ALBERT

Description: Deep eutectic solvents (DESs) have high viscosities, but known to be mitigated by addition of suitable co-solvent. The effect of such co-solvent on the extraction efficiency of the hybrid solvent is hardly known. This study examined the effect of ethanol on three choline chloride-based DESs (glyceline, reline, and ethaline) by mixing each in turn with ethanol in various volume proportions. The hybrid solvents were evaluated for the extraction of benzene from n-hexane. Pseudo-ternary liquid–liquid equilibrium data were obtained using the refractive index method at 303 K and 1 atm for the systems, n-hexane (1) + benzene (2) + hybrid solvent (glyceline/ethanol, ethaline/ethanol, reline/ethanol) (3), and used to evaluate distribution coefficient (D) and selectivity (S). Furthermore, the physicochemical properties of the hybrid solvents were also determined. The results indicate increase in selectivity with increasing ethanol addition up to 50% and decrease with further addition. All hybrid solvents with 50% ethanol outperform sulfolane and are suitable replacement for same as green and sustainable extractant for aromatics from aliphatics. The glyceline + 50% ethanol emerged the overall best with 49.73% elevation in selectivity and 41.15% reduction in viscosity relative to the neat glyceline. The finding of this study is expected to fillip the drive for paradigm shift in petrochemical industries.

Description: The number of aroylethyl (ethyl)xanthates have been synthesized by the reaction of the exchange decomposition of β-dimethylaminopropiophenone hydrochlorides with potassium xanthate containing several functional groups (C=O, C=S, C–OH), which determine the use of these xanthates as stabilizers with internal synergy to polymeric materials. It was shown that the thermal stability of the compounds, depending on the nature of the substituent in the benzene ring of the molecule was observed in the temperature range of 149–196 °C. It was revealed that aroylethyl(ethyl)xanthates had a stabilizing effect due to the suppression of thermo-oxidative destruction of polyethylene; they increased the induction period of polyethylene oxidation by 2–6 times, and the oxidation rate was reduced by about 3–9 times. Among the studied compounds, 4-hydroxybenzoylethyl (ethyl)xanthate had the greatest stabilizing effect. The study of the mechanism of the stabilizing action of the compounds showed that xanthates react with cumene hydroperoxide (CHP), which proceeded through the stage of formation of an intermediate product that actively decomposed CHP, i.e., the oxidation chain was terminated by the decomposition of the CHP not by the initial xanthates but by their transformation products.

Description: 1-Hexene is one of the comonomers used to produce mainly low linear density polyethylene (LLDPE) and high-density polyethylene (HDPE). The production of 1-hexene by ethylene trimerization method gained much interest in petrochemical industry due to its high selectivity towards 1-hexene in comparison to traditional ethylene oligomerization method. In literature, many catalyst systems are reported for ethylene trimerization reaction, but only few of them qualify for the commercial applications. In the present review, activity and selectivity of commercially viable catalyst systems and amount of polyethylene formed as a by-product on using these catalyst systems were discussed. Special attention is given to Chevron Phillips ethylene trimerization technology which is one of the dominant technologies in the production of 1-hexene. The challenges such as fouling issues at commercial plant due to polyethylene by-product formation were discussed and the progress made to overcome the challenges were also discussed. New generation nontoxic titanium catalysts look promising and challenges involved in commercializing these catalysts were presented in the review. Graphic abstract

Description: To find novel classes of potential fuel additives of multivalent activity, particularly antioxidants, a series of recently synthesized ethyl-6-amino-5-cyan-methyl-4-aryl-4H-pyran-3-carboxylates have been investigated using model oxidative reactions. The compounds studied appear to be prospective inhibitors of hydrocarbons oxidation. Some of them are antioxidants of combined action, breaking the chains of the oxidative reactions with cumene peroxide radicals and catalytically decomposing cumene hydroperoxide.

Description: Wax crystallization and deposition is a major flow assurance problem in production and transportation of waxy crude oil. Conventional flow improvers are mainly high molecular weight synthetic polymers, many of which are eco-toxic. Bio-based flow improvers derived from natural products are promising as inexpensive, eco-friendly alternatives to existing products. In this study, natural cashew nut shell liquid (CNSL) extracted from waste shells of Anacardium occidentale was esterified with polyethylene glycol (PEG). CNSL derivative reduced the pour point of waxy crude oil by 12 °C at 1000 ppm. The effects of CNSL derivatives on wax crystal morphology and micro-structure were studied by cross-polarized microscopy. Micrographs were processed and analyzed with ImageJ software. Addition of CNSL derivatives to oil resulted in changes in wax crystal morphology and micro-structure evidenced by a reduction in average crystal Feret diameter and aspect ratio and increase in boundary fractal dimension, indicative of formation of increasing number of smaller, rounder crystals. Effect of the additives on flow properties of the waxy oil was determined using a co-axial cylinder rotational viscometer. Dynamic viscosity of oil at shear rate of 17 s−1 was reduced by 79.7–90.5%. CNSL-PEG esters show good prospects as low-cost additives for production, storage and pipeline transportation of waxy crude oil.

Description: The effect of the chemical composition of the hydrotreated light cycle oil (HDT LCO) on the benzene, toluene, ethylbenzene, and xylene (BTEX) production by a hydrocracking (HCK) procedure, is presented. Six different types of HDT LCOs were obtained by submitting two types of LCOs to hydrotreating (HDT) with different catalysts and experimental conditions. The products were analyzed as mono-, di- and tri-aromatic compounds using the supercritical fluid chromatography (SFC) method (ASTM D5186). The HDT LCOs were subjected to HCK with a 50/50 in weight mixture of nickel-molybdenum on alumina (NiMo/Al2O3) and H-ZSM5 (NiMo/H-ZSM5, 50/50) at 375 °C, 7.5 MPa, 1.2 h−1, and 750 m3/m3 H2/Oil. The HCK products were analyzed by gas chromatography with a flame ionization detector (GC-FID) and divided into five groups: gas, light hydrocarbons (LHCs), BTEX, middle hydrocarbons (MHCs), and heavy hydrocarbons (HHCs).The results showed that the BTEX formation ranged from 27.0 to 29.8 wt.% and it did not show a significant dependence on the mono-aromatic (59.9 and 75.6 wt.%), total aromatic (61.1–84.2 wt.%) contents or MHCs conversion (58.3–64.3 wt.%) from the departing HDT LCO feedstock. This result implies that, contrary to previous expectations, the BTEX formation does not directly depend on the amounts of total or mono-aromatic compounds when departing from real feedstocks. A GC-PIONA (paraffin, isoparaffin, olefin, naphthene, aromatic) characterization method (ASTM D6623) for mechanism understanding purpose was also carried out.

Description: Dehydroaromatization of methane (MDA) reaction was investigated over platinum modified Mo/H-ZSM-5 catalysts which were pre-carbided at 750 °C. The influence of platinum on the catalytic performance and product selectivity of Mo/H-ZSM-5 catalysts for the MDA reaction at 700 °C were studied. The presence of platinum led to a slight decrease in methane conversion from 7.5 to 4.2%. Aromatic selectivities above 90% were obtained with catalysts containing low platinum loadings (0.5 and 1.0 wt.%), with benzene being the most prominent product. A decrease in coke selectivity and coke deposits was noted with the platinum modified Mo/H-ZSM-5 zeolite catalysts. A comparative study was performed to compare platinum, palladium and ruthenium promoted Mo/H-ZSM-5 zeolite catalysts with un-promoted Mo/H-ZSM-5. The ruthenium promoted catalyst proved to be superior in catalytic performance, with a higher methane conversion obtained than that found for platinum promoted and palladium promoted Mo/H-ZSM-5 catalysts. Benzene selectivity of about 60% was obtained for ruthenium and palladium promoted Mo/H- ZSM-5 catalysts and the total aromatic selectivity was maintained at 90%. TGA results showed a total reduction of 50% by weight of carbon deposited on the promoted Mo/H-ZSM-5 catalyst. Graphic abstract

Description: Three bio-based crude oil emulsion breakers have been prepared from agricultural waste by chemical treatment of cashew nutshell liquid (CNSL) extract with triethanolamine via a one-pot reaction at 120 ℃. The triethanolamine-ester derivatives were characterized by Fourier Transform–InfraRed spectroscopy. Their effectiveness as crude oil emulsion breakers were investigated experimentally using the bottle test method. The effect of solvent type, water content, and concentration of the emulsion breaker, was used to study the demulsification process and determine their demulsification efficiency at a temperature of 60 ℃ for a contact time of 180 min. A commercial demulsifier, PhaseTreat 4633 (PT-4633) was used as a benchmark. Performance evaluation of the prepared emulsion breakers revealed their effectiveness in descending order as: triethanolamine dianacardate (TED) 〉 triethanolamine trianacardate (TET) 〉 triethanolamine anacardate (TEA). The data reveals that their emulsion breaking efficiency increases with increasing emulsion water content, and concentration. PT-4633 exhibited better demulsification efficiency than the triethanolamine-esters in xylene across the concentration and water content studied. Improved water separation was however observed for the triethanolamine-esters in butanol, as triethanolamine trianacardate (TET) performed better than PT-4633 at 10 ppm to 20 ppm at 30% water content with a water separation of 83.33% and 80% respectively. The evaluated triethanolamine ester derivatives exhibited better emulsion breaking potentials in butanol than xylene at shorter times, which may be due to the synergistic effect of butanol. Therefore, butanol could be used as a sustainable solvent substitute for xylene in demulsifier formulations.

Description: This paper measured the significant factors leading to performance challenges across state-owned refineries in Nigeria based on experts’ views. The study was carried out with a view of making policy recommendations to help address these issues and thereby improve performance. A quantitative approach was adopted to sample the viewpoints of the professionals who work across the NNPC refineries. Using a Likert-type questionnaire, the professionals’ expert opinions were ranked across four main categories covering political, economic, social, and technical (PEST) factors. A Cronbach alpha test was performed to certify the consistency and reliability of the sub-category factors included on the Likert scale. In addition, a multivariate analysis of variance (MANOVA) was carried out to check for any statistically significant differences in the respondents’ opinions as a result of their different years of work experience. The study revealed that while all four PEST factors are crucial to the performance of the state-owned refineries in Nigeria, political, economic, and technical factors were viewed as more significant than the social factors. A comparative analysis of the sub-category factors using the relative significance index (RSI) and the respondents’ mean scores of importance (RMSI) revealed that government interference, funding issues, political indecision, theft and pipeline attacks, cost of spare parts, maintenance issues, operating capital, feedstock supply, staff training and competence issues are some of the significant factors that affect the performance of the refineries. The identified performance challenges from this study were used to inform policy recommendations to help address the problems of the refineries.

Description: A suitable green solvent for extraction of aromatics from aliphatics must possess good solvation and physicochemical properties, a rare occurrence in a single deep eutectic solvent (DES). Mixture of DESs could enable synergy and provide a good candidate extractant. In this study, DESs of glyceline, ethaline, and reline were synthesized and their binary mixtures (glyceline/ethaline, reline/ethaline, and glyceline/reline) produced by blending in various volume proportions. Twelve of such mixed solvents were prepared and their extraction efficiency for separating benzene from n-hexane investigated in a batch equilibrium process. Liquid–liquid equilibria (LLE) data for the pseudo-ternary systems of n-hexane + benzene + mixed DESs were measured at 303 K and 101.3 kPa. The distribution coefficient (D) and selectivity (S) of each pseudo-ternary system were determined to elicit extraction efficiency. The physicochemical properties of the mixed DESs were also measured. The results show that generally the distribution coefficients, selectivities, and physicochemical properties of the mixed DESs lie between the corresponding values for the constituent DES. The best performance was given by the mixed solvent of glyceline and ethaline in the 80:20 volume ratio, respectively, with D = 0.75 and S = 422.485. This assertion was further corroborated by higher percent recovery of benzene obtained from the said mixed DES (57.88%) relative to other mixed DESs (≤ 49.11%) examined in this study. Furthermore, its separation efficiency is superior to sulfolane but lower than glyceline, though there was a 9.4% reduction in its viscosity relative to glyceline.