In this work, solubility of hydrogen in some alkenes was investigated at different temperatures and pressures. Solubility values were calculated using the Peng–Robinson equation of state. Binary interaction parameters were calculated using fitting the equation of state on experimental data, Group contribution method and Moysan correlations and total average absolute deviation for these methods was 3.90, 17.60 and 13.62, respectively. Because hydrogen solubility in Alkenes is low, Henry’s law for these solutions were investigated, too. Results of calculation showed with increasing temperature, Henry’s constant was decreased. The temperature dependency of Henry’s constants of hydrogen in ethylene and propylene was higher than to other alkenes. In addition, using Van’t Hoff equation, the thermodynamic parameters for dissolution of hydrogen in various alkenes were calculated. Results indicated that the dissolution of hydrogen was spontaneous and endothermic. The total average of dissolution enthalpy ( $${\Delta H}^{^\circ }$$ ) and Gibbs free energy ( $${\Delta G}^{^\circ }$$ ) for these systems was 3.867 kJ/mol and 6.361 kJ/mol, respectively. But dissolution of hydrogen in almost of alkenes was not an entropy-driven process.
Two semi-synthetic clay-based catalysts were prepared. These catalysts were obtained by incorporating lanthanum oxide (Cat1) and chromium oxide (Cat2). They were then tested for catalytic cracking of a heavy petroleum residue (fuel). The two formulations were carried out in the presence of silica to improve their acidity then underwent an acid activation. The catalysts obtained were characterized by various methods (XRD, FTIR, ICP-OES, SEM). The results showed that the incorporation of oxides and the addition of silica improves the structural characteristics of the final products. The support used was a kaolinite rich clay, having a specific surface area of 15.26 m(2)/g and acidity of 14 meq/g. These values increase, respectively, to 456.14 m(2)/g and 50 meq/g for Cat1 and to 475.12 m(2)/g and 57 meq/g for Cat2. The influence of the type of oxide incorporated, the specific surface area, the porosity and the acidity of the catalysts on their catalytic activity was studied. The nature of the oxide used proved to be decisive on the quality of the catalyst. Thus Cat1, prepared with lanthanum oxide, showed the best performance in cracking the petroleum residue achieving a conversion rate of 74.13% compared to 66.53% for cat2.
Catalysts to produce the important petrochemicals like benzene, toluene, and xylene (BTX) from refinery feedstocks, like light cycle oil (LCO) are reviewed here by covering published papers using model mixtures and real feeds. Model compounds experiments like tetralin and naphthalene derivatives provided a 53–55% total BTX yield. Higher yields were never attained due to the inevitable gas formation and other C 9+ -alkylbenzenes formed. For tetralin, the best catalysts are those conformed by Ni, CoMo, NiMo, or NiSn over zeolite H-Beta. For naphthalene derivatives, the best catalysts were those conformed by W and NiW over zeolite H-Beta silylated. Real feeds produced a total BTX yield of up to 35% at the best experimental conditions. Higher yields were never reached due to the presence of other types of hydrocarbons in the feed which can compete for the catalytic sites. The best catalysts were those conformed by Mo, CoMo, or NiMo over zeolite H-Beta. Some improvements were obtained by adding ZSM-5 to the support or in mixtures with other catalysts.
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.
The complicated nature of crude oil emulsions is part of the major setbacks associated with the postulation of methods for phase separation and demulsification in the oil industry. Despite the increasing efforts in generating efficient and dependable demulsification methods, the majority of emulsions cannot be shattered in reduced times. This review examines the trending techniques of crude oil demulsification in the petroleum industry. Several approaches have been examined to discover the best method of demulsification. Hence, this reports reviewed the past studies on the emulsion, formation of oil emulsions, methods of demulsification, characteristics of demulsifier, mechanism of demulsification, kinetics in demulsification, operating parameters influencing the demulsification processes, the structure of demulsifier, and formulations that are involved in the demulsification. The formulations of crude oil demulsification have been investigated to unveil adequate demulsifiers for crude oil. Therefore, demulsification approaches have several applications due to wider varieties of crude oil, separation equipment, brines, chemical demulsifiers, the method in which demulsifiers is been formulated, and product specifications.
The oil and gas business is serious business and involves millions of dollars so whatever mitigates flow assurance is taken seriously. One of such things is natural gas hydrates. Hydrates are crystalline solids formed when water under low temperatures and high pressures encapsulated natural gases (C 1 –C 4 ). They form blockages and impede the flow of gas which can lead to the loss of millions of dollars and at times lead to personnel death. Mitigation of gas hydrates has always been with chemicals especially for areas like deep offshore where accessibility is difficult. The chemicals that are in use currently are generally synthetic, expensive and hazardous to lives and environment hence the need for readily available locally sourced materials that are eco-friendly. This study considers and screens a locally sourced surfactant from the plant family caricaceae’ Extract (CE) as a gas hydrate inhibitor in a locally fabricated 39.4-inch mini flow loop of ½ inch internal diameter (ID) which mimics the offshore environment. Various pressure plots (pressure versus time, initial and final pressure versus time and change in pressure versus time) show that the CE performed better than MEG with percentage volumes of gas left in the system for 0.01–0.05 wt% of the extract having values that ranged from 76.7 to 87.33, while volume left for MEG ranged between 70 and 74.67% (1–5 wt%). The CE performed better in small doses compared to those of MEG, in all weight percentages of study. Furthermore, the inhibition capacities which show the level of performance of the inhibitors was also used as a measure of inhibition for both inhibitors. The CE inhibited systems had values of 69.3, 80.7, 78.07, 79.82, and 83.3%, while that of the MEG inhibited system was 60.53, 55.26, 73.68, 72.81, and 66.67% for the various weight percentages considered. The CE should be developed as gas hydrate inhibitors due to its effectiveness and eco-friendliness.
Different alumina samples prepared with sol–gel, chemical precipitation and hydrothermal synthesis were used as supports of Fe-promoted Rh-based catalysts for ethanol synthesis via CO hydrogenation. The samples were characterized by means of N 2 -adsorpotion, XRD, H 2 -TPR, XPS, STEM, H 2 -TPD, DRIFTS, H 2 and CO chemisorption. The results indicated that the Al 2 O 3 prepared by hydrothermal synthesis exhibited nano-fiber morphology and constituted of mixed crystal phases, while Al 2 O 3 prepared by sol–gel and chemical precipitation shows no changes of morphology and crystal phases compared with the commercial Al 2 O 3 . In addition, nano-fiber Al 2 O 3 -supported Rh-based catalyst shows higher ethanol selectivity, which is ascribed to the lower metal–support interaction, higher dispersion and stronger CO insertion ability.
The sodium form of Faujasite Y (Na-FAU) zeolite has been synthesized by the hydrothermal method, and it has been exchanged with ammonium sulphate and later with lanthanum (III) chloride solutions to obtain the La-FAU catalyst. The three zeolites Na-FAU, NH 4 + -FAU and La-FAU have been characterized by microcrystalline X-ray diffraction, X-ray fluorescence, surface area, pore volume and Brönsted acid sites. The La-FAU catalyst has been successfully activated with boron trifluoride etherate, and it has been tested in the alkylation reaction of isobutane with isobutene up to 112 h of time on stream, since the raw La-FAU catalyst showed a rapid deactivation.
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.
Waste tyre pyrolysis gasoline (WTPG) contain significant amount of aromatics such as benzene, toluene and xylenes (BTX) and thus provide a good source for these value-added chemicals. Separation of aromatics from aliphatic media as obtained in WTPG and naphtha is done commercially by solvent extraction using volatile organic solvents such as sulfolane (SUF), dimethylformamide (DMF) and diethylene glycol (DEG). The high cost of this state-of-the art separation method and environmental consideration have necessitated search for non-volatile and green solvent such as deep eutectic solvent (DES). This study intends to conduct a comparative evaluation of the performance of five solvents (SUF, DMF, DEG, and two DESs) for the extraction of BTX from WTPG. The two DESs are choline chloride/ethylene glycol (DES1) and choline chloride/glycerol (DES2) in molar ratios 1:2. An ASPEN plus simulation was carried out to generate liquid–liquid equilibria (LLE) data for the pseudo-ternary systems {WTPG + BTX + solvent (SUF/DMF/DEG/DES)}. Performance evaluation was based on selectivity (S) and solute (BTX) distribution coefficient (D). The propriety of the simulation protocol was validated using literature data. The results revealed the following maximum values of selectivity and distribution coefficients for the solvents: DES2 (S = 378.283, D = 0.656); DES1 (S = 77.364, D = 1.423); SUF (S = 55.371, D = 0.756); DMF (S = 25.336, D = 0.786) and DEG (S = 17.531, D = 0.793). The DESs therefore performed better than the organic solvents and can suitably replace same in the extraction of BTX from waste tyre pyrolysis gasoline.
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.
γ-Al2O3 was synthesized by the Sol–gel method, Ni (NO3)2 was placed in the pores by the impregnation method, and Ni-γ-Al2O3 was obtained by pyrolysis in a hydrogen stream in a CVD device. By the method of chemical vapors phase deposition (CVD) on Ni-Al2O3 catalytic converter with decomposition of methane in the natural gas produced carbon nanotubes (CNT) (Chunduri et al. in Mater Express 4(3):235–241, 2014; Zhou et al. in Appl Catal B 208:44–59, 2017). The catalytic activity of the catalysts in methane decomposition was examined from 650 °C to 900 °C by the method of chemical vapors phase deposition (CVD), the yield of CNTs tends to increase with the growth at the ratio of natural gas supply to hydrogen. The specific surface increases with an increase of nickel content and can reach 265.5 m2/g for a sample of 2% Ni-A12O3 at 850 °C. Growth at the temperature of methane decomposition leads to reduction in its specific surface. It has been established that the use of the Ni-Cu/γ-Al2O3 catalytic system, in which copper acts as a stabilizing additive, makes it possible to double the maximum yield of the carbon product during the decomposition of natural gas.
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.
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.
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
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.
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.
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.
A thermoresponsive system of a nanoemulsion-based gel with favorable characteristics to enhanced oil recovery (EOR) application is presented. A full factorial design study with different formulations of thermosensitive nanoemulsion-based gels was performed to assess the influence of the oil chain length, concentration of polyethylene glycol (PEG 400) and concentration of oil on the rheological behavior of the system. A formulation with low viscosity at room temperature and high viscosity at the temperature of the oil extraction well was presented. Hexane (6-carbon chain), capric acid (10-carbon chain) and isopropyl myristate (17-carbon chain) were used in concentrations of 5%, 10%, 15% and 20% wt%, also varying the concentration of PEG 400 in 0%, 3%, 6% and 9% wt%. The thermosensitive polymer used was a mixture of Pluronic® F-127 and Pluronic® F-68 6:1 wt% at 4.7% concentration. The surfactants used were Tween 80 and Span 80 (HLB = 13) at 20%. The formulation containing 20% isopropyl myristate (IPM) without the addition of PEG 400 showed a better response, with an increase in viscosity of more than 38 times in relation to its viscosity at 25 °C, and the maximum viscosity was reached at 53 °C. This is a promising formulation for EOR technology.
