 kJ mol⁻¹ at maximum, which proves that the catalytic promotion effect of silicate was greater than the inhibition effect of carbonate. The pyrolysis products obtained by Flash pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) under isothermal pyrolysis conditions were primarily composed of aliphatic hydrocarbon structures, which had different degrees of impact on the production of heteroatoms. This work provides a reliable theoretical basis for future studies on the influence of minerals on pyrolysis of organic matter in oil shale.

In this paper, the effect of in situ minerals on the pyrolysis of Fushun oil shale is studied by combining isothermal and non isothermal experiments.     

Development of quantitative 13C NMR characterization and simulation of C,H, and O content for pyrolysis oils based on 13C NMR analysis

Bio-oil is a valuable liquid product obtained from pyrolysis of biomass and it contains tens of hundreds of compounds, which brings about difficulties for characterization with various analytical methods. ¹³C NMR has advantages over other detection methods as it can characterize the entire composition of bio-oil and distinguish different types of carbon. But various shortcomings limit the application of ¹³C NMR. This study was carried out to develop a quantitative ¹³C NMR method to determine different functional groups in pyrolysis bio-oils with short NMR time and good accuracy, and propose a simulation of C, H, and O content for pyrolysis oils based on ¹³C NMR analysis. In order to solve long-term NMR problems, relax reagent has been added and the results show that it is an effective way to shorten the NMR time. Moreover, the aging problem is not obvious in the short-term NMR test, so the effect of aging on the test results can be neglected. Three types of substances with different oxygen content have been employed to verify the feasibility of the C, H, and O calculation methods and the result errors of all elements are small, which shows it is reliable for the simulation data of C, H and O content.

This work develops an effective way to characterize bio-oil by quantitative ¹³C NMR despite the complexity of bio-oil and proposes a simulation of C, H, and O content for pyrolysis oils based on ¹³C NMR analysis.     

Molecular selectivity in the water flooding heavy oil process from porous rocks

Water flooding increases the recovery factor of crude oil and has been proven to be an economical and viable technique for enhancing the oil recovery of oil fields. The process has been systematically studied previously, in which the oil was considered a substance of constant composition. However, the molecular selectivity during the water flooding process has rarely been addressed, especially for heavy oil. Herein, the properties and compositional changes of heavy oil have been investigated in a simulated water flooding process at 60 °C and 85 °C. The crude oil and produced oils from different water flooding stages were characterized by gas chromatography, gas chromatography-mass spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry. The results show that with the increase in temperature, the content of resins in the produced oils from different water flooding stages decreases, and the content of asphaltenes increases slightly. The viscosity of the produced oils increases at low temperatures and decreases at high temperatures as the water cut increases. The composition of the produced oils from different water flooding stages is different. Compared with the no water cut and high water cut stages, the changes in the produced oils of the low water cut stages are significant at different temperatures. The molecular selectivity of heteroatoms is higher than that of hydrocarbons in the water flooding process. Water flooding preferentially extracts small-molecule low-carbon hydrocarbons and small-molecule heteroatoms with low condensation degrees. The compositional differences between the produced oils were characterized by the double bond equivalent versus carbon number distribution of the S, N, and O-containing compounds. This study can not only provide some explanations on the viscosity-forming mechanism of heavy oil but also explains the watered-out phenomena in the development of oilfields.

The composition of heavy oil changes during the water flooding process. Water flooding preferentially extracts small-molecular components with the increase in temperature.     

A review on non-edible oil as a potential feedstock for biodiesel: physicochemical properties and production technologies

There is increasing concern regarding alleviating world energy demand by determining an alternative to petroleum-derived fuels due to the rapid depletion of fossil fuels, rapid population growth, and urbanization. Biodiesel can be utilized as an alternative fuel to petroleum-derived diesel for the combustion engine. At present, edible crops are the primary source of biodiesel production. However, the excessive utilization of these edible crops for large-scale biodiesel production might cause food supply depletion and economic imbalance. Moreover, the utilization of edible oil as a biodiesel feedstock increases biodiesel production costs due to the high price of edible oils. A possible solution to overcome the existing limitations of biodiesel production is to utilize non-edible crops oil as a feedstock. The present study was conducted to determine the possibility and challenges of utilizing non-edible oil as a potential feedstock for biodiesel production. Several aspects related to non-edible oil as a biodiesel feedstock such as overview of biodiesel feedstocks, non-edible oil resources, non-edible oil extraction technology, its physicochemical and fatty acid properties, biodiesel production technologies, advantages and limitation of using non-edible oil as a feedstock for biodiesel production have been reviewed in various recent publications. The finding of the present study reveals that there is a huge opportunity to utilize non-edible oil as a feedstock for biodiesel production.

There is increasing concern regarding alleviating world energy demand by determining an alternative to petroleum-derived fuels due to the rapid depletion of fossil fuels, rapid population growth, and urbanization.     

Comparative study on the pyrolysis behavior and pyrolysate characteristics of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis

Injected steam can be converted to the sub/supercritical state during the in situ exploitation of oil shale. Thus, the pyrolysis behavior and pyrolysate characteristic of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis were fully compared. The results revealed that the discharged oil yields from sub/supercritical water pyrolysis were 5.44 and 14.33 times that from anhydrous pyrolysis at 360 °C and 450 °C, which was due to the extraction and driving effect of sub/supercritical water. Also, sub/supercritical water could facilitate the discharge and migration of shale oil from the pores and channels. The H₂ and CO₂ yields in sub/supercritical water pyrolysis were higher than that in anhydrous pyrolysis, resulting from the water–gas shift reaction. The component of shale oil was dominated by saturated hydrocarbons in anhydrous pyrolysis, which accounted for 50–65%. In contrast, a large amount of asphaltenes and resins was formed during pyrolysis in sub/supercritical water due to the solvent effect and weak thermal cracking. The shale oil from anhydrous pyrolysis was lighter than that from sub/supercritical water pyrolysis. Sub/supercritical water reduced the geochemical characteristic indices and lowered the hydrocarbon generation potential and maturity of solid residuals, which can be attributed to the fact that more organic matter was depolymerized and released. The pyrolysate characteristic of oil shale in sub/supercritical water pyrolysis was controlled by multiple mechanisms, including solvent and driving effect, chemical hydrogen-donation and acid–base catalysis.

Sub/supercritical water can directly extract oil and gas from oil shale due to the solvent and driving effects. Also, they can be considered as an acid–base catalyst, which can catalyze some reactions such as hydrolysis, addition and rearrangement.     

Analytical methods for the determination of oil carryover from CNG/biomethane refueling stations recovered in a solvent

Vehicle gas is often compressed to about 200 bar at the refueling station prior to charging to the vehicle''s tank. If a high amount of oil is carried over to the gas, it may cause damage to the vehicles; it is therefore necessary to accurately measure oil carryover. In this paper, three analytical methods for accurate quantification of the oil content are presented whereby two methods are based on gas chromatography and one on FTIR. To better evaluate the level of complexity of the matrix, 10 different compressor oils in use at different refueling stations were initially collected and analysed with GC and FTIR to identify their analytical traces. The GC traces could be divided into three different profiles: oils exhibiting some well resolved peaks, oils exhibiting globally unresolved peaks with some dominant peaks on top of the hump and oils exhibiting globally unresolved peaks. After selection of three oils; one oil from each type, the three methods were evaluated with regards to the detection and quantification limits, the working range, precision, trueness and robustness. The evaluation of the three measurement methods demonstrated that any of these three methods presented were suitable for the quantification of compressor oil for samples. The FTIR method and the GC/MS method both resulted in measurement uncertainties close to 20% rel. while the GC/FID method resulted in a higher measurement uncertainty (U = 30% rel.).

Vehicle gas is often compressed to about 200 bar at the refueling station prior to charging to the vehicle''s tank.     

Enhanced biocrude production from hydrothermal conversion of municipal sewage sludge via co-liquefaction with various model feedstocks

Hydrothermal co-liquefaction has the potential to improve biocrude yield. To investigate the influence of various types of biomass on co-liquefaction with municipal sewage sludge (MSS), experiments on MSS with three kinds of model feedstocks (soy oil, soy protein, and starch) were carried out. Reaction temperatures of 300, 320, and 340 °C proved to be the appropriate reaction temperatures for the highest biocrude yield for soy oil, soy protein, and starch, respectively. A synergistic effect on the biocrude yield of co-liquefaction was proved, and starch showed the highest synergistic effect with a 57.25% increase in biocrude yield, while soy oil only presented a slight synergistic effect. Thermal gravimetric analysis (TGA) results suggested that co-liquefaction with soy oil increased the light oil fractions in biocrude by 20.81%, but protein and starch led to more heavy oil fractions. Gas chromatography-mass spectrometry (GC-MS) indicated that co-liquefaction with protein or starch produced more cyclic compounds in the biocrude, while almost no new components appeared from co-liquefaction with soy oil.

Hydrothermal co-liquefaction has the potential to improve biocrude yield.     

Organic–inorganic hybrid coating materials derived from renewable soybean oil and amino silanes

Novel organic–inorganic hybrid coating materials were developed using amino silanes and acetoacetylated soybean oil. The acetoacetylated soybean oil was prepared from soybean oil (a renewable resource) using a solvent-free method involving a thiol–ene and transesterification reactions, and the chemical structure was characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), Fourier-transform infrared (FTIR) spectroscopy, and viscosity analyses. On the basis of the acetoacetylated soybean oil, several organic–inorganic hybrid coating materials were prepared using different amino silanes by a catalyst-free method involving one-step comprising two reactions (an amine–acetoacetate reaction and an in situ sol–gel technique), and their crosslinked structures were determined from their FT-IR and solid-state ²⁹Si NMR spectra. The resulting coating materials have good mechanical/chemical performance. This method for preparing renewable organic–inorganic hybrid coating materials may have wide uses because plant oils contain many unsaturated C C bonds and easy access to acetoacetate functional groups.

A novel coating material was synthesized in one-step comprising two reactions (an amine–acetoacetate reaction and an in situ sol–gel technique).